CN106882784B - The preparation and application of one-dimension oriented orderly cross-linked fibrous grading-hole carbon material - Google Patents
The preparation and application of one-dimension oriented orderly cross-linked fibrous grading-hole carbon material Download PDFInfo
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Abstract
The present invention relates to the preparations and application of one-dimension oriented orderly cross-linked fibrous grading-hole carbon material, using metal salt and organic ligand as raw material, it is prepared with one-dimension oriented metal organic framework (MOF), one-dimension oriented orderly cross-linked fibrous grading-hole carbon material is made by temperature programming carbonization, etching template, activation；The organic ligand is one of trimesic acid, melamine, cyanuric acid, trithiocyanuric acid or two kinds or more；The metal salt is one of ferric nitrate, copper nitrate, nickel nitrate, zinc nitrate or two kinds or more.One-dimension oriented orderly cross-linked fibrous grading-hole carbon material all shows big advantage in terms of material preparation process, electronics and ion, has a good application prospect as lithium sulfur battery anode material.
Description
Technical field
The present invention relates to a kind of one-dimension oriented orderly cross-linked fibrous grading-hole carbon materials of lithium-sulfur cell.
Background technique
In commercialized secondary cell, lithium ion battery is the highest secondary cell of current energy density, but is based on
The lithium ion battery of " deintercalation " theory, theoretical specific capacity are currently less than 300mA h g-1, actual energy density is less than 200Wh
kg-1, far from meet people to electric car 500km continue a journey the needs of.Lithium-sulfur cell is as a kind of new electrochemical energy storage two
Primary cell, different from traditional lithium ion " deintercalation " formula material, during discharge, two electron reactions occur for sulphur and lithium metal,
Very high specific capacity (1675mAh g can be released-1), theoretical specific energy is also up to 2600Wh kg-1, meanwhile, active material sulphur
At low cost with resourceful, low toxicity, advantages of environment protection, therefore, lithium-sulfur cell are considered as alternative lithium ion battery
One of new secondary battery, have a good application prospect.
Positive electrode is the important component in lithium-sulfur cell, it plays the work of building electrodes conduct network and solid sulphur
With.But the electron transmission mode of " point-to-point " of conventional powder carbon material and more single pore-size distribution have seriously affected it
The transmission of electronics and ion, to limit performance and the high rate performance of its capacity.One-dimension oriented orderly cross-linked fibrous point
Grade hole carbon material can well solve problem as above.Its one-dimensional orientation texture is conducive to construct three-dimensional electronic transmission network, will
The electron transmission mode of traditional " point-to-point " becomes the electron transmission mode of " Line To Line ", greatly improves the conduction of electrode
Property；Orderly cross-linked structure can eliminate the contact resistance between fiber, shorten electron-transport path, further improve electrode
Electric conductivity.Moreover, wherein micropore can be spread by the dissolution of powerful capillarity power limit polysulfide, mesoporous and macropore
It is capable of providing biggish pore volume, is conducive to the infiltration of electrolyte and the transmission of lithium ion.Therefore, with one-dimension oriented orderly friendship
" high speed " channel can be provided for lithium sulfur battery anode material for electronics and ion by joining fibrous grading-hole carbon material, so as to
Meet requirement under the conditions of high magnification to electronics and ion transport.And traditional preparation method, generally by carbon nanometer
The traditional one-dimensionals material such as pipe, carbon fiber is coated, is modified, to obtain one-dimension oriented orderly grading-hole carbon material.But
By traditional one-dimensional material specific surface (generally less than 200m2g-1) and pore volume (generally less than 0.2cm3g-1) constraint, it is synthesized
Material specific surface and pore volume it is lower, the serious capacity for affecting lithium-sulfur cell plays, cycle performance and fills sulfur content.And
And need to add various template agent in the synthesis process, it can be just successfully prepared by the synergistic effect of template, process is cumbersome,
It is complicated for operation, and be difficult to be crosslinked between fiber, it is difficult to eliminate the contact resistance between fiber.And with one-dimension oriented MOF
As presoma can be synthesized under the action of not adding any template have high-ratio surface, macropore volume it is one-dimension oriented
Orderly cross-linked fibrous grading-hole carbon material.Because having one-dimension oriented orderly MOF to be still able to maintain that in carbonisation
