CN104925785A - Preparation methods of porous graphene and supercapacitor with porous graphene - Google Patents
Preparation methods of porous graphene and supercapacitor with porous graphene Download PDFInfo
- Publication number
- CN104925785A CN104925785A CN201510110365.4A CN201510110365A CN104925785A CN 104925785 A CN104925785 A CN 104925785A CN 201510110365 A CN201510110365 A CN 201510110365A CN 104925785 A CN104925785 A CN 104925785A
- Authority
- CN
- China
- Prior art keywords
- porous graphene
- graphene
- inorganic salt
- ultracapacitor
- porous
- 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.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to the technical field of supercapacitor, and discloses preparation methods of porous graphene and a supercapacitor with the porous graphene. The porous graphene is prepared through the following steps: a graphene oxide water solution and inorganic salt are mixed and stirred for 0.5h according to a mass ratio that graphene oxide to inorganic salt is 1:1-10; the mixture is placed in a tubular furnace, and is heated to 200-300 DEG C with a heating speed of 1-10 DEG C/min under nitrogen gas protection; the temperature is maintained for 1-3h and the obtained material is naturally cooled to room temperature; the material is placed in a water solution and is boiled and stirred for 1h; and filtering is carried out, such that porous graphene with a high specific surface area is obtained. The filtrate can be recrystallized, and the original inorganic salt can be obtained and can be reused. The method provided by the invention has the advantages of simple preparation process, and low environment pollution. With the method, industrialized productions can be easily realized. The produced porous graphene has a high specific surface area and a developed mesoporous structure. The porous graphene can perform relatively high specific capacitance.
Description
Technical field
The present invention relates to supercapacitor technologies field, be specifically related to a kind of porous graphene and adopt its preparation method of ultracapacitor.
Background technology
Ultracapacitor is as a kind of novel energy-storing device having both battery and capacitor technology advantage, there is high power density, (cycle life is up to more than 1,000,000 times for long service life, expection reaches life-span of 30 years), use temperature wide ranges (-40 ~ 70 DEG C), charge velocities fast (completing in tens seconds), storage period long, high-efficiency energy-storage and the advantage such as energy-conservation, safety and environmental protection, therefore it has been widely used in the fields such as wind-power electricity generation, electromobile, military project and harbour machinery.
Superelevation electric conductivity (the theoretical value 2500 S m of Graphene
-1) and superhigh specific surface area (theoretical value 2630 m
2g
-1) effectively can reduce the internal resistance of ultracapacitor and improve the object of specific energy, therefore Graphene is the focus of electrode material for super capacitor research.But the π between graphene sheet layer-pi-conjugated effect, is easy to the reunion causing Graphene, causes Graphene to become compact structure, and specific surface area is less than 300 m
2g
-1, affect its absorption to electrolyte ion in ultracapacitor, reduce the specific energy of ultracapacitor.Therefore the pore-creating of Graphene and the preparation of porous graphene are that it plays the key of good characteristic in supercapacitor applications.At present, the porous graphene of most of high-specific surface area is by physics or chemical activation method, water heat transfer, but these methods all need High Temperature High Pressure, and whole process is complicated, causes the price of product higher.
There is the relatively low problem of ratio capacitance in current ultracapacitor, and adopts Graphene can improve its ratio capacitance.But there is above-mentioned problem in porous graphene.
Summary of the invention
The object of the invention is to solve the problem, a kind of porous graphene being provided and adopting its preparation method of ultracapacitor.The method preparation process is simple, environmental pollution is little, and be easy to realize suitability for industrialized production, the porous graphene produced has flourishing mesopore pore texture (mesopore duct is 2-50 nm) of high-ratio surface sum, and porous graphene can show higher ratio capacitance simultaneously.
