CN101376715A - Preparation of large area flexible self-supporting polyaniline nanostructured film - Google Patents
Preparation of large area flexible self-supporting polyaniline nanostructured film Download PDFInfo
- Publication number
- CN101376715A CN101376715A CNA200810156273XA CN200810156273A CN101376715A CN 101376715 A CN101376715 A CN 101376715A CN A200810156273X A CNA200810156273X A CN A200810156273XA CN 200810156273 A CN200810156273 A CN 200810156273A CN 101376715 A CN101376715 A CN 101376715A
- Authority
- CN
- China
- Prior art keywords
- polyaniline
- paper
- preparation
- film
- reaction
- 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.)
- Granted
Links
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002120 nanofilm Substances 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 13
- 239000002086 nanomaterial Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000000835 fiber Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000001599 direct drying Methods 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229920000547 conjugated polymer Polymers 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- YFSUTJLHUFNCNZ-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-M 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 230000002269 spontaneous effect Effects 0.000 claims description 3
- 239000000178 monomer Substances 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract 6
- 239000010408 film Substances 0.000 description 24
- 239000000463 material Substances 0.000 description 15
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 4
- 239000002216 antistatic agent Substances 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 239000002071 nanotube Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 235000019082 Osmanthus Nutrition 0.000 description 1
- 241000333181 Osmanthus Species 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to a preparation method for a large-area flexible self-supporting polyaniline nano-structured film, which comprises the following steps: (1) a MnO2 template with long fibers of 1 micron to 10 centimeters and polyaniline with the long fibers of 1 micron to 10 centimeters are mixed according to the weight proportion of 100: 0.5 to 5: 95 and dispersed in water, and a raw material paper/film is prepared through the filtration method, the direct drying method or the drying method; (2) the raw material paper/film is converted to a polyaniline paper by the in-situ chemical reaction, the raw material paper is immersed in a solvent which dissolves proton acid and polyaniline monomer for carrying out the reaction for 10min to 72 hours; pH value is 0-6.8; (3) the MnO2 template participates the reaction and can be spontaneously removed after the completion of the reaction; (4) the appearance of the synthesized polyaniline product accurately copies the micro-nano-structure of the MnO2 template, so as to prepare the large-area polyaniline nano-structured paper/film.
Description
Technical field:
The present invention relates to a kind of preparation method of polyaniline nanostructured film, the controllable method for preparing of flexible polyaniline nano structure paper of especially novel big area self-supporting or film.
Background technology:
The nanostructure of conjugated polymers has very big potentiality in the application of device, especially with transistor [1], transmitter [2] and secondary cell aspects such as [3] are comparatively outstanding, polyaniline has stable physicochemical property as a kind of important conjugated conductive polymer, controlled redox state and electric conductivity advantages of higher [4], thereby be widely used in solar cell by people, electromagnetic shielding material [5], antistatic material [6], electrode materials [7], high capacity capacitor material [8], thermoelectric material [9], triode, numerous areas such as sensor material and gas separation material.The final application forms of device such as most of electron device or electrochemical device such as battery, ultracapacitor, artificial-muscle are films, and usually the synthetic polyaniline all is a powder, and the film of making by methods such as compressing tablets has then lost the high-ratio surface activity of its nanostructure.Therefore be necessary to seek and make polyaniline both effectively keep its nanostructure, again the method that can exist with the self-supporting film form.If can prepare the polyaniline paper, then it is configured to feature with interlacing macrofiber, has not only kept the independent one-dimentional structure of fiber but also exists with the general form of self-supporting film, will have been widely used on using.
Relating to polyaniline synthetic method also can be referring to the open CN1415645 of Chinese patent, the preparation method of soluble conductive polyaniline, disclose a kind of preparation method of soluble conductive polyaniline, its key step is that polyaniline in eigenstate and macromole function protonic acid are carried out hot doping in water and solubility promoter composition mixed solvent.It is oxygenant chemical oxidization method compositing conducting polyaniline that Chinese patent discloses 1446839 usefulness Manganse Dioxide, the sour water suspension that aniline monomer is added and contain Manganse Dioxide carries out oxidizing reaction, its invention compositing conducting polyaniline is simple, the residual quantity of Manganse Dioxide is very low in the product, but does not relate to the preparation of polyaniline nano structure paper.Chinese patent discloses 1667021 and utilizes under the thermal and hydric environment mineral acid of different concns to mix to control the microscopic appearance of polyaniline, but does not relate to the synthetic of polyaniline self-supporting film equally.
[1]A.N.Aleshin，Adv.Mater.2006，18，17.