Its is one-dimension oriented, and partial melting can occur for organic matter under the conditions of high temperature cabonization, can be cross-linked to each other between fiber.Secondly, MOF
It itself is the porous material based on micropore, it is very high as micropore proportion in the carbon material that presoma obtains using it.Again, exist
In carbonisation, metal ion can be changed into corresponding metal or metal oxide, be limited by the size of synthesized material,
Grain size is generally tens nanometer, arrives after etching template mesoporous.Finally, the institute in organic matter decomposition and classification process
Under the double action for generating gas, part macropore is easily formed.In conclusion with one-dimension oriented orderly MOF synthesizing one-dimensional
The orderly cross-linked fibrous grading-hole carbon material of orientation, using it as lithium sulfur battery anode material, conductive good, material choosing
With the advantages that range is wide, material preparation process is simple.Before to one-dimension oriented orderly cross-linked fibrous grading-hole carbon material
The adjusting for driving body technology parameter is realized to one-dimension oriented orderly cross-linked fibrous grading-hole carbon material pore size, aperture point
The regulation of cloth, specific surface, pore volume further increases its captured sulfur result, and then improves lithium-sulfur cell performance, has important reality
Use meaning.
Summary of the invention
It is an object of that present invention to provide a kind of one-dimension oriented orderly cross-linked fibrous grading-hole carbon materials of lithium-sulfur cell
And its application.
To achieve the above object, The technical solution adopted by the invention is as follows:
A kind of positive material for lithium-sulfur battery,
Using metal salt and organic ligand as raw material, it is prepared with one-dimension oriented metal organic framework (MOF), passes through
One-dimension oriented orderly cross-linked fibrous grading-hole carbon material is made in temperature programming carbonization, etching template, activation；
The organic ligand be one of trimesic acid, melamine, cyanuric acid, trithiocyanuric acid or two kinds with
On；
The metal salt is one of ferric nitrate, copper nitrate, nickel nitrate, zinc nitrate or two kinds or more.
The preparation method of above-mentioned one-dimension oriented orderly cross-linked fibrous grading-hole carbon material, this method use following steps
Preparation:
(1) 1:2 by organic ligand and dissolving metal salts or disperses in a solvent in molar ratio, is 25~100 DEG C in temperature
0.5~2h of lower stirring, makes to be uniformly mixed；
(2) mixture prepared by step (1) is transferred in reaction kettle, reaction kettle is placed in Muffle furnace or air dry oven
In, program is warming up to greater than 25 to 250 DEG C in 25 DEG C of room temperature or from room temperature, at such a temperature 5~96h of isothermal reaction, program
It is cooled to room temperature, heating rate is 0.5~5 DEG C of min-1, the warm rate that cools down is 0.1~2 DEG C of min-1；
(3) product that step (2) obtains is placed in tube furnace, program is warming up to carbonization from room temperature in different atmosphere
Temperature carbonization；Different atmosphere is following one kind, Ar, N2、H2With Ar gaseous mixture or NH3With Ar gaseous mixture；Gas flow rate be 30~
300mL min-1, heating rate is 1~10 DEG C of min-1, carburizing temperature be 500~2100 DEG C, in carburizing temperature constant temperature time be 1
~15h；
(4) ingredient in product obtained according to step (3) is different, is not contained or contained metal, metal oxide
The carbon material of middle one or two or more kinds template；
The carbon material containing templates one or two or more kinds of in metal, metal oxide that step (3) is obtained is set respectively
In HCl or HNO3One or two or more kinds of in etching metal, metal oxide in solution, HCl concentration is 3~36wt%, HNO3
Concentration is 5~40wt%；
The product of wherein metal or metal oxide can not be wherein completely removed due to the coating function of carbon, then passes through water
Steam activation or the method for KOH activation destroy carbon shell, further repeat above-mentioned etching process, metal or metal in etachable material
Oxide；
Wherein steam activation, the flow velocity of vapor are 30~100mL min-1, activation temperature is 600~1000 DEG C, living
The change time is 0.5~5h；
Wherein KOH is activated, and the mass ratio of KOH and corrosion material to be etched is 1~10；Activation temperature is 600~900 DEG C, living
The change time is 0.5~5h；
The carbon material without containing templates one or two or more kinds of in metal, metal oxide that step (3) obtains is without carving
Template is lost, next-step operation use can be directly carried out；
(5) carbon material in step (4) is taken out, with ethyl alcohol and water washing, after drying, obtains one-dimension oriented orderly of finished product
Cross-linked fibrous grading-hole carbon material.