In order to reach foregoing invention object, the present invention by the following technical solutions:
A kind of porous graphene; described porous graphene is prepared from by following steps: the proportioning mix and blend 0.5h being 1:1-10 with graphene oxide and inorganic salt mass ratio by graphene oxide water solution and inorganic salt; after mixed solution is placed in tube furnace; 200-300 DEG C is risen to the heat-up rate of 1-10 DEG C/min under nitrogen protection atmosphere; insulation 1-3h; Temperature fall is to room temperature; after be placed in again the aqueous solution boil stir 1h; the porous graphene of high-specific surface area is obtained after filtration; filtrate crystallization can obtain original inorganic salt again, and reusable.
Preferably, described graphene oxide water solution is the aqueous solution containing 5-7wt. % graphene oxide.
Preferably, described inorganic salt are: NaCl, KCl, Na
2cO
3or K
2cO
3.
Adopt a preparation method for the ultracapacitor of porous graphene, specifically comprise the following steps:
(1) porous graphene, graphitized carbon black, binding agent being mixed according to the proportioning that mass ratio is 8:1:1 and be adjusted to pulpous state, is slurry;
(2) coating machine is then utilized to be coated on aluminium foil by slurry shaping, preparing thickness is 240 μm of carbon electrodes, then adopt rolling machine with the speed of the pressure of 40 tons and 10 m/min by carbon electrode compacting, the carbon electrode of compacting is washed into the carbon electrode sheet of 75 × 55 mm by rear stamping machine;
(3) the carbon electrode sheet that step (2) obtains is placed in 170 DEG C of vacuum drying oven inner drying 12h, obtains electrode slice finished product;
(4) the electrode slice finished product two steps (3) that quality is equal, thickness is equal obtained respectively, as positive and negative electrode, take cellulose paper as barrier film, with organic system solution for electrolytic solution, in the glove box being full of high-purity argon gas, is assembled into ultracapacitor.
Preferably, the binding agent of described step (1) is massfraction is the PTFE emulsion of 10% or the SBR emulsion of 30%.
Compared with prior art, beneficial effect is in the present invention:
1) in the preparation process of porous graphene, inorganic salt are reusable, pollution-free;
2) porous graphene preparation technology is simple, controlled and be easy to realize suitability for industrialized production;
3) ultracapacitor of porous graphene assembling has high ratio capacitance.
Accompanying drawing explanation
The transmission microscopy figure of the porous graphene of Fig. 1 obtained by embodiment 1;
The high power transmission microscopy figure of the porous graphene of Fig. 2 obtained by embodiment 1;
The N of the porous graphene of Fig. 3 obtained by embodiment 1
2adsorption desorption curve;
The graph of pore diameter distribution of the porous graphene of Fig. 4 obtained by embodiment 1;
The high rate performance of the ultracapacitor of Fig. 5 obtained by embodiment 1 and cycle performance figure.
Embodiment
Below by specific embodiment, explanation is further described to technical scheme of the present invention.
If without specified otherwise, the raw material adopted in embodiments of the invention is the conventional raw material in this area, and the method adopted in embodiment, is the ordinary method of this area.
Embodiment 1:
By the proportioning mix and blend 0.5h that the aqueous solution containing 6wt.% graphene oxide and NaCl are 1:4 with graphene oxide and NaCl mass ratio; after mixed solution is placed in tube furnace; 200 DEG C are risen to the heat-up rate of 2 DEG C/min under nitrogen protection atmosphere; insulation 1h; Temperature fall is to room temperature; after be placed in again the aqueous solution boil stir 1h, after filtration, filter residue is porous graphene.The transmission electron microscope picture of porous graphene as illustrated in fig. 1 and 2.The N of porous graphene
2it is 1743 m that adsorption desorption curve and graph of pore diameter distribution (see Fig. 3 and Fig. 4) show its specific surface area
2/ g, and show that porous graphene has flourishing mesopore pore texture (mesopore duct is 2-50 nm), namely have micropore-mesopore-macroporous structure.