[2]M.Kanungo，A.Kumar，A.Q.Contractor，Anal.Chem.2003，758，5673.
[3]F.Y.Cheng，W.Tang，C.S.Li，J.Chen，H.K.Liu，P.W.Shen，S.X.Dou，Chem.-Eur.J.2006，12，3082.
[4]A.G.MacDiarmid，Synthetic?metals：A?Novel?role?for?organic?polymers，Angew.Chem.Int.Ed.2001，40，2581-2590
[5] a kind of conductive high-polymer microwave absorbent and method for making thereof such as Wan Meixiang, CN1110786
[6] E Rodri osmanthus JW Lin Desai now, antistatic fibers and preparation method thereof, CN1145720
[7] Wang Wanxi, solid polymer high-energy battery, CN 1156911
[8] beam road, superhigh-capacitance capacitor with composite carbon nanotube and manufacture method thereof, CN1388540
[9] Zhang Zuxun, Zhang Shengtang, Hao Jixiang can directly change the heat energy in the environment into the polyaniline composition of electric energy and use its metal sandwich spare, CN1254728
[10]Z.Wei，M.X.Wan?Adv.Mater.2002，14，1314.
[11]M.Kanungo，A.Kumar，A.Q.Contractor，Anal.Chem.2003，75，5673.
[12]M.Yang，J.Ma，C.L.Zhang，Z.Z.Yang，Y.F.Lu，Angew.Chem.2005，117，6885；Angew.Chem.Int.Ed.2005，44，6727.
Summary of the invention:
The objective of the invention is to propose the preparation method that a self-supporting film in-situ chemical template method prepares large area flexible self-supporting polyaniline nanostructured paper or film, and template can spontaneously be removed in the reaction process.
Technical scheme of the present invention is: the in-situ chemical template method prepares the preparation method of large area flexible self-supporting polyaniline nanostructured paper or film,
(1) preparation of raw material paper is with macrofiber MnO
2The part by weight that template (1 micron～10 cm long) and macrofiber polyaniline (1 micron～10 cm long) are pressed 100:0.5～5:95 mixes, and is dispersed in the water and makes paper by filtration method, direct drying method or dry method.As in filtering net or container, forming material film/paper.
(2) raw material paper/film in-situ chemical reaction is converted to the preparation of polyaniline paper, the raw material paper is immersed to be dissolved with in protonic acid (comprising organic acid or mineral acid) and the monomeric solvent reacted 10 minutes～72 hours; PH value scope is between 0～7, and temperature of reaction is in 0 ℃～100 ℃ scopes, and organic acid can be selected as Witco 1298 Soft Acid, perfluorooctane sulfonate etc., or mineral acid such as sulfuric acid, hydrochloric acid etc.
(3), MnO
2Masterplate itself participates in reaction, and can spontaneous removing after reaction is finished.
(4), the pattern of synthesized polyaniline product has duplicated MnO accurately
2The micro-nano structure of masterplate is prepared into large-area polyaniline nano structure paper/film.
(5), because oxidation synthesis method and the polyaniline of other conjugated polymerss such as polypyrrole, polythiophene class are identical, this synthetic method also is used for synthesizing the paper of other conjugated polymerss.
The invention particularly relates to the nanofiber that utilizes overlength and prepare the polyaniline paper, by metal oxide (MnO synthetic and that the preparation overlength has oxidisability
2Deng) nano wire or nanotube, and their preparations are become the paper of nanostructure, then be template polymerization aniline monomer generation polyaniline under sour environment.After reaction was finished, what template was spontaneous removed, the polyaniline nano structure paper.It is that the field of film obtains potential and uses that the micrometer/nanometer structure polyaniline paper is expected to have nanometer microscopic appearance and main form concurrently at needs, for example fields such as ultracapacitor, heavy metal containing wastewater treatment, lithium ion battery, transmitter, gas separation material, electromagnetic shielding material and antistatic material.
The invention has the beneficial effects as follows: the reaction soln system is simpler, and its preparation is reacted the later stage and purified simply easily, and step that need not be special is separated template.
Description of drawings
Fig. 1 is the photo or the detection figure of polyaniline film/paper of the present invention: the photo that (a) is mixed with the polyaniline film/paper of 10% carbon nanotube; (b) polyaniline film/paper has good flexibility;
Fig. 2 is that sem photograph (SEM) shows, paper is interweaved by the polyaniline fiber of about 80～90 nanometers and constitutes;
Fig. 3 is the SEM figure in polyaniline film/paper cross section;
Fig. 4 is the TEM sign demonstration to the fiber that come out by ultra-sonic dispersion on the paper, and the polyaniline paper is to be made of nanotube.Scale length: be 1 micron.
