CN109301182A - Static Spinning cobalt/N doping porous carbon nano-composite fiber and its preparation and application - Google Patents
Static Spinning cobalt/N doping porous carbon nano-composite fiber and its preparation and application Download PDFInfo
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- CN109301182A CN109301182A CN201811030567.8A CN201811030567A CN109301182A CN 109301182 A CN109301182 A CN 109301182A CN 201811030567 A CN201811030567 A CN 201811030567A CN 109301182 A CN109301182 A CN 109301182A
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The present invention provides a kind of Static Spinning cobalt/N doping porous carbon nano-composite fiber and its preparation and application.The Static Spinning cobalt/N doping porous carbon nano-composite fiber, it is characterized in that, by situ aggregation method on Static Spinning porous fibre growth in situ poly-dopamine, so that cobalt ions is attached to fiber surface by infusion process, after high temperature cabonization, distillation is blended with sulphur and is prepared.The cobalt of Static Spinning prepared by the present invention/N doping porous carbon nano-composite fiber has many advantages, such as that chemical property stabilization, good conductivity, mechanical property are good.Static Spinning cobalt prepared by the present invention/N doping porous carbon nano-composite fiber morphology controllable has high porosity and high-specific surface area.Composite fibre prepared by the present invention is a kind of ideal electrode material of lithium-sulfur cell, the electric conductivity of sulphur anode, buffer volumes variation can be improved, and effectively inhibit shuttle effect, and accelerate the dynamics of oxidation-reduction of polysulfide, significantly improves its chemical property.
Description
Technical field
The invention belongs to carbon material technical fields, and in particular to Static Spinning cobalt/N doping porous carbon nano-composite fiber and
Its preparation and application.The material is a kind of ideal electrode material of lithium-sulfur cell, and the electric conductivity of sulphur anode, buffer volumes can be improved
Variation effectively inhibits shuttle effect, while cobalt nano-particle can effectively accelerate the dynamics of oxidation-reduction of polysulfide, shows
It writes and improves its chemical property.
Background technique
Carbon nano-fiber has the excellent properties such as high conductivity, Gao Kongrong, high-specific surface area, light density is low, thus quilt
It is widely used in the fields such as energy conversion and memory device, high molecule nano composite material, it is considered to be future ten is big most latent
One of new material of power.Wherein, method of electrostatic spinning be prepare carbon nano-fiber materials a kind of equipment is simple, low-cost side
Method, obtained fiber have many advantages, such as that preparation process is simple and efficient, diameter is evenly distributed, and controllable, load sulfur content is high.
In addition, acting on by the physics confinement of carbonaceous material Different Pore Structures merely, polysulfide cannot be entirely limited
It shuttles, and the surface chemical property of carbonaceous material largely affects the chemical property of lithium-sulfur cell, passes through carbonaceous
At material surface function dough (such as hydroxylating, carboxylated, amination) and heteroatom (such as nitrogen, sulphur, phosphorus, boron) hydridization
Reason, can be improved the interaction of itself and sulphur, polysulfide.Dopamine is a kind of imitative mussel Fibronectin, can single step reaction conjunction
At poly-dopamine, with good biocompatibility, a variety of functional groups (such as phenolic hydroxyl group, quinonyl, amido and carboxylic are rich in structure
Base etc.), not only intermolecular interaction can occur with analyte and be used for enrichment and separation, but also can send out under certain condition
Raw specific chemical reaction provides possibility for the further modification and modification of a variety of materials, is a kind of ideal in separation science field
Surface modified function material.Poly-dopamine is converted into nitrogenous carbon as a kind of high activity nitrogenous macromolecular material after carbonization
Material has the atomic structure and electric conductivity of similar multi-layer graphene, has good application prospect in energy field.
Meanwhile the introducing of cobalt nano-particle can effectively accelerate the dynamics of oxidation-reduction of polysulfide.By simple
Infusion process, using a large amount of active group in dopamine surface, cobalt ions can be directly adsorbed in fiber surface, after heat treatment
It is changed into cobalt nano-particle.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation process environmental protection, preparation cost are cheap, electrochemical performance quiet
Electrospinning cobalt/N doping porous carbon nanometer composite fiber material.
In order to achieve the above object, the present invention provides a kind of Static Spinning cobalt/N doping porous carbon nano-composite fiber,
Be characterized in that, by situ aggregation method on Static Spinning porous fibre growth in situ poly-dopamine, adhere to cobalt ions by infusion process
In fiber surface, after high temperature cabonization, distillation is blended with sulphur and is prepared.
