CN104064377B - Method for preparing manganese titanate/graphene composite material used for capacitors - Google Patents
Method for preparing manganese titanate/graphene composite material used for capacitors Download PDFInfo
- Publication number
- CN104064377B CN104064377B CN201410331140.7A CN201410331140A CN104064377B CN 104064377 B CN104064377 B CN 104064377B CN 201410331140 A CN201410331140 A CN 201410331140A CN 104064377 B CN104064377 B CN 104064377B
- Authority
- CN
- China
- Prior art keywords
- titanate
- manganese
- composite material
- graphene composite
- stock solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for preparing a manganese-titanate-loaded graphene composite material. A graphite oxide stock solution containing manganese dioxide is mixed with n-butyl titanate or titanium tetrachloride, the mixture undergoes a hydrolysis reaction after the temperature of the mixture is raised to the range from 80 DEG C to 200 DEG C, and then the manganese titanate/graphene composite material is obtained after water washing, filtration, purification and drying; or the mixture is dried after undergoing the hydrolysis reaction for 5 hours to 7 hours and then sintered at the high temperature ranging from 500 DEG C to 800 DEG C for 2 hours to 5 hours, and the manganese titanate/graphene composite material is obtained after water washing, filtration, purification and drying. In the mixed solution of the graphite oxide stock solution containing manganese dioxide and the n-butyl titanate or the titanium tetrachloride, the molar ratio of manganese to titanium is 1:(2-0.5). The manganese titanate/graphene composite material is directly prepared with a hydrothermal method, while the excellent performance of the composite material as the electrode material of the capacitors is guaranteed, the preparation method is easy to achieve, the manganese dioxide in the graphite oxide stock solution is fully utilized, and large-scale production is facilitated.
Description
Technical field
The invention belongs to field of capacitor material technology is and in particular to a kind of system of graphene-supported manganese titanate composite
Preparation Method.
Background technology
Graphene causes the concern of vast researcher with its excellent electrical and mechanical performance in worldwide.By
In its good electric conductivity and big specific surface area it is contemplated that it will have before wide application as electrode material for super capacitor
Scape.But because the Van der Waals force that causes of Graphene π pi accumulation, so that Graphene is reunited in the solution, reduces graphite
The chemical property of alkene.Through the Graphene of functionalization, the functional group that marginal surface contains can effectively stop Graphene molten
Reunion in liquid.Graphene oxide is a kind of important functionalised forms of Graphene, is equally the presoma preparing Graphene, table
The oxygen-containing functional group being rich on face and edge, not only can increase the repulsion resistance of graphene film interlayer because of the electronegativity of functional group
Only reunite, the absorption that can also serve as avtive spot for metal or metal-oxide provides anchor point thus bearing to prepare Graphene
Carry the composite of metal or metal-oxide.
Manganese titanate is a kind of conductor oxidate, has high dielectric constant, has very in terms of super capacitor material
Big use value, but its electric conductivity is poor, and the active substance as ultracapacitor requires good conductivity, the internal resistance of electrode
As far as possible little, to ensure that it can carry out high current charge-discharge.Therefore when by the use of manganese titanate as capacitor active substance, for understanding
Certainly the defect of manganese titanate it is necessary to be combined it with other materials.It is combined with material with carbon element, nanostructured can be prepared
Manganese titanate, to increase its specific surface area, improve its utilization rate, thus reaching the purpose improving manganese titanate than electric capacity.To simultaneously
Manganese titanate and material with carbon element conductive material are combined, and have both improved the electrical conductivity of manganese titanate, overcome that manganese titanate is closelypacked to ask again
Topic, the skeleton confinement effect of conducting base simultaneously also can improve its cycle performance.Material with carbon element is with cheap price, excellent conduction
Performance and physical and chemical stability are famous, and manganese titanate and material with carbon element recombination energy significantly improve the hardness of material, conductivity, electrochemistry
The performances such as capacity, are useful as the materials such as conductive and heat-conductive, catalyst carrier, sensor, are widely used as lithium ion battery, solar-electricity
The new energy devices such as pond, ultracapacitor.
At present, prepare the capacitance material of related Graphene how based on graphene-supported polymer, but polymer is not
Stability influences whether the efficiency of actual of capacitance material.