In order to improve the compatibility of metal ion and organic matter in step (1), it is added in the mixture of step (1) a small amount of
Surfactant, final concentration of 0.00005~0.0005M of surfactant；
The surfactant be polyvinylpyrrolidone, neopelex, cetyl trimethylammonium bromide,
It is one or two or more kinds of in F127, P123.
The solvent is water, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, ethyl alcohol, methanol, one in ethylene glycol
Kind or two kinds or more.
The one-dimension oriented orderly cross-linked fibrous grading-hole carbon material prepared.
In the one-dimension oriented orderly cross-linked fibrous grading-hole carbon material micropore be 2nm hereinafter, it is mesoporous be 2~
50nm, macropore are 50~2000nm；
The diameter of the one-dimension oriented orderly cross-linked fibrous grading-hole carbon material is 10~5000nm, length 50
~5000 μm, specific surface is 100~5000m2g-1, pore volume is 0.1~4.5cm3g-1。
The one-dimension oriented orderly cross-linked fibrous grading-hole carbon material is applied in lithium-sulfur cell as positive electrode.
Beneficial outcomes of the invention are as follows:
(1) one-dimension oriented orderly cross-linked fibrous grading-hole carbon material can pass through the ratio of adjusting organic ligand and metal salt
Example, carburizing temperature, carbonization time, activation method, activation temperature, activation time optimize one-dimension oriented orderly cross-linked fibrous
The parameters such as grading-hole carbon material pore size, pore-size distribution, specific surface, pore volume, the utilization rate of Lai Tigao active material improve
Captured sulfur result further increases the comprehensive performance of lithium-sulfur cell.
(2) one-dimension oriented orderly cross-linked fibrous grading-hole carbon material prepared by the present invention is not by traditional one-dimensional material
Constraint, specific surface area is high, and pore volume is big.
(3) one-dimension oriented orderly cross-linked fibrous grading-hole carbon material prepared by the present invention is without adding any template
Agent, synthesis step is few, easy to operate.
(4) one-dimension oriented orderly cross-linked fibrous grading-hole carbon material MOF prepared by the present invention by metal ion and has
Machine ligand is combined by stronger coordinate bond, its basic size and orientation are able to maintain that in carbonisation.Therefore, to have one
The orderly MOF of dimension orientation is that carbon material synthesized by presoma is still able to maintain that its orderly one-dimension oriented structure.Secondly,
Partial melting can occur for organic matter under the conditions of high temperature cabonization, can be cross-linked to each other between fiber.Again, MOF itself is with micro-
Porous material based on hole is very high as micropore proportion in the carbon material that presoma obtains using it；In carbonisation, metal
Ion can be changed into corresponding metal or metal oxide, be limited by the size of synthesized material, and granular size generally counts
It ten nanometers, is arrived after etching template mesoporous；The double action of produced gas in organic matter decomposition and decomposable process
Under, easily form part macropore.In conclusion using with one-dimension oriented MOF as presoma, be not necessarily to any template effect
Under, can synthesizing one-dimensional orientation orderly cross-linked fibrous and there is micropore simultaneously, the grading-hole carbon materials of mesoporous and big pore size distribution
Material.Compared with the conventional powder carbon material for being applied to lithium-sulfur cell, one-dimensional orientation texture is conducive to construct three-dimensional electronic transmission
Network, to improve the electric conductivity of electrode, be cross-linked to each other the contact resistance that can be further decreased between fiber between fiber, has
Sequence structure can shorten electron-transport path, therefore being capable of the good electronics biography of microelectronics offer using the material as positive electrode
Defeated channel.Moreover, micropore can be spread by the dissolution of powerful capillarity power limit polysulfide, mesoporous and macropore can
Biggish pore volume is provided, the infiltration of electrolyte and the transmission of lithium ion are conducive to.Since such carbon material has good electricity
Son and ion transport capability, so there is good high rate performance using it as the lithium-sulfur cell of electrode material.In conclusion one
The orderly cross-linked fibrous grading-hole carbon material of orientation is tieed up as lithium sulfur battery anode material, material preparation process, electronics and
Ionic conduction etc. all shows big advantage, has a good application prospect.