Preferably, Static Spinning cobalt/N doping porous carbon nano-composite fiber specific surface area is 150~400m2/
G, cobalt content are 5~30%, and sulfur content is 60~70%.
The present invention also provides above-mentioned Static Spinning cobalt/N doping porous carbon nano-composite fiber preparation methods, special
Sign is, comprising:
Step 1: preparing Static Spinning porous fibre；
Step 2: Static Spinning porous fibre being impregnated in the mixed solution of Tris hydrochloric acid and Dopamine hydrochloride, adjusting pH is
8~10, in-situ polymerization is carried out in 50~90 DEG C of heating water baths, obtains the polystyrene porous fiber of poly-dopamine cladding；
Step 3: the polystyrene porous fiber that poly-dopamine coats being impregnated in acetic acid cobalt liquor, has obtained cobalt ions
The poly-dopamine of attachment coats polystyrene porous fiber；
Step 4: by the poly-dopamine cladding polystyrene porous fiber of cobalt ions attachment in nitrogen or inert gas shielding
Static Spinning cobalt/N doping porous carbon nano-composite fiber is prepared in lower 600~1000 DEG C of progress high temperature cabonization；
Step 5: sublimed sulfur is mixed with Static Spinning cobalt/N doping porous carbon nanofiber with mass ratio 1.5:1~4:1,
Static Spinning cobalt/N doping porous carbon nano-composite fiber is obtained in 150~180 DEG C of reactions.
Preferably, the preparation method of the Static Spinning porous fibre includes: that polymer chips is added in solvent, is held
Resulting polymer solution is carried out electrostatic spinning by continuous stirring, is received with receiving bath, is obtained Static Spinning porous fibre.
It is highly preferred that the polymer is polystyrene, solvent is n,N-Dimethylformamide, and polymer solution is consolidated
Content is 15~40%, and receiving bath is ethyl alcohol.
It is highly preferred that the technological parameter of the electrostatic spinning are as follows: spinning cathode voltage is set as 9~10kV, negative electricity
Pressure is set as -1~-2kV, and receiving distance between bath foam face and spinning syringe needle is 9~10cm.
Preferably, the concentration of Tris hydrochloric acid is 0.005~0.015mol/L, preferably 0.01mol/ in the mixed solution
L, the concentration of Dopamine hydrochloride are 0.005~0.05mol/L, preferably 0.01~0.02mol/L.
Preferably, the soaking time range in the step 2 is 1~4h, preferably 2~3h；PH preferably 8.5~9；Water-bath
Preferably 70~80 DEG C of heating temperature；Reaction time range is 12~30h, preferably 20~for 24 hours.
Preferably, the cobalt acetate solution concentration range in the step 3 be 0.01~1mol/L, preferably 0.05~
0.4mol/L；Soaking time range be 8~for 24 hours, preferably 12~16h.
Preferably, the pH is adjusted by the potassium hydroxide solution that concentration is 0.05~0.2mol/L, and preferred concentration is
0.1mol/L。
Preferably, the temperature of the high temperature cabonization is 700~800 DEG C, and the high temperature cabonization time is 1~3h, preferably 2h.
Preferably, the mass ratio of the sublimed sulfur and N doping porous carbon nanofiber is 2:1~3:1, reaction temperature
It is 155~160 DEG C, reaction time range is 12~30h, preferably 20~26h.
The present invention also provides the three-dimensional network knots that above-mentioned Static Spinning cobalt/N doping porous carbon nano-composite fiber is formed
Application of the structure in the electrode material as lithium-sulfur cell.
It is prepared for porous polymer nanofiber using electrostatic spinning technique in the present invention, poly-dopamine is coated on porous
Cobalt ions is attached to the polymer that poly-dopamine coats as decorative layer, then by infusion process by the surface of polymer nanofiber
Fiber surface obtains Static Spinning cobalt/N doping porous carbon nanofiber through high temperature cabonization, is obtained by melt-blending process multiple with sulphur
The Static Spinning cobalt of conjunction/N doping porous carbon nanofiber composite material.Use highly conductive, three-dimensional net structure cobalt/N doping
Porous carbon nanofiber provides three-dimensional porous network structure as carrier, for electrode material, improves the load capacity of sulphur, also mentions
The high electric conductivity of sulphur anode, and volume expansion can be inhibited to keep the integrity and stability of anode structure.In addition, N doping
The adsorbable more lithium sulfides of porous carbon nanofiber, inhibit the shuttle effect problem of polysulfide, and cobalt nano-particle can accelerate more sulphur
The dynamics of oxidation-reduction of compound.Therefore, Static Spinning cobalt/N doping porous carbon is introduced in lithium-sulphur cell positive electrode system to receive
The electric conductivity of sulphur anode, buffer volumes variation can be improved in rice composite fibre, and effectively inhibits shuttle effect, to significantly improve
Its chemical property.