Content of the invention
It is an object of the invention to provide a kind of preparation method of capacitor manganese titanate/graphene composite material.This is multiple
Condensation material can be used in capacitor material aspect because having high capacitive property.
A kind of preparation method of capacitor manganese titanate/graphene composite material, comprises the following steps:
Mixed with tetrabutyl titanate or titanium tetrachloride using the graphite oxide stock solution containing manganese dioxide, be warming up to 80-200
DEG C hydro-thermal reaction, washing, filtration, remove impurity, is dried to obtain manganese titanate/graphene composite material.
By such scheme, the hydro-thermal reaction time is 20-28h.
The preparation method of above-mentioned manganese titanate/graphene composite material, further comprising the steps of:
After hydro-thermal reaction 5-7h be dried, then in 500-800 DEG C of high temperature sintering 2-5h, then wash, filter, remove impurity, drying
Obtain manganese titanate/graphene composite material.
By such scheme, described high-temperature sintering process is carried out under protective gas atmosphere.
By such scheme, the described graphite oxide stock solution containing manganese dioxide and tetrabutyl titanate or titanium tetrachloride mixed liquor
In, manganese element is 1 with the mol ratio of titanium elements:(2-0.5).
The beneficial effects of the present invention is:
Hydro-thermal method of the present invention directly prepares manganese titanate/graphene composite material, is ensureing as electrode for capacitors material
While material excellent properties, preparation method is simple, makes full use of the manganese dioxide in graphite oxide stock solution, is easy to give birth on a large scale
Produce.
The present invention is using the manganese dioxide retaining in the graphite oxide stock solution containing manganese dioxide as the manganese preparing manganese titanate
Source, adds tetrabutyl titanate or titanium tetrachloride to be titanium source in the graphite oxide stock solution containing manganese dioxide, is prepared under high temperature
To manganese titanate/graphene composite material that capacitive property is excellent.
The present invention extensively can should be used as the new energy devices such as lithium ion battery, solaode, ultracapacitor, especially suitable
As materials such as conductive and heat-conductive, catalyst carrier, sensors, have a extensive future.
Specific embodiment
Following examples explain technical scheme further, but not as limiting the scope of the invention.
The preparation process of capacitor of the present invention manganese titanate/graphene composite material is as follows:
Mixed with tetrabutyl titanate or titanium tetrachloride using the graphite oxide stock solution containing manganese dioxide, be warming up to 80-200
DEG C stirring hydro-thermal reaction, washing, filtration, remove impurity, is dried to obtain manganese titanate/graphene composite material.
The hydro-thermal reaction time can obtain the higher manganese titanate/graphene composite material of yield for 20-28h.Wherein, hydro-thermal
Add sodium borohydride in reaction, have more preferable effect.Tetrabutyl titanate and titanium tetrachloride are 5 with the mass ratio of sodium borohydride:
1-15.
Or it is anti-with tetrabutyl titanate or titanium tetrachloride mix and blend hydro-thermal in the graphite oxide stock solution containing manganese dioxide
Answer and be dried after 5-7h, then after in 500-800 DEG C of high temperature sintering 2-5h, washing, filtration, remove impurity, be dried to obtain manganese titanate/graphite
Alkene composite.Sintering process on the basis of hydro-thermal method can more quickly and effectively rate prepared manganese titanate/graphene composite material.
The present invention contains graphite oxide stock solution and the manganese element in tetrabutyl titanate or titanium tetrachloride mixed liquor of manganese dioxide
Mol ratio with titanium elements is 1:(2-0.5).
Wherein, the graphite oxide stock solution preparation process containing manganese dioxide is as follows:
In mass ratio 1:1, by graphite powder and sodium nitrate mixing, adds 98% concentrated sulphuric acid to stir 30min under ice bath;So
Add the potassium permanganate accounting for graphite powder quality 10-15 times afterwards, stir 60min;It is transferred in 40 DEG C of environment and continue stirring 30min,
It is subsequently adding deionized water;Temperature is increased to 98 DEG C and stirs 5~15min;Be cooled to room temperature to add mass fraction is 30%
H2O2, to not producing bubble, after stirring, obtain the graphite oxide stock solution containing manganese dioxide.