Embodiment:
Utilize MnO
2The exemplary steps of paper synthesized polyaniline nanotube is as follows: 1, at first with MnO
2Especially 10～1000 microns long of macrofibers, the length of fiber also can adopt millimeter level or other length M nO
2Macrofiber (the long more final paper strength of fiber is good more).The part by weight that the polyaniline macrofiber is pressed 100:0.5～5:95 mixes, and be dispersed in the water, at the container inner drying is that the baseplane preparation of container forms raw material paper/film, can also form material film/paper on superfine filtering net, perhaps by dry method of paper-making preparation becoming film.
Then material film/paper is put into solvent reaction (room temperature condition the best of protonic acids such as being dissolved with perfluorooctane sulfonate (scope of pH value is controlled between 0～6.8) and aniline monomer, can also adopt 0 to 100 ℃ temperature), reaction time range is very wide, can get 15-30 minute, also can get 3-10 hour, even 2-3 days, film quality does not have remarkable difference; 2, the film that obtains after the reaction end cleans to remove the survivor ion and the oligopolymer on surface repeatedly through deionized water and ethanol, and last products therefrom will be dried (12 hours) under 60 ℃ of vacuum environments.Obtain final product polyaniline paper or film.The yet available Witco 1298 Soft Acid of protonic acid, perfluor acetate or sulfuric acid etc. do not have remarkable difference in quality.
The pattern of final product is by the MnO that adopts
2The microtexture decision of template, and can prepare big area polyaniline paper.This controllable synthesis method has been simplified experimental procedure, ensured product quality, being expected to obtain potential in the field of needs maintenance nanometer microscopic appearance and thin-film material uses, electrode materials for example, the high capacity capacitor material, sensor material, gas separation material, electromagnetic shielding material and antistatic material etc.
The present invention also can prepare the polyaniline paper of even carbon-doped nanometer tube, and method is carbon nanotube that adds the Manganse Dioxide parcel in the step for preparing the raw material paper at first step or the carbon nanotube that polyaniline wraps up.All the other steps are the same.
Claims (5)
1, the preparation method of large area flexible self-supporting polyaniline nanostructured film is characterized in that
(1) with 1 micron～10 cm long fiber MnO
2The part by weight that template and 1 micron～10 cm long fiber polyanilines are pressed 100:0.5～5:95 mixes, and is dispersed in the water and makes raw material paper/film by filtration method, direct drying method or dry method;
(2) raw material paper/film in-situ chemical reaction is converted to the polyaniline paper, the raw material paper is immersed to be dissolved with in protonic acid and the monomeric solvent of polyaniline reacted 10 minutes～72 hours; Between the pH value 0～6.8;
(3) MnO
2Masterplate itself participates in reaction, and can spontaneous removing after reaction is finished;
(4), the pattern of synthesized polyaniline product has duplicated MnO accurately
2The micro-nano structure of masterplate is prepared into large-area polyaniline nano structure paper/film.
2, the preparation method of large area flexible self-supporting polyaniline nanostructured film according to claim 1 is characterized in that organic acid can adopt Witco 1298 Soft Acid or perfluorooctane sulfonate, and mineral acid adopts as sulfuric acid or hydrochloric acid.
3, the preparation method of large area flexible self-supporting polyaniline nanostructured film according to claim 1 is characterized in that 0 to 100 ℃ of temperature of reaction.
4, the preparation method of large area flexible self-supporting polyaniline nanostructured film according to claim 1, it is characterized in that preparing the polyaniline paper of even carbon-doped nanometer tube, when (1) step preparation raw material paper, add the carbon nanotube of Manganse Dioxide parcel or the carbon nanotube of polyaniline parcel.