Compared with prior art, the beneficial effects of the present invention are:
(1) preparation process is simple and environmentally-friendly, easily operated, is a kind of Green Chemistry preparation method.
(2) experimental design is ingenious.Poly- DOPA is grown in Static Spinning styroflex surface in situ using situ aggregation method
Amine makes cobalt ions be attached directly to porous fibre surface, then prepares cobalt/N doping porous carbon through high temperature cabonization method by infusion process
Nano-composite fiber has successfully constructed the porous composite fibre with high-specific surface area.
(3) Static Spinning cobalt/N doping porous carbon nano-composite fiber prepared by, nitrogen, cobalt element doping can be effective
Inhibit shuttle effect and accelerates the dynamics of oxidation-reduction of polysulfide, and the three-dimensional porous network knot that carbon fiber is constructed
The electric conductivity of sulphur anode, buffer volumes variation can be improved in structure, so that collaboration significantly improves its chemical property, it is with higher
Specific discharge capacity and cyclical stability are the ideal electrode materials of lithium-sulfur cell.
(4) Static Spinning cobalt/N doping porous carbon nano-composite fiber prepared by the present invention has chemical property stabilization, leads
The advantages that electrically good, mechanical property is good.Static Spinning cobalt prepared by the present invention/N doping porous carbon nano-composite fiber pattern can
Control has high porosity and high-specific surface area.The cobalt of Static Spinning prepared by the present invention/N doping porous carbon nano-composite fiber is
A kind of ideal electrode material of lithium-sulfur cell, can be improved the electric conductivity of sulphur anode, and buffer volumes variation effectively inhibits the effect that shuttles
It answers, and accelerates the dynamics of oxidation-reduction of polysulfide, significantly improve its chemical property.
Detailed description of the invention
Fig. 1 is Static Spinning cobalt in the present invention/N doping porous carbon nano-composite fiber scanning electron microscope (SEM) photo.
Fig. 2 is Static Spinning cobalt in the present invention/N doping porous carbon nano-composite fiber X-ray diffraction (XRD) style.
Fig. 3 is after Static Spinning cobalt in the present invention/N doping porous carbon nano-composite fiber anode is assembled into lithium-sulfur cell
Cyclic voltammetric (CV) curve.
Fig. 4 is that Static Spinning cobalt in the present invention/N doping porous carbon nano-composite fiber anode is assembled into after lithium-sulfur cell
First and second, five circles charging and discharging curve obtained under the current density of 0.1C.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Specific surface area in following embodiment is measured using specific area measuring method (BET), and cobalt content and sulfur content use
Thermogravimetry (TGA) measurement.
Embodiment 1
A kind of Static Spinning cobalt/N doping porous carbon nano-composite fiber, by situ aggregation method on Static Spinning porous fibre
Growth in situ poly-dopamine makes cobalt ions be attached to fiber surface by infusion process, and after high temperature cabonization, distillation preparation is blended with sulphur
It forms.Its specific surface area is 210m2/ g, sulfur content 61%, cobalt content 15%.
The Static Spinning cobalt/N doping porous carbon nano-composite fiber the preparation method comprises the following steps:
Step 1: prepare Static Spinning porous fibre: by 9g polystyrene pellets (manufacturer: J&KCHEMICA, the trade mark:
918904, molecular weight: 250000) being added in 30mL n,N-Dimethylformamide, lasting to stir, and is by resulting concentration
30% uniform sticky polymers solution carries out electrostatic spinning, technological parameter are as follows: spinning cathode voltage is set as 9.7kV, cathode
Voltage is set as -1.1kV, and distance is 10cm between reception device ethyl alcohol liquid level and syringe needle, receives bath with ethyl alcohol and receives, obtains electrostatic
Spin porous fibre.