Embodiment 1:
A. graphite powder (2g) and sodium nitrate (2g) are added in beaker and are mixed, the concentrated sulphuric acid of addition 98% is in ice bath
Lower stirring 30 minutes, is then slowly added to potassium permanganate (20g) in beaker, stirs 60 minutes, this process equally keeps frozen water
In bath.Transfer beaker continues stirring 30 minutes to 40 DEG C of water-baths, is then slowly added into 200ml deionized water, by the temperature of water-bath
Degree is increased to 98 DEG C and stirs 5 minutes, takes out beaker and add the H that 50ml mass fraction is 30% from water-bath2O2, to not producing
Till angry bubble, after stirring, obtain the graphite oxide stock solution containing manganese dioxide;
B. the mixing stock solution of step a gained is placed in rustless steel politef autoclave, is subsequently adding metatitanic acid
N-butyl or titanium tetrachloride, add sodium borohydride as graphene oxide reducing agent, and reaction temperature remains 80 DEG C, reaction
Time is 24 hours, then takes out and naturally cools to room temperature.The amount ratio of described reactant is tetrabutyl titanate (or four chlorinations
Titanium):Sodium borohydride=1g:1g;
C. the product of b step gained is gone the removal of impurity through washing filtering, it is multiple that finally vacuum drying obtains manganese titanate/Graphene
Condensation material.
Using constant current charge-discharge measuring, when electric current density is for 0.50A/g, this composite, it is up to than electric capacity
220F/g.
Embodiment 2:
A. graphite powder (2g) and sodium nitrate (2g) are added in beaker and are mixed, the concentrated sulphuric acid of addition 98% is in ice bath
Lower stirring 30 minutes, is then slowly added to potassium permanganate (25g) in beaker, stirs 60 minutes, this process equally keeps frozen water
In bath.Transfer beaker continues stirring 30 minutes to 40 DEG C of water-baths, is then slowly added into 250ml deionized water, by the temperature of water-bath
Degree is increased to 98 DEG C and stirs 10 minutes, takes out beaker and add the H that 75ml mass fraction is 30% from water-bath2O2, to not producing
Till angry bubble, after stirring, obtain the graphite oxide stock solution containing manganese dioxide;
B. the mixing stock solution of step a gained is placed in rustless steel politef autoclave, is subsequently adding metatitanic acid
N-butyl or titanium tetrachloride, add sodium borohydride as graphene oxide reducing agent, reaction temperature remains 140 DEG C, instead
It is 24 hours between seasonable, then take out and naturally cool to room temperature.The amount ratio of described reactant is tetrabutyl titanate (or four chlorinations
Titanium):Sodium borohydride=3g:2g;
C. the product of b step gained is gone the removal of impurity through washing filtering, it is multiple that finally vacuum drying obtains manganese titanate/Graphene
Condensation material.
Using constant current charge-discharge measuring, when electric current density is for 0.50A/g, this composite, it is up to than electric capacity
233F/g.
Embodiment 3:
A. graphite powder (2g) and sodium nitrate (2g) are added in beaker and are mixed, the concentrated sulphuric acid of addition 98% is in ice bath
Lower stirring 30 minutes, is then slowly added to potassium permanganate (30g) in beaker, stirs 60 minutes, this process equally keeps frozen water
In bath.Transfer beaker continues stirring 30 minutes to 40 DEG C of water-baths, is then slowly added into 300ml deionized water, by the temperature of water-bath
Degree is increased to 98 DEG C and stirs 15 minutes, takes out beaker and add the H that 100ml mass fraction is 30% from water-bath2O2, to not
Till producing bubble, after stirring, obtain the graphite oxide stock solution containing manganese dioxide;
B. the mixing stock solution of step a gained is placed in rustless steel politef autoclave, is subsequently adding metatitanic acid
N-butyl or titanium tetrachloride, add sodium borohydride as graphene oxide reducing agent, reaction temperature remains 200 DEG C, instead
It is 24 hours between seasonable, then take out and naturally cool to room temperature.The amount ratio of described reactant is tetrabutyl titanate (or four chlorinations
Titanium):Sodium borohydride=5g:3g;
C. the product of b step gained is gone the removal of impurity through washing filtering, it is multiple that finally vacuum drying obtains manganese titanate/Graphene
Condensation material.
Using constant current charge-discharge measuring, when electric current density is for 0.50A/g, this composite, it is up to than electric capacity
215F/g.