Then by the porous graphene of above-mentioned steps gained and graphitized carbon black, 10% PTFE emulsion to mix according to the proportioning that mass ratio is 8:1:1 and be adjusted to pulpous state.Then coating machine is utilized, slurry is coated on aluminium foil shaping by adjustment scraper height, preparing thickness is 240 μm of carbon electrodes, and rear employing rolling machine is with the speed of the pressure of 40 tons and 15 m/min by carbon electrode compacting, and the carbon electrode of compacting is washed into the carbon electrode sheet of 75 × 55 mm by rear stamping machine.Step carbon electrode sheet is placed in 170 DEG C of vacuum drying oven inner drying 12h.Respectively using equal for equal for two dried quality, thickness electrode slice as positive and negative electrode, take cellulose paper as barrier film, with 1 M TEABF
4acetonitrile solution be electrolytic solution, in the glove box being full of high-purity argon gas, be assembled into ultracapacitor.This ultracapacitor is under current density is 0.05 A/g, and ratio capacitance is 136 F/g; Current density is under 20 A/g, and ratio capacitance is that 86 F/g(are shown in Fig. 5).Ultracapacitor is under current density is 20 A/g, and after circulation 10000, capability retention is shown in Fig. 5 up to 99.3%().
Embodiment 2:
The present embodiment process is identical with embodiment 1, difference is: the solute solubility of the graphene oxide water solution in step 1 is changed by 6wt.% into 7wt.%, graphene oxide and NaCl mass ratio change 1:10 into by 1:4, temperature rise rate changes 8 DEG C/min into by 2 DEG C/min, be warming up to 200 DEG C changes 270 DEG C into, and the specific surface area finally obtaining porous graphene is 1678 m
2/ g, and porous graphene has flourishing mesopore pore texture (mesopore duct is 2-50 nm); The PTFE emulsion of 10% in step 1 is changed into the SBR emulsion of 30%, 1 M TEABF
4acetonitrile solution change 1 M SBPBF into
4acetonitrile solution, the ultracapacitor of gained is under current density is 0.05 A/g, and ratio capacitance is 139 F/g; Current density is under 20 A/g, and ratio capacitance is 88F/g.Under current density is 20 A/g, after circulation 10000, the capability retention of ultracapacitor is up to 99.1%.
Embodiment 3:
By the aqueous solution containing 4.5wt.% graphene oxide and Na
2cO
3with graphene oxide and Na
2cO
3mass ratio is the proportioning mix and blend 0.5h of 1:1; after mixed solution is placed in tube furnace; 230 DEG C are risen to the heat-up rate of 5 DEG C/min under nitrogen protection atmosphere; insulation 2h; Temperature fall to room temperature, after be placed in again the aqueous solution boil stir 1h, after filtration; filter residue is porous graphene, and result shows that its specific surface area is 1702 m
2/ g, and porous graphene has flourishing mesopore pore texture (mesopore duct is 2-50 nm).
Then by the porous graphene of above-mentioned steps gained and graphitized carbon black, 10% PTFE emulsion to mix according to the proportioning that mass ratio is 8:1:1 and be adjusted to pulpous state.Then coating machine is utilized, slurry is coated on aluminium foil shaping by adjustment scraper height, preparing thickness is 240 μm of carbon electrodes, and rear employing rolling machine is with the speed of the pressure of 40 tons and 15 m/min by carbon electrode compacting, and the carbon electrode of compacting is washed into the carbon electrode sheet of 75 × 55 mm by rear stamping machine.Step carbon electrode sheet is placed in 170 DEG C of vacuum drying oven inner drying 12h.Respectively using equal for equal for two dried quality, thickness electrode slice as positive and negative electrode, take cellulose paper as barrier film, with the acetonitrile solution of 1 M SBPBF4 for electrolytic solution, in the glove box being full of high-purity argon gas, be assembled into ultracapacitor.This ultracapacitor is under current density is 0.05 A/g, and ratio capacitance is 132 F/g; Current density is under 20 A/g, and ratio capacitance is 81 F/g.Ultracapacitor is under current density is 20 A/g, and after circulation 10000, capability retention is up to 99.7%.
