CN108899519A - A kind of biomass-based manganese dioxide-carbon fibre composite and preparation method thereof - Google Patents
A kind of biomass-based manganese dioxide-carbon fibre composite and preparation method thereof Download PDFInfo
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- CN108899519A CN108899519A CN201810725618.2A CN201810725618A CN108899519A CN 108899519 A CN108899519 A CN 108899519A CN 201810725618 A CN201810725618 A CN 201810725618A CN 108899519 A CN108899519 A CN 108899519A
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- manganese dioxide
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
Abstract
The invention discloses a kind of biomass-based manganese dioxide-carbon fibre composite and preparation method thereof, which is mainly by being the carbon fiber structural that is prepared of raw material and the manganese dioxide clad that is coated on carbon fiber surface using biological material.It is that raw material have been prepared into the manganese dioxide@carbon fibre composite with perfect core-shell structure by way of high temperature graphitization process and a step electro-deposition using the biomass being widely present.The distinguishing feature of the composite material is to take full advantage of the advantage of the larger porosity of biomass fiber and surface area, while uniform and fine and close manganese dioxide clad can be grown in fiber surface, forms complicated core-shell structure.The preparation-obtained manganese dioxide@carbon fibre composite of the present invention is used not only for electrode material for super capacitor, moreover it is possible to be applied to manganese dioxide-lithium primary cell positive electrode, be with a wide range of applications.
Description
Technical field
The invention belongs to electrode material technical fields, are related to combination electrode material, specially a kind of biomass-based titanium dioxide
Manganese-carbon fibre composite and preparation method thereof.
Background technique
In primary battery electrode material field, MnO2It has been a concern, has and be quite widely applied.It is not only because it
Electrochemical performance, also have benefited from its rich reserves, it is cheap, environmentally friendly the advantages that.The past more than ten years by
In Li-MnO2Primary battery has high specific energy, low self-discharge rate, stable operating voltage, wide operating temperature range
And the advantages that easy to use, become one of ideal mating power supply of portable military equipment.However in practical applications,
Li-MnO2The heavy-current discharge performance performance of battery is but not so good as people's will, and being primarily due to manganese dioxide is a kind of semiconductor,
Its electric conductivity is poor.In order to solve this problem, traditional way is MnO2Material granule carries out nanosizing processing, and by one
Quantitative conductive agent is mixed into wherein, allows to be coated on manganese dioxide particle, increase electrode interior active material particle with
Contact between active material particle and between active material and collector accelerates electronics to reduce electrode ohmic resistance
Rate travel, improve the fan-out capability of electrode.However, the uniform mixing of conductive agent and reuniting effect make it in practical application
In be difficult to realize high current output.
Summary of the invention
In order to solve the above-mentioned technical problems, the present invention provides a kind of biomass-based manganese dioxide-carbon fibre composites
And preparation method thereof.Based on biological material, more uniform carbon fibre material is obtained by high-temperature process, is made full use of
The characteristics of higher specific surface area and high conductivity of carbon fibre material, then using graphited carbon fiber as conducting matrix grain, benefit
With the mode of electrochemical deposition, on its surface, cladding has the manganese bioxide material of certain electro-chemical activity, so that manganese dioxide
Positive electrode and conductive material completely and come into full contact with, and effectively enhance the transfer ability of its electronics, realize heavy-current discharge
Characteristic.
In order to completely realize that above-mentioned technical purpose, the present invention are realized especially by following technical scheme：
A kind of preparation method of biomass-based manganese dioxide-carbon fibre composite, includes the following steps：
1) biological material is handled into 1-2h using dilute hydrochloric acid, is placed in air dry oven and dries surface moisture；
2) obtained biological material is placed in pipe type sintering furnace, is warming up to 300-350 DEG C of progress carbonization treatment 5-8h,
Ar or N is passed through into pipe type sintering furnace2It is protected, is continuously heating to 800-1000 DEG C of further progress carbonization treatment 5h,
It is increased to 1550-1800 DEG C of progress surface graphitization processing again；
3) graphitized fibre obtained is placed in progress acidification 8-12h in the concentrated sulfuric acid, is scattered in water and/or organic solvent
In, carbon-fiber film is made in vacuum filtration or dissolution volatilization；
4) using carbon-fiber film as working electrode, platinized platinum is heavy as the electricity for carrying out manganese dioxide to electrode and reference electrode
Product；
5) the electro-deposition product obtained is placed in 80-100 DEG C of dry 2h in air dry oven, is placed in Muffle furnace in 250-
It is made annealing treatment under the conditions of 800 DEG C.