Detailed description of the invention
Fig. 1: the schematic diagram of one-dimension oriented orderly cross-linked fibrous grading-hole carbon material preparation (by taking embodiment 1 as an example)；
Fig. 2: the SEM picture of 1 presoma MOF of embodiment；
Fig. 3: the SEM (left figure) and TEM (right figure) picture of embodiment 1；
Fig. 4: the adsorption desorption curve (left figure) and graph of pore diameter distribution (right figure) of comparative example and embodiment 1-2；
Fig. 5: it is tested with the ohmage of comparative example and embodiment 1-2 assembling lithium-sulfur cell；
Fig. 6: it is tested with the high rate performance of comparative example and embodiment 1-2 assembling lithium-sulfur cell.
Specific embodiment
The following examples are not intended to limit the scope of the invention to further explanation of the invention.Comparative example
0.4g is commercialized KB 600 and 0.6g S after evenly mixing, is dissolved in 10mL CS2In, to CS2After volatilization completely, it is placed in
In tube furnace, 155 DEG C are warming up to, heating rate is 1 DEG C of min-1, constant temperature 20h takes 0.2g sample dispersion therein in 2.36g N-
Methyl pyrrolidone (NMP) after ultrasonic 20min, stirs 1h, and 0.25g 10wt% Kynoar (PVDF) solution is added, molten
Agent is NMP, stirs 5h, adjusts scraper to 150 μm, film forming is scratched in aluminum laminated films, after 70 DEG C of dryings overnight, cuts into diameter
For 14mm sequin, after weighing, after 60 DEG C of vacuum drying for 24 hours, to be coated with the sequin of synthesized carbon material, for anode, (monolithic is carried
Sulfur content is about 0.5mg cm-2), lithium piece is cathode, and celgard 2325 is diaphragm, molten with bis- (the trifluoromethyl semi-annular jade pendant acyl) imine lithiums of 1M
Liquid (LiTFSI) is electrolyte solution, and solvent is mixed liquor (the volume ratio v/v of 1,3-dioxolane (DOL) and dimethyl ether (DME)
=1:1), assembled battery carries out high rate performance charge-discharge test under 0.5C~15C multiplying power.
Under 0.5C multiplying power, first circle specific discharge capacity is 1311mA h g-1, after 40 circulations, under 15C multiplying power, put
Electric specific capacity is 195mA h g-1。
Embodiment 1
0.42g trimesic acid and 0.96g copper nitrate are weighed, 0.5h is stirred at room temperature, is transferred in 100mL hydrothermal reaction kettle,
With 3 DEG C of min-1Heating temperature rate be warming up to 180 DEG C, constant temperature for 24 hours, then with 0.3 DEG C of min-1Rate of temperature fall be down to room temperature, will
It is transferred in tube furnace after resulting blue floccule washing, with 3 DEG C of min-1Heating temperature rate be warming up to 900 DEG C, constant temperature 4h, then
With 1 DEG C of min-1Rate of temperature fall be down to room temperature.Product after carbonization is placed in the HNO of 10wt%3In, after standing 24, after drying,
After mixing (mass ratio of KOH and carbon is 4:1) with KOH, it is placed in nickel tube tube furnace, with 10 DEG C of min-1Heating temperature rate heating
To 700 DEG C, constant temperature 1h, then with 2 DEG C of min-1Rate of temperature fall be down to room temperature, products therefrom is again placed in the HNO of 10wt%3
In, after standing 24, washing and drying, it is resulting while be cross-linked to each other with one-dimension oriented, orderly, fiber with micropore,
The one-dimension oriented orderly cross-linked fibrous grading-hole carbon material of mesoporous, big pore size distribution is finished product.Subsequent to fill sulphur, assembled battery is surveyed
Try is equal to comparative example suddenly.