Embodiment 4:
The present embodiment process is identical with embodiment 3, and difference is: change the solute solubility of the graphene oxide water solution in step 1 into 5wt.%, inorganic salt NaCO by 4.5wt.%
3change that KCl, graphene oxide and KCl mass ratio change 1:6 into by 1:1, temperature rise rate changes 7 DEG C/min into by 2 DEG C/min, be warming up to 200 DEG C changes 257 DEG C into into, the specific surface area finally obtaining porous graphene is 1600m
2/ g, and porous graphene has flourishing mesopore pore texture (mesopore duct is 2-50 nm); The PTFE emulsion of 10% in step 1 is changed into the SBR emulsion of 30%, the ultracapacitor of gained is under current density is 0.05 A/g, and ratio capacitance is 128 F/g; Current density is under 20 A/g, and ratio capacitance is 80 F/g.Under current density is 20 A/g, after circulation 10000, the capability retention of ultracapacitor is up to 99.0%.
Embodiment 5:
The present embodiment process is identical with embodiment 4, and difference is: change the solute solubility of the graphene oxide water solution in step 1 into 5.5wt.% by 5wt.%, inorganic salt KCl changes K into
2cO
3, graphene oxide and K
2cO
3mass ratio changes 1:7 into by 1:6, temperature rise rate changes 4 DEG C/min into by 2 DEG C/min, be warming up to 200 DEG C changes 240 DEG C into, and the specific surface area finally obtaining porous graphene is 1693 m
2/ g, and porous graphene has flourishing mesopore pore texture (mesopore duct is 2-50 nm); The ultracapacitor of gained is under current density is 0.05 A/g, and ratio capacitance is 135 F/g; Current density is under 20 A/g, and ratio capacitance is 87 F/g.Under current density is 20 A/g, after circulation 10000, the capability retention of ultracapacitor is up to 99.5%.
Embodiment 6:
The present embodiment process is identical with embodiment 5, and difference is: change the solute solubility of the graphene oxide water solution in step 1 into 6wt.%, graphene oxide and K by 5.5wt.%
2cO
3mass ratio changes 1:3 into by 1:7, temperature rise rate changes 6 DEG C/min into by 2 DEG C/min, be warming up to 200 DEG C changes 230 DEG C into, and the specific surface area finally obtaining porous graphene is 1720 m
2/ g, and porous graphene has flourishing mesopore pore texture (mesopore duct is 2-50 nm); The SBR emulsion of 30% in step 1 is changed into the PTFE emulsion of 10%, the ultracapacitor of gained is under current density is 0.05 A/g, and ratio capacitance is 136 F/g; Current density is under 20 A/g, and ratio capacitance is 85 F/g.Under current density is 20 A/g, after circulation 10000, the capability retention of ultracapacitor is up to 99.2%.
Claims (5)
1. a porous graphene, it is characterized in that, described porous graphene is prepared from by following steps: the proportioning mix and blend 0.5h being 1:1-10 with graphene oxide and inorganic salt mass ratio by graphene oxide water solution and inorganic salt, after mixed solution is placed in tube furnace, 200-300 DEG C is risen to the heat-up rate of 1-10 DEG C/min under nitrogen protection atmosphere, insulation 1-3h, Temperature fall is to room temperature, after be placed in again the aqueous solution boil stir 1h, the porous graphene of high-specific surface area is obtained after filtration, filtrate crystallization can obtain original inorganic salt again, and it is reusable.
2. a kind of porous graphene according to claim 1, is characterized in that, described graphene oxide water solution is the aqueous solution containing 5-7wt. % graphene oxide.
3. a kind of porous graphene according to claim 1, is characterized in that, described inorganic salt are: NaCl, KCl, Na
2cO
3or K
2cO
3.