5, the preparation method of large area flexible self-supporting polyaniline nanostructured film according to claim 1 is characterized in that the oxypolymerization method and the polyaniline of conjugated polymers is identical.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810156273XA CN101376715B (en) | 2008-09-26 | 2008-09-26 | Preparation of large area flexible self-supporting polyaniline nanostructured film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810156273XA CN101376715B (en) | 2008-09-26 | 2008-09-26 | Preparation of large area flexible self-supporting polyaniline nanostructured film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101376715A true CN101376715A (en) | 2009-03-04 |
| CN101376715B CN101376715B (en) | 2011-03-23 |
Family
ID=40420457
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810156273XA Expired - Fee Related CN101376715B (en) | 2008-09-26 | 2008-09-26 | Preparation of large area flexible self-supporting polyaniline nanostructured film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101376715B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102568865A (en) * | 2012-02-22 | 2012-07-11 | 华中科技大学 | Preparation method of flexible super capacitor based on paper and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1446839A (en) * | 2003-03-03 | 2003-10-08 | 华东理工大学 | Chemistry oxidation process for synthesizing electric polyanion with use of manganese dioxide as oxidant |
| CN100497761C (en) * | 2007-05-25 | 2009-06-10 | 南京大学 | Method for synthesizing controllable template of nano polyaniline tube |
-
2008
- 2008-09-26 CN CN200810156273XA patent/CN101376715B/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102568865A (en) * | 2012-02-22 | 2012-07-11 | 华中科技大学 | Preparation method of flexible super capacitor based on paper and application thereof |
| CN102568865B (en) * | 2012-02-22 | 2014-06-18 | 华中科技大学 | Preparation method of flexible super capacitor based on paper and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101376715B (en) | 2011-03-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gong et al. | Shape-controlled synthesis of Ni-CeO2@ PANI nanocomposites and their synergetic effects on supercapacitors | |
| CN101481500B (en) | Preparation of conductive polymer / carbon nano-tube composite mesoporous nano-tube | |
| Xie et al. | MOF-derived CoFe2O4 nanorods anchored in MXene nanosheets for all pseudocapacitive flexible supercapacitors with superior energy storage | |
| Pan et al. | Template-Free Synthesis of VO 2 Hollow Microspheres with Various Interiors and Their Conversion into V 2 O 5 for Lithium-Ion Batteries. | |
| Zhang et al. | Graphene–encapsulated selenium/polyaniline core–shell nanowires with enhanced electrochemical performance for Li–Se batteries | |
| Palsaniya et al. | Hierarchical PANI-RGO-ZnO ternary nanocomposites for symmetric tandem supercapacitor | |
| Yang et al. | Supercapacitor electrode of hollow spherical V2O5 with a high pseudocapacitance in aqueous solution | |
| CN103903879B (en) | Porous grapheme/ MnO2 composite film and preparation method and application thereof | |
| Zhang et al. | Hierarchical mesoporous nickel cobaltite nanoneedle/carbon cloth arrays as superior flexible electrodes for supercapacitors | |
| Zhang et al. | Facile preparation, optical and electrochemical properties of layer-by-layer V2O5 quadrate structures | |
| Punnoose et al. | Preparation and electrochemical performances of NiS with PEDOT: PSS chrysanthemum petal like nanostructure for high performance supercapacitors | |
| Zhu et al. | Core@ shell β-FeOOH@ polypyrolle derived N, S-codoped Fe3O4@ N-doped porous carbon nanococoons for high performance supercapacitors | |
| Zhao et al. | Porous CoFe2O4 nanowire arrays on carbon cloth as binder-free anodes for flexible lithium-ion batteries | |
| Shi et al. | Rapid microwave synthesis of self-assembled hierarchical Mn2O3 microspheres as advanced anode material for lithium ion batteries | |
| CN102924718A (en) | Preparation method of nanostructured polypyrrole | |
| Kang et al. | One-pot synthesis of vanadium dioxide nanoflowers on graphene oxide | |
| US20180034055A1 (en) | Composite including porous graphene and carbon nanotube material | |
| CN100497761C (en) | Method for synthesizing controllable template of nano polyaniline tube | |
| Qiao et al. | Microwave-assisted synthesis of Fe-doped NiMnO 3 as electrode material for high-performance supercapacitors | |
| Xu et al. | Conducting polythiophene-wrapped Li4Ti5O12 spinel anode material for ultralong cycle-life Li-ion batteries | |
| Wang et al. | Fabrication of N-doped carbon coated spinel copper cobalt sulfide hollow spheres to realize the improvement of electrochemical performance for supercapacitors | |
| Wei et al. | Metal–organic frameworks-derived hollow octadecahedron nanocages for supercapacitors and wearable self-powered tactile stress sensor | |
| Dai et al. | Self-sacrificing template method to controllable synthesize hollow SnO2@ C nanoboxes for lithium-ion battery anode | |
| Gangaraju et al. | In-situ preparation of silk-cocoon derived carbon and LiFePO4 nanocomposite as cathode material for Li-ion battery | |
| Hsiao et al. | Hierarchical nanostructured electrospun carbon fiber/NiCo2O4 composites as binder‐free anodes for lithium‐ion batteries |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110323 Termination date: 20110926 |