Under 0.5C multiplying power, first circle specific discharge capacity is 1562mA h g-1, after 40 circulations, under 15C multiplying power, put
Electric specific capacity is 543mA h g-1。
Embodiment 2
0.42g trimesic acid and 1.20g zinc nitrate are weighed, 0.5h is stirred at room temperature, is transferred in 100mL hydrothermal reaction kettle,
With 3 DEG C of min-1Heating temperature rate be warming up to 180 DEG C, constant temperature for 24 hours, then with 0.3 DEG C of min-1Rate of temperature fall be down to room temperature, will
It is transferred in tube furnace after resulting white product washing, with 3 DEG C of min-1Heating temperature rate be warming up to 950 DEG C, constant temperature 4h, then with
1℃min-1Rate of temperature fall be down to room temperature.Products therefrom is without carrying out post-processing direct use.Subsequent to fill sulphur, assembled battery is surveyed
The rapid equivalent integers 1 of try.
Under 0.5C multiplying power, first circle specific discharge capacity is 1384mA h g-1, after 40 circulations, under 15C multiplying power, put
Electric specific capacity is 344mA h g-1。
Embodiment 3
0.42g trimesic acid and 1.20g copper nitrate are weighed, 0.5h is stirred at room temperature, is stood for 24 hours, by resulting blue color
It is transferred in tube furnace after product washing, with 3 DEG C of min-1Heating temperature rate be warming up to 900 DEG C, constant temperature 4h, then with 1 DEG C of min-1's
Rate of temperature fall is down to room temperature.Subsequent activation fills sulphur, assembled battery testing procedure equivalent integers 1.
Under 0.5C multiplying power, first circle specific discharge capacity is 1365mA h g-1, after 40 circulations, under 15C multiplying power, put
Electric specific capacity is 325mA h g-1。
Embodiment 4
0.42g trimesic acid and 1.62g ferric nitrate are weighed, 0.5h is stirred at room temperature, is transferred in 100mL hydrothermal reaction kettle,
With 3 DEG C of min-1Heating temperature rate be warming up to 180 DEG C, constant temperature for 24 hours, then with 0.3 DEG C of min-1Rate of temperature fall be down to room temperature, will
It is transferred in tube furnace after resulting faint yellow product washing, with 3 DEG C of min-1Heating temperature rate be warming up to 800 DEG C, constant temperature 4h, then
With 1 DEG C of min-1Rate of temperature fall be down to room temperature.Products therefrom is without carrying out post-processing direct use.Subsequent activation fills sulphur, assembling
Battery testing step equivalent integers 1.
Under 0.5C multiplying power, first circle specific discharge capacity is 1328mA h g-1, after 40 circulations, under 15C multiplying power, put
Electric specific capacity is 287mA h g-1。
The presoma of embodiment 1 is with super large draw ratio (L/D it can be seen from the SEM figure of 1 presoma of Fig. 2 embodiment
≈ 1000) one-dimension oriented orderly MOF, through carbonization cremate after as can be seen that embodiment 1 as shown in Figure 3 still it is maintained to have
The one-dimension oriented structure of sequence is cross-linked to each other between fiber, and ordered fiber and its branch have been cross-linked to form a large amount of hundred nanometers
The macropore of grade.Be conducive to the electron-transport network of three-dimensional " Line To Line " of building, orderly fiber with one-dimension oriented fiber
Electron-transport distance can be shortened, the two provides high-speed channel jointly for electronics, greatly improves the electric conductivity of electrode.Its
Secondary, the macropore of formation is conducive to the infiltration of electrolyte and the transmission of lithium ion, and single aperture is (in view of the cyclicity of battery under subtracting
Can, generally with the carbon material in single aperture with micropore or it is small it is mesoporous based on, ion transport resistance is larger) ion transport resistance.