Embodiment 4:
A. graphite powder (2g) and sodium nitrate (2g) are added in beaker and are mixed, the concentrated sulphuric acid of addition 98% is in ice bath
Lower stirring 30 minutes, is then slowly added to potassium permanganate (20g) in beaker, stirs 60 minutes, this process equally keeps frozen water
In bath.Transfer beaker continues stirring 30 minutes to 40 DEG C of water-baths, is then slowly added into 200ml deionized water, by the temperature of water-bath
Degree is increased to 98 DEG C and stirs 5 minutes, takes out beaker and add the H that 50ml mass fraction is 30% from water-bath2O2, to not producing
Till angry bubble, after stirring, obtain the graphite oxide stock solution containing manganese dioxide;
B. tetrabutyl titanate or titanium tetrachloride (1g) will be added in the stock solution of step a gained, under room temperature, stir 6h, vacuum
It is placed in after drying in tube furnace, under nitrogen or other protective gas atmosphere are protected, reaction temperature is 500 DEG C, during reaction
Between be 5h, then take out and naturally cool to room temperature;
C. the product of b step gained is gone the removal of impurity through washing filtering, it is multiple that finally vacuum drying obtains manganese titanate/Graphene
Condensation material.
Using constant current charge-discharge measuring, when electric current density is for 0.50A/g, this composite, it is up to than electric capacity
242F/g.
Embodiment 5:
A. graphite powder (2g) and sodium nitrate (2g) are added in beaker and are mixed, the concentrated sulphuric acid of addition 98% is in ice bath
Lower stirring 30 minutes, is then slowly added to potassium permanganate (25g) in beaker, stirs 60 minutes, this process equally keeps frozen water
In bath.Transfer beaker continues stirring 30 minutes to 40 DEG C of water-baths, is then slowly added into 250ml deionized water, by the temperature of water-bath
Degree is increased to 98 DEG C and stirs 10 minutes, takes out beaker and add the H that 75ml mass fraction is 30% from water-bath2O2, to not producing
Till angry bubble, after stirring, obtain the graphite oxide stock solution containing manganese dioxide;
B. tetrabutyl titanate or titanium tetrachloride (3g) will be added in the stock solution of step a gained, under room temperature, stir 6h, vacuum
It is placed in after drying in tube furnace, under nitrogen or other protective gas atmosphere are protected, reaction temperature is 600 DEG C, during reaction
Between be 4h, then take out and naturally cool to room temperature;
C. the product of b step gained is gone the removal of impurity through washing filtering, it is multiple that finally vacuum drying obtains manganese titanate/Graphene
Condensation material.
Using constant current charge-discharge measuring, when electric current density is for 0.50A/g, this composite, it is up to than electric capacity
223F/g.
Embodiment 6:
A. graphite powder (2g) and sodium nitrate (2g) are added in beaker and are mixed, the concentrated sulphuric acid of addition 98% is in ice bath
Lower stirring 30 minutes, is then slowly added to potassium permanganate (30g) in beaker, stirs 60 minutes, this process equally keeps frozen water
In bath.Transfer beaker continues stirring 30 minutes to 40 DEG C of water-baths, is then slowly added into 300ml deionized water, by the temperature of water-bath
Degree is increased to 98 DEG C and stirs 15 minutes, takes out beaker and add the H that 100ml mass fraction is 30% from water-bath2O2, to not
Till producing bubble, after stirring, obtain the graphite oxide stock solution containing manganese dioxide;
B. tetrabutyl titanate or titanium tetrachloride (5g) will be added in the stock solution of step a gained, under room temperature, stir 6h, vacuum
It is placed in after drying in tube furnace, under nitrogen or other protective gas atmosphere are protected, reaction temperature is 700 DEG C, during reaction
Between be 3h, then take out and naturally cool to room temperature;
C. the product of b step gained is gone the removal of impurity through washing filtering, it is multiple that finally vacuum drying obtains manganese titanate/Graphene
Condensation material.
Using constant current charge-discharge measuring, when electric current density is for 0.50A/g, this composite, it is up to than electric capacity
241F/g.