The biological material is selected from the life that stalk, sawdust, long-staple cotton, bagasse or rice chaff etc. have abundant cellulose
Material.
The concentration of the dilute hydrochloric acid is 1-3mol/L, and the concentration of the concentrated sulfuric acid is 12~18.4mol/L.
The electro-deposition uses the water for containing manganese cation or organic solution as electric depositing solution, and manganese is cationic
Concentration is 0.01-1mol/L.
The mode of the electro-deposition is using constant current deposition, constant pressure deposition or pulsed deposition.
The current density of the constant current deposition is 1-10mA/cm2, the voltage of constant pressure deposition is 0.6-2V, pulsed deposition
Current density or voltage and constant current deposition and constant pressure deposition it is consistent.
The constant current sedimentation time is 5-30min, and constant pressure sedimentation time is 5-30min, the burst length of pulsed deposition
For 0.1-2s, pulse number is 10-200 times.
Manganese dioxide-carbon fiber composite material of core-shell structure that the above-mentioned preparation method of the present invention is prepared is also in the present invention
Protection scope in, the manganese dioxide-carbon fiber composite material of core-shell structure by using biological material as raw material prepare
Obtained carbon fiber structural and the manganese dioxide clad composition for being coated on carbon fiber surface, with MnO2The form of@C core-shell structure
In the presence of.
Beneficial effects of the present invention are：
The graphited carbon fiber skeleton of composite material surface of the present invention has splendid electric conductivity, can greatly increase
The electron conduction of material；Manganese dioxide is coated on carbon fiber surface by way of electrochemical deposition, can make full use of fibre
The characteristics of tieing up structure large specific surface area, can satisfy the area requirements of heavy-current discharge；Using carbon fiber as the nucleocapsid of conducting matrix grain
The interfacial contact of structure is complete and sufficient, can be electronics there is no there is the case where individual manganese dioxide does not coat
Transfer enough transfer passages are provided, these are all that traditional preparation method is irrealizable.Meanwhile it is a large amount of in nature
Existing biological material can also guarantee a large amount of preparations of this composite material of core-shell structure.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram piece of biomass-based carbon fiber structural prepared by the embodiment of the present invention 2；
Fig. 2 is manganese dioxide-carbon fiber composite material of core-shell structure scanning electron microscopy prepared by the embodiment of the present invention 2
Mirror picture；
Manganese dioxide-carbon fiber composite material of core-shell structure prepared by Fig. 3 embodiment of the present invention 2 is bent to the electric discharge of lithium metal
Line.
Specific embodiment
Below in conjunction with specific embodiment of the present invention, clear, complete description is carried out to technical solution of the present invention, is shown
So, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the reality in the present invention
Example is applied, every other embodiment obtained by those of ordinary skill in the art without making creative efforts all belongs to
In the scope of protection of the invention.