By the TEM figure of Fig. 3 and the BET figure of Fig. 4 as can be seen that embodiment 1 is other than macropore, there is also big in its fiber skeleton
The mesoporous and micropore of amount, one side micropore is capable of providing biggish specific surface, sulphur can be contacted with carbon material more preferable, another
Aspect, micropore can also be hindered the dissolution of polysulfide to spread by powerful capillary force, realized " Gu sulphur ".It is mesoporous can be with
It provides biggish pore volume to be used to store up sulphur, while the interface channel as micropore and macropore, lithium ion biography can be further decreased
Defeated resistance.Its advantage in terms of electronics and ion transmission can be verified further by the electrochemical impedance of Fig. 5.By scheming
As can be seen that embodiment 1 not only has the smallest ohmage, also there is the smallest electrochemical impedance.It can be seen that one
It is true to tie up the orderly cross-linked fibrous grading-hole carbon material being orientated powder carbon material more traditional in terms of the transmitting of electronics and ion
Real storage is in biggish advantage.It therefore, is anode compared with comparative example for the lithium-sulfur cell of positive electrode with embodiment 1 and embodiment 2
The high rate performance of the battery of material is significantly improved.Especially embodiment 1, under 0.5C multiplying power, initial discharge specific capacity can
To reach 1562mA h g-1(about theoretical specific capacity 1672mA h g-193.4%), illustrate that the material can be good at mentioning
The utilization rate of high active substance；Secondly under 15C multiplying power, capacity still can achieve 543mA h g-1, illustrate that the material can
Meet the transmission requirement to electronics and ion under high multiplying power well.The high rate performance of battery and the knot of electrochemical impedance
Fruit height is consistent.
Claims (6)
1. the preparation method of one-dimension oriented orderly cross-linked fibrous grading-hole carbon material, it is characterised in that:
Using metal salt and organic ligand as raw material, it is prepared with one-dimension oriented metal organic framework (MOF), passes through program
One-dimension oriented orderly cross-linked fibrous grading-hole carbon material is made in heating carbonization, etching template, activation；
The organic ligand is one of trimesic acid, melamine, cyanuric acid, trithiocyanuric acid or two kinds or more；
The metal salt is one of ferric nitrate, copper nitrate, nickel nitrate, zinc nitrate or two kinds or more；
The preparation step of the one-dimension oriented orderly cross-linked fibrous grading-hole carbon material is as follows,
(1) 1:2 by organic ligand and dissolving metal salts or disperses in a solvent, to stir at being 25~100 DEG C in temperature in molar ratio
0.5~2 h is mixed, makes to be uniformly mixed；
(2) mixture prepared by step (1) is transferred in reaction kettle, reaction kettle is placed in Muffle furnace or air dry oven, in
25 DEG C of room temperature or program is warming up to greater than 25 to 250 DEG C from room temperature, at such a temperature 5 ~ 96 h of isothermal reaction, program cooling
To room temperature, heating rate is 0.5~5 DEG C of min-1, rate of temperature fall is 0.1~2 DEG C of min-1；
(3) product that step (2) obtains is placed in tube furnace, program is warming up to carburizing temperature from room temperature in different atmosphere
Carbonization；Different atmosphere is following one kind, Ar, N2、H2With Ar gaseous mixture or NH3With Ar gaseous mixture；Gas flow rate is 30~300
mL min-1, heating rate is 1~10 DEG C of min-1, carburizing temperature be 500~2100 DEG C, in carburizing temperature constant temperature time be 1
~15 h；
(4) ingredient in product obtained according to step (3) is different, is not contained or containing in metal, metal oxide one
The carbon material of kind or two kinds of template above；
The carbon material containing templates one or two or more kinds of in metal, metal oxide that step (3) is obtained is respectively placed in HCl
Or HNO3One or two or more kinds of in etching metal, metal oxide in solution, HCl concentration is 3~36 wt%, HNO3Concentration
For 5~40 wt%；
The product of wherein metal or metal oxide can not be wherein completely removed due to the coating function of carbon, then passes through vapor
The method of activation or KOH activation destroys carbon shell, further repeats above-mentioned etching process, metal or metal oxidation in etachable material
Object；
Wherein steam activation, the flow velocity of vapor are 30~100 mL min-1, activation temperature is 600 ~ 1000 DEG C, when activation
Between be 0.5~5 h；
Wherein KOH is activated, and the mass ratio of KOH and corrosion material to be etched is 1 ~ 10；Activation temperature is 600 ~ 900 DEG C, activation time
For 0.5~5 h；
The carbon material without containing templates one or two or more kinds of in metal, metal oxide that step (3) obtains is without etching mould
Plate can directly carry out next-step operation use；
(5) carbon material taken out in step (4) after drying, obtains the one-dimension oriented orderly crosslinking of finished product with ethyl alcohol and water washing
Fibrous grading-hole carbon material.