Embodiment 7:
A. graphite powder (2g) and sodium nitrate (2g) are added in beaker and are mixed, the concentrated sulphuric acid of addition 98% is in ice bath
Lower stirring 30 minutes, is then slowly added to potassium permanganate (35g) in beaker, stirs 60 minutes, this process equally keeps frozen water
In bath.Transfer beaker continues stirring 30 minutes to 40 DEG C of water-baths, is then slowly added into 350ml deionized water, by the temperature of water-bath
Degree is increased to 98 DEG C and stirs 20 minutes, takes out beaker and add the H that 125ml mass fraction is 30% from water-bath2O2, to not
Till producing bubble, after stirring, obtain the graphite oxide stock solution containing manganese dioxide;
B. tetrabutyl titanate or titanium tetrachloride (7g) will be added in the stock solution of step a gained, under room temperature, stir 6h, vacuum
It is placed in after drying in tube furnace, under nitrogen or other protective gas atmosphere are protected, reaction temperature is 800 DEG C, during reaction
Between be 2h, then take out and naturally cool to room temperature;
C. the product of b step gained is gone the removal of impurity through washing filtering, it is multiple that finally vacuum drying obtains manganese titanate/Graphene
Condensation material.
Using constant current charge-discharge measuring, when electric current density is for 0.50A/g, this composite, it is up to than electric capacity
232F/g.
Claims (5)
1. a kind of preparation method of capacitor manganese titanate/graphene composite material is it is characterised in that comprise the following steps:
Mixed with tetrabutyl titanate or titanium tetrachloride using the graphite oxide stock solution containing manganese dioxide, be warming up to 80-200 DEG C of water
Thermal response, washing, filtration, remove impurity, is dried to obtain manganese titanate/graphene composite material;
The described graphite oxide stock solution preparation process containing manganese dioxide is as follows:
In mass ratio 1:1, by graphite powder and sodium nitrate mixing, adds 98% concentrated sulphuric acid to stir 30min under ice bath;Then plus
Enter to account for the potassium permanganate of graphite powder quality 10-15 times, stir 60min;It is transferred in 40 DEG C of environment and continues stirring 30min, then
Add deionized water;Temperature is increased to 98 DEG C and stirs 5~15min;Be cooled to room temperature to add mass fraction is 30%
H2O2, to not producing bubble, after stirring, obtain the graphite oxide stock solution containing manganese dioxide.
2. the preparation method of capacitor as claimed in claim 1 manganese titanate/graphene composite material is it is characterised in that hydro-thermal is anti-
It is 20-28h between seasonable.
3. the preparation method of capacitor manganese titanate/graphene composite material as claimed in claim 1 is it is characterised in that also include
Following steps:
It is dried after hydro-thermal reaction 5-7h, then in 500-800 DEG C of high temperature sintering 2-5h, then wash, filter, remove impurity, being dried to obtain
Manganese titanate/graphene composite material.
4. the preparation method of capacitor as claimed in claim 3 manganese titanate/graphene composite material is it is characterised in that described height
Warm sintering process is carried out under protective gas atmosphere.
5. the preparation method of capacitor manganese titanate/graphene composite material as claimed in claim 1 is it is characterised in that described contain
Have in the graphite oxide stock solution and tetrabutyl titanate or titanium tetrachloride mixed liquor of manganese dioxide, the mol ratio of manganese element and titanium elements
For 1:(2-0.5).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410331140.7A CN104064377B (en) | 2014-07-11 | 2014-07-11 | Method for preparing manganese titanate/graphene composite material used for capacitors |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410331140.7A CN104064377B (en) | 2014-07-11 | 2014-07-11 | Method for preparing manganese titanate/graphene composite material used for capacitors |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104064377A CN104064377A (en) | 2014-09-24 |
CN104064377B true CN104064377B (en) | 2017-02-15 |
Family
ID=51552044
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201410331140.7A Expired - Fee Related CN104064377B (en) | 2014-07-11 | 2014-07-11 | Method for preparing manganese titanate/graphene composite material used for capacitors |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN104064377B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109529771A (en) * | 2019-01-11 | 2019-03-29 | 北方工业大学 | In-situ self-regeneration adsorbent and preparation method thereof |