Embodiment 1
A kind of biomass-based manganese dioxide-carbon fibre composite, is prepared especially by following methods：
1) by stalk 200g, it is placed in dilute hydrochloric acid ultrasonic treatment 2h spare among beaker, being 3mol/L with concentration；
2) obtained raw material are placed in 80 DEG C of drying surface moistures in air dry oven；
3) raw material that step (2) obtains are placed in pipe type sintering furnace, are warming up to 300 DEG C of progress carbonization treatment 8h；
4) it is passed through Ar into pipe type sintering furnace to be protected, and temperature is warming up to 800 DEG C of further progress carbonization treatments
5h；
5) carbon fibre that step (4) obtains is transferred in high temperature sintering furnace, 1800 DEG C of progress surface graphitization processings；
6) the dense sulfuric acid treatment 2h for the product 12mol/L for obtaining step (5)；
7) product that step (6) obtains is dispersed in the mixed solution of second alcohol and water, is then filtered, obtain thickness
For the carbon fiber self-crosslinking film of 1mm；
8) weighing quality is that 24.5 grams of manganese acetate is dissolved in 1000 milliliters of aqueous solution, and electro-deposition is spare；
9) using obtained carbon-fiber film as working electrode, platinized platinum is used as to electrode and reference electrode, is deposited using constant current
Mode carry out the electro-deposition of manganese dioxide；
10) deposition current is 10 milliamperes every square centimeter, and sedimentation time is 15 minutes；
11) step (10) is obtained into sedimentation products and is placed in 80 DEG C of dry 2h in air dry oven, be subsequently placed in Muffle furnace
350 DEG C of annealing 4h are to get manganese dioxide-carbon fiber composite material of core-shell structure.
Using the manganese dioxide being prepared-carbon fiber composite material of core-shell structure as anode, lithium metal adds as cathode
Enter corresponding electrolyte composition lithium-manganese dioxide primary battery and carries out discharge test.Discharge current density is 200mAg- as the result is shown
When 1, blanking voltage 1.0V, specific discharge capacity 205mAh/g shows biggish capacity advantage.
Embodiment 2
A kind of biomass-based manganese dioxide-carbon fibre composite, is prepared especially by following methods：
1) by long-staple cotton 100g, it is placed in dilute hydrochloric acid ultrasonic treatment 2h spare among beaker, being 3mol/L with concentration；
2) raw material that step (1) obtains are placed in 80 DEG C of drying surface moistures in air dry oven；
3) raw material that step (2) obtains are placed in pipe type sintering furnace, are warming up to 350 DEG C of progress carbonization treatment 5h；
4) N is passed through into pipe type sintering furnace2It is protected, and temperature is warming up to 700 DEG C of further progress carbonization treatments
5h；
5) carbon fibre that step (4) obtains is transferred in high temperature sintering furnace, 2100 DEG C of progress surface graphitization processings；
6) the dense sulfuric acid treatment 1h for the product 18.4mol/L for obtaining step (5)；
7) product that step (6) obtains is dispersed in ethanol solution, is then filtered, obtained with a thickness of 0.5mm's
Carbon fiber self-crosslinking film, as shown in Figure 1；
8) weighing quality is that 24.5 grams of manganese acetate is dissolved in 100 milliliters of aqueous solution, and electro-deposition is spare；
9) using carbon-fiber film as working electrode, platinized platinum is used as to electrode and reference electrode；By the way of constant pressure deposition
Carry out the electro-deposition of manganese dioxide；
10) deposition voltage is 1.6V, and sedimentation time is 10 minutes；
11) sedimentation products that step (10) obtains are placed in 80 DEG C of dry 2h in air dry oven, are subsequently placed in Muffle furnace
In 350 DEG C of annealing 4h to get manganese dioxide-carbon fiber composite material of core-shell structure, as shown in Figure 2.
Using the manganese dioxide being prepared-carbon fiber composite material of core-shell structure as anode, lithium metal adds as cathode
Enter corresponding electrolyte composition lithium-manganese dioxide primary battery and carries out discharge test.As shown in figure 3, discharge current is close as the result is shown
Degree is 200mAg-1, when blanking voltage 1.0V, specific discharge capacity 230mAh/g, capacity is than the MnO that obtains under normal condition2Have
Greater advantage.
