CN109281224A - A kind of porous graphene fabric nonwoven cloth and preparation method thereof - Google Patents
A kind of porous graphene fabric nonwoven cloth and preparation method thereof Download PDFInfo
- Publication number
- CN109281224A CN109281224A CN201811110354.6A CN201811110354A CN109281224A CN 109281224 A CN109281224 A CN 109281224A CN 201811110354 A CN201811110354 A CN 201811110354A CN 109281224 A CN109281224 A CN 109281224A
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- Prior art keywords
- fiber
- graphene oxide
- graphene
- woven fabrics
- nonwoven cloth
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Classifications
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/36—Inorganic fibres or flakes
- D21H13/46—Non-siliceous fibres, e.g. from metal oxides
- D21H13/50—Carbon fibres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21J—FIBREBOARD; MANUFACTURE OF ARTICLES FROM CELLULOSIC FIBROUS SUSPENSIONS OR FROM PAPIER-MACHE
- D21J5/00—Manufacture of hollow articles by transferring sheets, produced from fibres suspensions or papier-mâché by suction on wire-net moulds, to couch-moulds
Abstract
The invention discloses a kind of porous graphene fiber non-woven fabrics and preparation method thereof, it constitutes inside the graphene fiber of non-woven fabrics and a large amount of micropores is contained on surface, the multi-stage artery structure being made of macropore and micropore is formd in non-woven fabrics, significantly increase the specific surface area of this novel graphene fabric nonwoven cloth, simultaneously, there is stronger interaction between fiber, mutually overlapped flexible network skeleton can be formed, therefore is had broad application prospects in fields such as absorption, catalysis, energy storage electrode materials.
Description
Technical field
The present invention relates to graphene fiber and fabric more particularly to a kind of porous graphene fabric nonwoven cloth and its preparation sides
Method.
Background technique
Graphene fiber non-woven fabrics is a kind of one assembled by graphene fiber by the interfibrous effect of fusion certainly
Kind there is the fiber assembly (Nature Communications, 2016,13684) of reticular structure.Certainly due to graphene fiber
The performances such as the preferable mechanics of body, conduction, and it is relatively strong to interact after fiber fusion, and contact resistance is lower, therefore graphene is fine
Tieing up non-woven fabrics has excellent mechanical stability, flexible and electric conductivity, as a kind of potential high-performance electrode material
Material, has broad application prospects in flexible energy storage device field.
As the electrode material of flexible device, other than with conductive capability, it is also necessary to meet two conditions, first is that soft
Property, second is that electro-chemical activity.Graphene fiber non-woven fabrics is overlapped to form reticular structure by flexible preferable graphene fiber, ensure that
To demand flexible；On the other hand, since the fibre structure of conventional graphene fiber non-woven fabrics is finer and close, electro-chemical activity compared with
It is low, restrict the electrode performance of non-woven fabrics.The present invention is by preparing porous graphene fiber and being assembled into non-woven fabrics, in nonwoven
The multi-stage artery structure that the different pore sizes such as macropore, mesoporous, micropore are constructed in cloth is remarkably improved the work of graphene fiber non-woven fabrics
Property surface area, to obtain better chemical property.It is expected to expand it in the application in flexible energy storage device field.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of porous graphene fiber non-woven fabrics and its
Preparation method.
The invention is realized by the following technical scheme: a kind of porous graphene fiber non-woven fabrics, by porous graphene fibre
The reticular structure that dimension mutually overlap joint is formed, porous graphene fiber is accumulated by graphene film with certain density, in fiber
Contain the hole of a large amount of micron order diameters in portion.
A kind of preparation method of porous graphene fabric nonwoven cloth, comprising the following steps:
(1) continuous wet spinning is carried out by spinning solution of graphene oxide dispersion.
(2) obtained graphene oxide fiber is being placed at room temperature for 12h or more, then not higher than 100 DEG C at a temperature of
It is dried in vacuo 3h.
(3) dry graphene oxide fiber is blended into length in deionized water using high shear homomixer is 1-
The staple fiber of 7mm, the graphene oxide staple fiber dispersion liquid being swollen.
(4) utilize Vacuum filtration device that graphene oxide gel deposit short fibres on strainer, are obtained graphene oxide
Fiber filter cake；
(5) it keeps filtering negative pressure, to reduce the moisture of fibrous inside.