Step 2: by Static Spinning porous fibre, in Tris hydrochloric acid (concentration 0.01mol/L) and Dopamine hydrochloride, (concentration is
3h is impregnated in mixed solution 0.01mol/L), it is 8.5 that the potassium hydroxide solution for being constantly 0.1mol/L with concentration, which adjusts pH,
80 DEG C of heating water baths carry out in-situ polymerization for 24 hours, obtain the polystyrene porous fiber of poly-dopamine cladding；
Step 3: by the polystyrene porous fiber of poly-dopamine cladding in acetic acid cobalt liquor (concentration 0.05mol/L)
12h is impregnated, the poly-dopamine cladding polystyrene porous fiber of cobalt ions attachment is obtained.
Step 4: by the poly-dopamine cladding polystyrene porous fiber of cobalt ions attachment 700 under high pure nitrogen protection
DEG C carry out high temperature cabonization 2h, Static Spinning cobalt/N doping porous carbon nano-composite fiber is prepared；
Step 5: sublimed sulfur being uniformly mixed with N doping porous carbon nanofiber with mass ratio 2:1, is reacted at 155 DEG C
For 24 hours, Static Spinning cobalt/N doping porous carbon nanofiber composite material that distillation preparation is blended with sulphur is obtained.
The preparation-obtained Static Spinning of the present invention is characterized using SEM, XRD, electrochemical workstation, battery test system
Cobalt/N doping porous carbon nano-composite fiber pattern and structure and its chemical property as lithium sulfur battery anode material,
Its result is as follows:
(1) SEM test result shows: prepared Static Spinning cobalt/N doping porous carbon nano-composite fiber in the present invention
With three-dimensional porous structure, the diameter of fiber is about 1~2 μm, and dopamine concentration appropriate can just obtain the more of structural integrity
Hole carbon nano-fiber.The high-specific surface area of porous carbon nanofiber improves the load capacity of sulphur, and volume expansion can be inhibited to protect
Hold the integrity and stability of anode structure.Referring to attached drawing 1.
(2) XRD test result shows: Static Spinning cobalt/N doping porous carbon nano-composite fiber XRD is at 44 ° and 52 °
There is the diffraction maximum of Co in left and right, corresponding with its (111), (200) crystal face respectively, indicates the nano combined fibre of N doping porous carbon
Dimension and cobalt nano-particle success are compound.Compound Static Spinning cobalt/N doping porous carbon nanofiber composite material XRD exists with sulphur
23 ° or so there is the characteristic diffraction peak of S, illustrate that Static Spinning cobalt/N doping porous carbon nano-composite fiber and S success are compound.Ginseng
See attached drawing 2.
(3) cyclic voltammetry the result shows that: obviously occur sulphur feature reversible electrochemical reduction and oxidation peak, 2.33V
Reduction reaction process of the sulphur simple substance to high-order sulphur, low order sulphur, lithium sulfide, the anode peak of 2.37V can be belonged to 2.03V cathode peak
Can belong to lithium sulfide to low order sulphur, high-order sulphur, sulphur simple substance oxidation reaction process.As the cycle progresses, anode peak is gradually
It is mobile to low potential, it finally tends towards stability, shows after being activated by several circles, the invertibity of sulphur anode is improved.
(4) constant current charge-discharge test the result shows that: Static Spinning cobalt/N doping porous carbon nano-composite fiber presents two
The discharge platform of standard, first lap specific discharge capacity are 1127mA h g-1, first and second, five, which enclose coulombic efficiencies, is respectively
100%, 99.4%, 98.5%.As it can be seen that Static Spinning cobalt/N doping porous carbon nano-composite fiber have very high specific capacity and
Coulombic efficiency.Thus illustrate, efficiently lead in the N doping porous carbon nanofiber internal build with three-dimensional net structure
Electric network, and the network-like ion transmission channel with higher porosity and better electrolyte wellability, accelerate
Ion and electron transfer rate in charge and discharge process, and then effectively increase its specific capacity.
Embodiment 2
A kind of Static Spinning cobalt/N doping porous carbon nano-composite fiber, by situ aggregation method on Static Spinning porous fibre
Growth in situ poly-dopamine makes cobalt ions be attached to fiber surface by infusion process, and after high temperature cabonization, distillation preparation is blended with sulphur
It forms.Its specific surface area is 200m2/ g, sulfur content 67%, cobalt content 10%.Preparation method is similar to embodiment 1, area
It is not the cobalt acetate solution concentration in embodiment 1 becoming 0.2mol/L, remaining is final obtained multiple with embodiment 1
Condensating fiber is denoted as Co@NCNF-1.