2. preparation method according to claim 1, it is characterised in that:
In order to improve the compatibility of metal ion and organic matter in step (1), a small amount of table is added in the mixture of step (1)
Face activating agent, final concentration of 0.00005 ~ 0.0005 M of surfactant；
The surfactant be polyvinylpyrrolidone, neopelex, cetyl trimethylammonium bromide,
It is one or two or more kinds of in F127, P123.
3. preparation method according to claim 1, it is characterised in that:
The solvent be one of water, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, ethyl alcohol, methanol, ethylene glycol or
Two kinds or more.
4. the one-dimension oriented orderly cross-linked fibrous grading-hole carbon materials that a kind of any preparation method of claim 1-3 prepares
Material.
5. according to carbon material described in claim 4, it is characterised in that:
Micropore is 2 nm hereinafter, mesoporous is 2 ~ 50 nm in the one-dimension oriented orderly cross-linked fibrous grading-hole carbon material,
Macropore is 50 ~ 2000 nm；
The diameter of the one-dimension oriented orderly cross-linked fibrous grading-hole carbon material be 10 ~ 5000 nm, length be 50 ~
5000 μm, specific surface is 100~5000 m2 g-1, pore volume is 0.1~4.5 cm3 g-1。
6. a kind of application of the one-dimension oriented orderly cross-linked fibrous grading-hole carbon material of claim 4 or 5, feature exist
In: the one-dimension oriented orderly cross-linked fibrous grading-hole carbon material is applied in lithium-sulfur cell as positive electrode.
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| CN109052360A (en) * | 2018-08-08 | 2018-12-21 | 东华大学 | A kind of nitrogen-doped carbon material and preparation method thereof with hollow polyhedron structure |
| CN109850866B (en) * | 2019-01-30 | 2021-03-09 | 青岛大学 | Hierarchical porous carbon material for flexible supercapacitor and preparation method thereof |
| CN109950472B (en) * | 2019-03-21 | 2020-11-24 | 华中科技大学 | Lithium-sulfur battery positive electrode material, preparation method thereof, electrode plate and lithium-sulfur battery |
| CN110181070A (en) * | 2019-06-04 | 2019-08-30 | 陕西科技大学 | A kind of the Ni/C composite material and preparation method and application of hollow ball-shape |
| CN110492065B (en) * | 2019-07-26 | 2022-02-08 | 江苏理工学院 | S/Co/CNF composite material based on waste cigarette ends and preparation method and application thereof |
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| CN112893858B (en) * | 2019-11-19 | 2021-12-28 | 中国科学院大连化学物理研究所 | Preparation method of nickel-carbon-based material |
| CN111224082A (en) * | 2019-12-02 | 2020-06-02 | 大连理工大学 | Copper/porous carbon material capable of being used as lithium-sulfur battery anode carrier material, preparation method and application |
| CN115347174B (en) * | 2022-08-31 | 2023-07-18 | 华南理工大学 | Porous Cu-MOF, copper selenide derivative and preparation method and application thereof |
| CN116462180A (en) * | 2023-05-06 | 2023-07-21 | 四川兴储能源科技有限公司 | Amorphous carbon, preparation method thereof, amorphous carbon cathode and application thereof |
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