(6) it uses liquid nitrogen frozen graphene oxide fiber filter cake and is freeze-dried, obtain porous graphene oxide fiber
Non-woven fabrics.
(7) the graphene oxide fabric nonwoven cloth after drying is subjected to further electronation or thermal reduction is more to obtain
Hole graphene fiber non-woven fabrics.
Further, spinning solution is the aqueous solution or n,N-Dimethylformamide solution of graphene oxide.It is corresponding, it spins
The coagulating bath that silk process uses is calcium chloride/water/alcohol mixeding liquid or ethyl acetate.
Further, the negative pressure retention time of step 5 is 1-120 minutes.
Further, the method for redox graphene fabric nonwoven cloth is to use hydroiodic acid, hydrazine hydrate, Vitamin C, boron
The reducing agents such as sodium hydride carry out electronation or 100-3000 DEG C of thermal reduction.
Compared with the prior art, the present invention has the following beneficial effects:
(1) a large amount of pore structures are contained in the inside and surface of graphene fiber, make to be formed in non-woven fabrics from micropore to macropore
Hierarchical porous structure has bigger active surface, is conducive to its application as electrode.
(2) flexibility that graphene fiber non-woven fabrics is maintained while obtaining porous structure, in flexible wearable accumulator
Part field is with a wide range of applications.
(3) preparation method is simple, the ginseng such as negative pressure retention time when the micro-structure of material can be by fibre diameter, suction filtration
Several selections control effectively.
Detailed description of the invention
Fig. 1 is the electron scanning micrograph in porous graphene fabric nonwoven cloth surface and section.
Specific embodiment
Present invention utilizes the hydrophily of graphene oxide, water absorption and swelling after impregnating graphene oxide fiber in water,
Graphene oxide fiber after swelling becomes gelatinous soft material, has certain deformability, therefore in vacuum filtration
The effects of can mutually fitting closely under suction function, and passing through the hydrogen bond and Van der Waals force between the graphene oxide layer of interface, is real
Existing interfibrous fusion, obtains the network skeleton of fiber composition.When the water in fiber does not parch completely carry out low-temperature treatment and
It is freeze-dried the template action for the ice crystal that sequence of operations can be formed using water, while aqueous solvent removing, makes graphite oxide
Alkene fibrous inside forms porous structure.Graphene oxide fiber filter cake can be changed by the control to negative pressure retention time when filtering
In water content, so that the hole content and hole size to fiber control.This method is easy to operate, can promote material
Its structural stability and flexibility are kept while electro-chemical activity, obtain high performance energy storage electrode material.
The present invention is specifically described below by embodiment, the present embodiment is served only for doing further the present invention
It is bright, it should not be understood as limiting the scope of the invention, those skilled in the art makes one according to the content of foregoing invention
A little nonessential changes and adjustment, all belong to the scope of protection of the present invention.
Embodiment 1:
(1) using concentration for 5mg/mL graphene oxide/aqueous solution as spinning solution, calcium chloride/water/alcohol mixeding liquid (matter
Amount is than 20:300:100) it is that coagulating bath carries out continuous wet spinning.
(2) obtained graphene oxide fiber is being placed at room temperature for 12h, then 80 DEG C at a temperature of be dried in vacuo 3h.
(3) dry graphene oxide fiber is blended using high shear homomixer in deionized water, is swollen
Graphene oxide staple fiber dispersion liquid.
(4) Vacuum filtration device is utilized on strainer, to drain graphene oxide gel deposit short fibres to surface solvent
It keeps filtering 10 minutes again afterwards.
(5) it uses liquid nitrogen frozen graphene oxide fiber filter cake and is freeze-dried, obtain porous graphene oxide fiber
Non-woven fabrics.
(6) the graphene oxide fabric nonwoven cloth after drying is used into hydrazine hydrate reduction.
By above step, obtained graphene fiber contains a large amount of pore structures, the specific surface of graphene fiber non-woven fabrics
Product is 332m2/ g, compared with the 52m of ordinary graphite alkene fabric nonwoven cloth2/ g is obviously improved.