4. adopt a preparation method for the ultracapacitor of porous graphene, it is characterized in that, specifically comprise the following steps:
(1) porous graphene, graphitized carbon black, binding agent being mixed according to the proportioning that mass ratio is 8:1:1 and be adjusted to pulpous state, is slurry;
(2) coating machine is then utilized to be coated on aluminium foil by slurry shaping, preparing thickness is 240 μm of carbon electrodes, then adopt rolling machine with the speed of the pressure of 40 tons and 10 m/min by carbon electrode compacting, the carbon electrode of compacting is washed into the carbon electrode sheet of 75 × 55 mm by rear stamping machine;
(3) the carbon electrode sheet that step (2) obtains is placed in 170 DEG C of vacuum drying oven inner drying 12h, obtains electrode slice finished product;
(4) the electrode slice finished product two steps (3) that quality is equal, thickness is equal obtained respectively, as positive and negative electrode, take cellulose paper as barrier film, with organic system solution for electrolytic solution, in the glove box being full of high-purity argon gas, is assembled into ultracapacitor.
5. a kind of preparation method adopting the ultracapacitor of porous graphene according to claim 4, is characterized in that, the binding agent of described step (1) is massfraction is the PTFE emulsion of 10% or the SBR emulsion of 30%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510110365.4A CN104925785A (en) | 2015-03-13 | 2015-03-13 | Preparation methods of porous graphene and supercapacitor with porous graphene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510110365.4A CN104925785A (en) | 2015-03-13 | 2015-03-13 | Preparation methods of porous graphene and supercapacitor with porous graphene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104925785A true CN104925785A (en) | 2015-09-23 |
Family
ID=54113259
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510110365.4A Pending CN104925785A (en) | 2015-03-13 | 2015-03-13 | Preparation methods of porous graphene and supercapacitor with porous graphene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104925785A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105329883A (en) * | 2015-10-14 | 2016-02-17 | 南京邮电大学 | Porous graphene preparation method |
| CN105854803A (en) * | 2016-05-17 | 2016-08-17 | 同济大学 | Preparation method of graphene capable of serving as adsorbent |
| CN107188281A (en) * | 2017-06-09 | 2017-09-22 | 北京理工大学 | A kind of research of porous graphene material in capacitive deionization |
| CN107324324A (en) * | 2017-07-18 | 2017-11-07 | 天津工业大学 | A kind of preparation method of fold porous graphene |
| CN110759335A (en) * | 2019-12-10 | 2020-02-07 | 齐鲁工业大学 | Porous graphene electrode and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757036A (en) * | 2011-04-26 | 2012-10-31 | 海洋王照明科技股份有限公司 | Preparation method of porous graphene |
| CN103180243A (en) * | 2010-12-29 | 2013-06-26 | 海洋王照明科技股份有限公司 | Porous graphene material and preparation method and uses as electrode material thereof |
| CN103413693A (en) * | 2013-05-24 | 2013-11-27 | 宁波南车新能源科技有限公司 | Method of manufacturing a supercapacitor |
| CN103811197A (en) * | 2014-02-26 | 2014-05-21 | 上海宝聚新化能源科技有限公司 | Manufacturing method of super capacitor |
-
2015
- 2015-03-13 CN CN201510110365.4A patent/CN104925785A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103180243A (en) * | 2010-12-29 | 2013-06-26 | 海洋王照明科技股份有限公司 | Porous graphene material and preparation method and uses as electrode material thereof |
| CN102757036A (en) * | 2011-04-26 | 2012-10-31 | 海洋王照明科技股份有限公司 | Preparation method of porous graphene |
| CN103413693A (en) * | 2013-05-24 | 2013-11-27 | 宁波南车新能源科技有限公司 | Method of manufacturing a supercapacitor |
| CN103811197A (en) * | 2014-02-26 | 2014-05-21 | 上海宝聚新化能源科技有限公司 | Manufacturing method of super capacitor |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105329883A (en) * | 2015-10-14 | 2016-02-17 | 南京邮电大学 | Porous graphene preparation method |