CN110589890B (en) * | 2019-10-17 | 2022-09-16 | 安徽工业大学 | Method for simultaneously preparing spinel type and perovskite type manganese titanate nanoparticles and application |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101937985A (en) * | 2010-08-19 | 2011-01-05 | 北京科技大学 | Graphene/titanium dioxide lithium ion battery cathode material and preparation method |
CN103035417A (en) * | 2012-12-17 | 2013-04-10 | 辽宁师范大学 | Lowcost preparation method of MnO2 / graphene composite electrode materials used for supercapacitor |
-
2014
- 2014-07-11 CN CN201410331140.7A patent/CN104064377B/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101937985A (en) * | 2010-08-19 | 2011-01-05 | 北京科技大学 | Graphene/titanium dioxide lithium ion battery cathode material and preparation method |
CN103035417A (en) * | 2012-12-17 | 2013-04-10 | 辽宁师范大学 | Lowcost preparation method of MnO2 / graphene composite electrode materials used for supercapacitor |
Non-Patent Citations (3)
Title |
---|
"Sodium Titanate Nanotubes as Negative Electrode Materials for Sodium-ion Capacitors";Jiao yin等;《ACS Appl. Mater. Interfaces》;20120413;第4卷;第2762-2768页 * |
"Synthesis and structural properties of manganese titanate MnTi03 nanoparticle";Guo Wei Zhou等;《Materials Science and Engineering C》;20040105;第24卷;第71-74页 * |
"Synthesis of manganese titanate MnTi03 powders by a sol-gel-hydrothermal method";Zhi-Qiang Song等;《Materials Science and Engineering B》;20041025;第113卷;第121-124页 * |
Also Published As
Publication number | Publication date |
---|---|
CN104064377A (en) | 2014-09-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107308977B (en) | Difunctional VPO catalysts of cobalt nitrogen sulphur codope carbon aerogels and its preparation method and application | |
CN103420352A (en) | High-fluoride-content graphite fluoride and preparation method thereof | |
Yang et al. | Cobalt–carbon derived from zeolitic imidazolate framework on Ni foam as high-performance supercapacitor electrode material | |
CN103078087B (en) | A kind of preparation method of lithium titanate/carbon nano tube composite cathode material | |
CN103318871A (en) | Preparation method for synthesizing graphite porous carbon material with activated carbon serving as raw material | |
CN104715936B (en) | A kind of classifying porous carbon electrode material and preparation method for ultracapacitor | |
CN102867654A (en) | Graphitized activated carbon electrode material for supercapacitor and preparation method thereof | |
CN105174260B (en) | A kind of low alkali process for preparing activated of asphalt based active carbon and application | |
CN108455596B (en) | Method for preparing nitrogen-rich hierarchical pore carbon material with high specific surface area by one-step carbonization method and application thereof | |
CN107032318B (en) | A kind of nitrogenous carbon material of sheet and preparation method thereof | |
CN105321726B (en) | High magnification active carbon/Activated Graphite alkene combination electrode material and preparation method thereof | |
CN107244664A (en) | The preparation method and application of class graphene-structured carbon electrode material | |
CN104528712B (en) | A kind of preparation method of graphene/metal oxide three-dimensional composite material | |
CN105198007A (en) | Preparation and stripping methods of mesoporous cobaltosic oxide nanosheet | |
CN107611412A (en) | A kind of tin ash/porous carbon composite lithium ion battery negative material and preparation method | |
CN105271231A (en) | Preparation method for two-dimensional nano Ti3C2 sheet | |
CN106058182B (en) | A kind of preparation method of the good lithium titanate/polyaniline composite material of high rate performance | |
CN112017868B (en) | Mesoporous hollow carbon micron cage material and preparation method and application thereof | |
CN111710529B (en) | Co/Mn-MOF/nitrogen-doped carbon-based composite material and preparation method and application thereof | |
CN108793147A (en) | A kind of novel graphite alkene material and preparation method thereof | |
CN104064377B (en) | Method for preparing manganese titanate/graphene composite material used for capacitors | |
CN111977651A (en) | Preparation method of potassium carbonate chemically activated low-order carbon source based porous carbon | |
Luo et al. | Construction of hierarchically porous biomass carbon using iodine as pore-making agent for energy storage | |
CN103523771A (en) | Graphene, activation method of graphene and supercapcitor using graphene | |
CN103545115A (en) | Graphene-carbon nano tube composite material, preparation method thereof and super capacitor |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170215 Termination date: 20200711 |