Embodiment 2:
(1) using concentration for 5mg/mL graphene oxide/n,N-Dimethylformamide solution as spinning solution, ethyl acetate is
Coagulating bath carries out continuous wet spinning.
(2) obtained graphene oxide fiber is placed at room temperature for 14h, 60 DEG C of vacuum drying 3h.
(3) dry graphene oxide fiber is blended using high shear homomixer in deionized water, is swollen
Graphene oxide staple fiber dispersion liquid.
(4) Vacuum filtration device is utilized on strainer, to drain graphene oxide gel deposit short fibres to surface solvent
It keeps filtering 15 minutes again afterwards.
(5) it uses liquid nitrogen frozen graphene oxide fiber filter cake and is freeze-dried, obtain porous graphene oxide fiber
Non-woven fabrics.
(6) the graphene oxide fabric nonwoven cloth after drying is used into 800 DEG C of thermal reductions.
By above step, obtained graphene fiber non-woven fabrics specific surface area reaches 360m2/ g, between the fiber of non-woven fabrics
Binding force is stronger, shows the certain elasticity of compression and flexibility.
Embodiment 3:
(1) using concentration for 15mg/mL graphene oxide/n,N-Dimethylformamide solution as spinning solution, ethyl acetate
Continuous wet spinning is carried out for coagulating bath.
(2) obtained graphene oxide fiber is placed at room temperature for 12h, 100 DEG C of vacuum drying 3h.
(3) dry graphene oxide fiber is blended using high shear homomixer in deionized water, is swollen
Graphene oxide staple fiber dispersion liquid.
(4) Vacuum filtration device is utilized on strainer, to drain graphene oxide gel deposit short fibres to surface solvent
It keeps filtering 50 minutes again afterwards.
(5) it uses liquid nitrogen frozen graphene oxide fiber filter cake and is freeze-dried.
By above step, obtained graphene fiber non-woven fabrics pore structure is less, specific surface area 83m2/g。
Embodiment 4:
Step 1-3 is the same as embodiment 2.
Step 4 are as follows: utilize Vacuum filtration device by graphene oxide gel deposit short fibres on strainer, to surface solvent
It keeps filtering 120 minutes again after draining.
Step 5-6 is the same as embodiment 2.
By above step, fusion degree is high between obtained graphene fiber non-woven fabrics fiber, specific surface area 220m2/
g。
Claims (5)
1. a kind of porous graphene fiber non-woven fabrics, which is characterized in that non-woven fabrics is mutually overlapped by porous graphene fiber
The reticular structure of formation, porous graphene fiber are accumulated by graphene film, and fibrous inside contains the hole of micron order diameter.
2. a kind of preparation method of porous graphene fabric nonwoven cloth, which comprises the following steps:
(1) continuous wet spinning is carried out by spinning solution of graphene oxide dispersion.
(2) obtained graphene oxide fiber is being placed at room temperature for 12h or more, then in the at a temperature of vacuum not higher than 100 DEG C
Dry 3h.
(3) dry graphene oxide fiber is blended into length in deionized water using high shear homomixer is 1-7mm
Staple fiber, the graphene oxide staple fiber dispersion liquid being swollen.
(4) utilize Vacuum filtration device that graphene oxide gel deposit short fibres on strainer, are obtained graphene oxide fiber
Filter cake；
(5) it keeps filtering negative pressure, to reduce the moisture of fibrous inside.
(6) it uses liquid nitrogen frozen graphene oxide fiber filter cake and is freeze-dried, obtain porous graphene oxide fiber non-woven
Cloth.
(7) the graphene oxide fabric nonwoven cloth after drying is subjected to further electronation or thermal reduction to obtain porous stone
Black alkene fabric nonwoven cloth.
3. according to the method described in claim 2, it is characterized in that, spinning solution is the aqueous solution or N of graphene oxide, N- diformazan
Base formamide solution.Corresponding, the coagulating bath that spinning process uses is calcium chloride/water/alcohol mixeding liquid or ethyl acetate.
4. according to the method described in claim 2, it is characterized in that, the suction filtration time of step 5 is 1-120 minutes.