| CN105854803A (en) * | 2016-05-17 | 2016-08-17 | 同济大学 | Preparation method of graphene capable of serving as adsorbent |
| CN107188281A (en) * | 2017-06-09 | 2017-09-22 | 北京理工大学 | A kind of research of porous graphene material in capacitive deionization |
| CN107324324A (en) * | 2017-07-18 | 2017-11-07 | 天津工业大学 | A kind of preparation method of fold porous graphene |
| CN110759335A (en) * | 2019-12-10 | 2020-02-07 | 齐鲁工业大学 | Porous graphene electrode and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhao et al. | Rose-derived 3D carbon nanosheets for high cyclability and extended voltage supercapacitors | |
| Fu et al. | Crab shell derived multi-hierarchical carbon materials as a typical recycling of waste for high performance supercapacitors | |
| Chen et al. | Biomass based N-doped hierarchical porous carbon nanosheets for all-solid-state supercapacitors | |
| Roy et al. | Preparation of hierarchical porous activated carbon from banana leaves for high‐performance supercapacitor: effect of type of electrolytes on performance | |
| Ye et al. | Nitrogen and oxygen-codoped carbon nanospheres for excellent specific capacitance and cyclic stability supercapacitor electrodes | |
| Du et al. | Designing synthesis of porous biomass carbon from wheat straw and the functionalizing application in flexible, all-solid-state supercapacitors | |
| Yang et al. | Pore structure regulation of hierarchical porous carbon derived from coal tar pitch via pre-oxidation strategy for high-performance supercapacitor | |
| Mehare et al. | Preparation of porous agro-waste-derived carbon from onion peel for supercapacitor application | |
| Mirzaeian et al. | Electrode and electrolyte materials for electrochemical capacitors | |
| Wang et al. | From trash to treasure: direct transformation of onion husks into three-dimensional interconnected porous carbon frameworks for high-performance supercapacitors in organic electrolyte | |
| Zhang et al. | Facile preparation of 3D hierarchical porous carbon from lignin for the anode material in lithium ion battery with high rate performance | |
| Bai et al. | Nickel-cobalt layered double hydroxide nanowires on three dimensional graphene nickel foam for high performance asymmetric supercapacitors | |
| Zhang et al. | One-step synthesis of hierarchically porous carbons for high-performance electric double layer supercapacitors | |
| Wang et al. | “Brick-and-mortar” sandwiched porous carbon building constructed by metal-organic framework and graphene: Ultrafast charge/discharge rate up to 2 V s− 1 for supercapacitors | |
| Mo et al. | Heteroatom-doped hierarchical porous carbon for high performance flexible all-solid-state symmetric supercapacitors | |
| Pu et al. | Impregnation assisted synthesis of 3D nitrogen-doped porous carbon with high capacitance | |
| Chen et al. | Facile synthesis of cellulose-based carbon with tunable N content for potential supercapacitor application | |
| Zou et al. | Porous carbon with interpenetrating framework from Osmanthus flower as electrode materials for high-performance supercapacitor | |
| Guo et al. | N, P, S co-doped biomass-derived hierarchical porous carbon through simple phosphoric acid-assisted activation for high-performance electrochemical energy storage | |
| CN104925785A (en) | Preparation methods of porous graphene and supercapacitor with porous graphene | |
| Li et al. | Multiple-heteroatom doped porous carbons from self-activation of lignosulfonate with melamine for high performance supercapacitors | |
| Muthu Balasubramanian et al. | Groundnut shell–derived porous carbon-based supercapacitor with high areal mass loading using carbon cloth as current collector | |
| CN108288547B (en) | Preparation method of nitrogen-phosphorus-sulfur ternary co-doped ordered mesoporous carbon material | |
| CN108054020B (en) | Preparation method and application of nitrogen-doped carbon particle/graphitized carbon-nitrogen composite material | |
| CN105375028A (en) | Contractive inner-structure-adjustable mesoporous inorganic salt nanotube material, preparation method therefor and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150923 |