Embodiment 3
A kind of sulphur/N doping porous carbon nano-composite fiber, is given birth on Static Spinning porous fibre in situ by situ aggregation method
Long poly-dopamine makes cobalt ions be attached to fiber surface by infusion process, after high temperature cabonization, distillation is blended with sulphur and is prepared.
Its specific surface area is 250m2/ g, sulfur content 64%, cobalt content 13%.Preparation method is similar to embodiment 1, and difference exists
In the cobalt acetate solution concentration in embodiment 1 is become 0.4mol/L, remaining is the same as embodiment 1, final composite wood obtained
Material is denoted as Co@NCNF-2.
Claims (10)
1. a kind of Static Spinning cobalt/N doping porous carbon nano-composite fiber, which is characterized in that more in Static Spinning by situ aggregation method
Growth in situ poly-dopamine on the fiber of hole, makes cobalt ions be attached to fiber surface by infusion process, after high temperature cabonization, is blended with sulphur
Distillation is prepared.
2. Static Spinning cobalt as described in claim 1/N doping porous carbon nano-composite fiber, which is characterized in that described is quiet
Electrospinning cobalt/N doping porous carbon nano-composite fiber specific surface area is 150~400m2/ g, cobalt content are 5~30%, and sulphur contains
Amount is 60~70%.
3. Static Spinning cobalt of any of claims 1 or 2/N doping porous carbon nano-composite fiber preparation method, feature exist
In, comprising:
Step 1: preparing Static Spinning porous fibre；
Step 2: Static Spinning porous fibre is impregnated in the mixed solution of Tris hydrochloric acid and Dopamine hydrochloride, adjust pH be 8~
10, in-situ polymerization is carried out in 50~90 DEG C of heating water baths, obtains the polystyrene porous fiber of poly-dopamine cladding；
Step 3: the polystyrene porous fiber that poly-dopamine coats being impregnated in acetic acid cobalt liquor, has obtained cobalt ions attachment
Poly-dopamine coat polystyrene porous fiber；
Step 4: by the poly-dopamine cladding polystyrene porous fiber of cobalt ions attachment 600 under nitrogen or inert gas shielding
~1000 DEG C of progress high temperature cabonizations, are prepared Static Spinning cobalt/N doping porous carbon nano-composite fiber；
Step 5: sublimed sulfur being mixed with Static Spinning cobalt/N doping porous carbon nanofiber with mass ratio 1.5:1~4:1,150
~180 DEG C of reactions obtain Static Spinning cobalt/N doping porous carbon nano-composite fiber.
4. Static Spinning cobalt as claimed in claim 3/N doping porous carbon nano-composite fiber, which is characterized in that described is quiet
The preparation method of electrospinning porous fibre includes: that polymer chips is added in solvent, lasting to stir, and resulting polymer is molten
Liquid carries out electrostatic spinning, is received with receiving bath, obtains Static Spinning porous fibre.
5. Static Spinning cobalt as claimed in claim 4/N doping porous carbon nano-composite fiber, which is characterized in that described is poly-
Conjunction object is polystyrene, and solvent is n,N-Dimethylformamide, and the solid content of polymer solution is 15~40%, and receiving bath is second
Alcohol；The technological parameter of the electrostatic spinning are as follows: spinning cathode voltage is set as 9~10kV, and cathode voltage is set as -1~-
2kV, receiving distance between bath foam face and spinning syringe needle is 9~10cm.
6. Static Spinning cobalt as claimed in claim 3/N doping porous carbon nano-composite fiber, which is characterized in that described is mixed
The concentration for closing Tris hydrochloric acid in solution is 0.005~0.015mol/L, and the concentration of Dopamine hydrochloride is 0.005~0.05mol/L,
Soaking time range in the step 2 is 1~4h, and pH is 8.5~9.
7. Static Spinning cobalt as claimed in claim 3/N doping porous carbon nano-composite fiber, which is characterized in that the step
Cobalt acetate solution concentration range in rapid 3 is 0.01~1mol/L, soaking time range is 8~for 24 hours.
8. Static Spinning cobalt as claimed in claim 3/N doping porous carbon nano-composite fiber preparation method, feature exist
In the temperature of the high temperature cabonization is 700~800 DEG C, and the high temperature cabonization time is 1~3h.
9. Static Spinning cobalt as claimed in claim 3/N doping porous carbon nano-composite fiber preparation method, feature exist
In, the mass ratio of the sublimed sulfur and N doping porous carbon nanofiber is 2:1~3:1, and reaction temperature is 155~160 DEG C,
Reaction time range is 12~30h.