5. according to the method described in claim 2, it is characterized in that, the method for redox graphene fabric nonwoven cloth is to use
The reducing agents such as hydroiodic acid, hydrazine hydrate, Vitamin C, sodium borohydride carry out electronation or 100-3000 DEG C of thermal reduction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201811110354.6A CN109281224A (en) | 2018-09-21 | 2018-09-21 | A kind of porous graphene fabric nonwoven cloth and preparation method thereof |
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| CN201811110354.6A CN109281224A (en) | 2018-09-21 | 2018-09-21 | A kind of porous graphene fabric nonwoven cloth and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110528170A (en) * | 2019-08-21 | 2019-12-03 | 杭州高烯科技有限公司 | A kind of compound nonwoven cloth of photocatalytic self-cleaning and preparation method thereof |
| CN111676591A (en) * | 2020-06-11 | 2020-09-18 | 南京信息工程大学 | Graphene oxide aerogel fiber fabric and preparation method and application thereof |
| CN112779632A (en) * | 2021-01-26 | 2021-05-11 | 南京捷纳思新材料有限公司 | Ordered porous high-conductivity graphene fiber and preparation method and application thereof |
| CN113215857A (en) * | 2021-04-13 | 2021-08-06 | 中国科学院电工研究所 | Heteroatom-doped graphene nanofiber non-woven fabric and preparation method thereof |
| CN114507981A (en) * | 2022-01-28 | 2022-05-17 | 南京工业大学 | Preparation method of graphene/molybdenum disulfide composite fiber fabric |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104229782A (en) * | 2014-09-10 | 2014-12-24 | 浙江碳谷上希材料科技有限公司 | Preparation method of ordered graphene porous membrane |
| CN106192201A (en) * | 2016-07-18 | 2016-12-07 | 浙江大学 | A kind of graphene fiber non-woven fabrics and preparation method thereof |
| CN107119346A (en) * | 2017-06-02 | 2017-09-01 | 东华大学 | A kind of preparation method of carbon nano tube/graphene composite fibre |
| CN107502995A (en) * | 2017-08-08 | 2017-12-22 | 杭州高烯科技有限公司 | Graphene fiber and graphene fiber non-woven fabrics of a kind of fold and preparation method thereof |
| CN107687086A (en) * | 2016-08-05 | 2018-02-13 | 中国科学院苏州纳米技术与纳米仿生研究所 | Porous graphene carbon nano tube composite fibre and its fast preparation method |
-
2018
- 2018-09-21 CN CN201811110354.6A patent/CN109281224A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104229782A (en) * | 2014-09-10 | 2014-12-24 | 浙江碳谷上希材料科技有限公司 | Preparation method of ordered graphene porous membrane |
| CN106192201A (en) * | 2016-07-18 | 2016-12-07 | 浙江大学 | A kind of graphene fiber non-woven fabrics and preparation method thereof |
| CN107687086A (en) * | 2016-08-05 | 2018-02-13 | 中国科学院苏州纳米技术与纳米仿生研究所 | Porous graphene carbon nano tube composite fibre and its fast preparation method |
| CN107119346A (en) * | 2017-06-02 | 2017-09-01 | 东华大学 | A kind of preparation method of carbon nano tube/graphene composite fibre |
| CN107502995A (en) * | 2017-08-08 | 2017-12-22 | 杭州高烯科技有限公司 | Graphene fiber and graphene fiber non-woven fabrics of a kind of fold and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110528170A (en) * | 2019-08-21 | 2019-12-03 | 杭州高烯科技有限公司 | A kind of compound nonwoven cloth of photocatalytic self-cleaning and preparation method thereof |
| CN111676591A (en) * | 2020-06-11 | 2020-09-18 | 南京信息工程大学 | Graphene oxide aerogel fiber fabric and preparation method and application thereof |
| CN112779632A (en) * | 2021-01-26 | 2021-05-11 | 南京捷纳思新材料有限公司 | Ordered porous high-conductivity graphene fiber and preparation method and application thereof |
| CN113215857A (en) * | 2021-04-13 | 2021-08-06 | 中国科学院电工研究所 | Heteroatom-doped graphene nanofiber non-woven fabric and preparation method thereof |
| CN114507981A (en) * | 2022-01-28 | 2022-05-17 | 南京工业大学 | Preparation method of graphene/molybdenum disulfide composite fiber fabric |
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