10. the three-dimensional net structure that Static Spinning cobalt of any of claims 1 or 2/N doping porous carbon nano-composite fiber is formed
Application in the electrode material as lithium-sulfur cell.
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| CN112786830A (en) * | 2021-03-30 | 2021-05-11 | 齐鲁工业大学 | Co-HCS/S composite lithium-sulfur battery positive electrode material and preparation method thereof |
| CN113594415A (en) * | 2021-07-28 | 2021-11-02 | 贵州大学 | Sandwich independent positive electrode for inhibiting shuttle effect of lithium-sulfur battery and preparation method thereof |
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103050689A (en) * | 2011-10-17 | 2013-04-17 | 中国科学院大连化学物理研究所 | Metal-doped carbon/sulfur compound, and preparation and application thereof |
| CN105529472A (en) * | 2015-12-09 | 2016-04-27 | 武汉理工大学 | Co-N double-doped flaky porous two-dimensional carbon material and preparation method thereof |
| CN105923629A (en) * | 2016-04-26 | 2016-09-07 | 哈尔滨工程大学 | Method for preparing transition metal composite hetero atom doped porous carbon material through dipping, recrystallizing and carbonizing biomasses |
| KR20170024918A (en) * | 2015-08-26 | 2017-03-08 | 울산과학기술원 | Positive electrode active material, method for manufacturing the same, and electrochemical device including the same |
| CN106920941A (en) * | 2017-03-31 | 2017-07-04 | 合肥国轩高科动力能源有限公司 | A kind of cobalt, titanium, nitrogen co-doped CNT/sulphur composite positive pole and preparation method thereof |
| CN107317011A (en) * | 2017-06-28 | 2017-11-03 | 合肥工业大学 | A kind of preparation method of the ordered porous carbon coating silicon nano composite material of N doping |
| CN107394218A (en) * | 2017-07-29 | 2017-11-24 | 湖南科技大学 | A kind of cobalt doped double-layer carbon nitrogen complex nano material, preparation method and applications |
| CN108075121A (en) * | 2017-12-12 | 2018-05-25 | 东华大学 | Sulphur/N doping porous carbon nano-composite fiber and its preparation and application |
| CN108172801A (en) * | 2017-12-28 | 2018-06-15 | 哈尔滨工业大学深圳研究生院 | A kind of method of porous carbon materials doping vario-property and application |
-
2018
- 2018-09-05 CN CN201811030567.8A patent/CN109301182A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103050689A (en) * | 2011-10-17 | 2013-04-17 | 中国科学院大连化学物理研究所 | Metal-doped carbon/sulfur compound, and preparation and application thereof |
| KR20170024918A (en) * | 2015-08-26 | 2017-03-08 | 울산과학기술원 | Positive electrode active material, method for manufacturing the same, and electrochemical device including the same |
| CN105529472A (en) * | 2015-12-09 | 2016-04-27 | 武汉理工大学 | Co-N double-doped flaky porous two-dimensional carbon material and preparation method thereof |
| CN105923629A (en) * | 2016-04-26 | 2016-09-07 | 哈尔滨工程大学 | Method for preparing transition metal composite hetero atom doped porous carbon material through dipping, recrystallizing and carbonizing biomasses |
| CN106920941A (en) * | 2017-03-31 | 2017-07-04 | 合肥国轩高科动力能源有限公司 | A kind of cobalt, titanium, nitrogen co-doped CNT/sulphur composite positive pole and preparation method thereof |
| CN107317011A (en) * | 2017-06-28 | 2017-11-03 | 合肥工业大学 | A kind of preparation method of the ordered porous carbon coating silicon nano composite material of N doping |
| CN107394218A (en) * | 2017-07-29 | 2017-11-24 | 湖南科技大学 | A kind of cobalt doped double-layer carbon nitrogen complex nano material, preparation method and applications |
| CN108075121A (en) * | 2017-12-12 | 2018-05-25 | 东华大学 | Sulphur/N doping porous carbon nano-composite fiber and its preparation and application |
| CN108172801A (en) * | 2017-12-28 | 2018-06-15 | 哈尔滨工业大学深圳研究生院 | A kind of method of porous carbon materials doping vario-property and application |
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| CN110060885A (en) * | 2019-04-23 | 2019-07-26 | 华南理工大学 | A kind of flexible fabric electrode and the preparation method and application thereof |
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