Embodiment 3
A kind of biomass-based manganese dioxide-carbon fibre composite, is prepared especially by following methods：
1) by bagasse 250g, it is placed in dilute hydrochloric acid ultrasonic treatment 4h spare among beaker, being 1mol/L with concentration；
2) raw material that step (1) obtains are placed in 90 DEG C of drying surface moistures in air dry oven；
3) raw material that step (2) obtains are placed in pipe type sintering furnace, are warming up to 300 DEG C of progress carbonization treatment 5h；
4) N is passed through into pipe type sintering furnace2It is protected, and temperature is warming up to 750 DEG C of further progress carbonization treatments
5h；
5) carbide that step (4) obtains is transferred in high temperature sintering furnace, 2500 DEG C of progress surface graphitization processings；
6) the dense sulfuric acid treatment 1h for the product 18.4mol/L for obtaining step (5)；
7) the product dispersion obtained step (6) in aqueous solution, is then filtered to obtain the carbon fiber with a thickness of 2.5mm
Tie up self-crosslinking film；
8) weighing quality is that 24.5 grams of manganese acetate is dissolved in 100 milliliters of aqueous solution, and electro-deposition is spare；
9) using carbon-fiber film as working electrode, platinized platinum is used as to electrode and reference electrode；By the way of constant-current pulse
Carry out the electro-deposition of manganese dioxide；
10) deposition current is 5mA/cm2, and sedimentation time 0.6s, pulse number is 200 times；
11) step (10) is obtained into sedimentation products and is placed in 80 DEG C of dry 2h in air dry oven, be subsequently placed in Muffle furnace
350 DEG C of annealing 4h.
Using the manganese dioxide being prepared-carbon fiber composite material of core-shell structure as anode, lithium metal adds as cathode
Enter corresponding electrolyte composition lithium-manganese dioxide primary battery and carries out discharge test.Discharge current density is 200mAg as the result is shown-1, when blanking voltage 1.0V, specific discharge capacity 210mAh/g, capacity has greater advantage.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (9)
1. a kind of preparation method of biomass-based manganese dioxide-carbon fibre composite, which is characterized in that include the following steps：
1) biological material is handled into 1-2h using dilute hydrochloric acid, is placed in air dry oven and dries surface moisture；
2) obtained biological material is placed in pipe type sintering furnace, is warming up to 300-350 DEG C of progress carbonization treatment 5-8h, Xiang Guan
Ar or N is passed through in formula sintering furnace2It is protected, is continuously heating to 800-1000 DEG C of further progress carbonization treatment 5h, then rise
Up to 1550-1800 DEG C progress surface graphitization processing；
3) graphitized fibre obtained is placed in progress acidification 8-12h in the concentrated sulfuric acid, is scattered in water and/or organic solvent,
Carbon-fiber film is made in vacuum filtration or dissolution volatilization；
4) using carbon-fiber film as working electrode, platinized platinum is as the electro-deposition for carrying out manganese dioxide to electrode and reference electrode；
5) the electro-deposition product obtained is placed in 80-100 DEG C of dry 2h in air dry oven, is placed in Muffle furnace at 250-800 DEG C
Under the conditions of make annealing treatment.
2. preparation method according to claim 1, which is characterized in that the biological material is selected from stalk, sawdust, length
Suede cotton, bagasse or rice chaff.
3. preparation method according to claim 1, which is characterized in that the concentration of the dilute hydrochloric acid is 1-3mol/L, institute
The concentrated sulfuric acid concentration stated is 12~18.4mol/L.
4. preparation method according to claim 1, which is characterized in that the electro-deposition uses the water containing manganese cation
Or organic solution, as electric depositing solution, the concentration of manganese cation is 0.01-1mol/L.
5. preparation method according to claim 1, which is characterized in that the mode of the electro-deposition using constant current deposition,
Constant pressure deposition or pulsed deposition.
6. preparation method according to claim 5, which is characterized in that the current density of the constant current deposition is 1-
10mA/cm2, the voltage of constant pressure deposition is 0.6-2V, and the current density or voltage and constant current deposition and constant pressure of pulsed deposition are heavy
Product is consistent.
7. preparation method according to claim 5, which is characterized in that the constant current sedimentation time is 5-30min, constant pressure
Sedimentation time is 5-30min, and the burst length of pulsed deposition is 0.1-2s, and pulse number is 10-200 times.
8. biomass-based manganese dioxide-carbon fibre composite is prepared in claim 1 preparation method.
9. biomass-based manganese dioxide-carbon fibre composite according to claim 8, which is characterized in that described two
Manganese oxide-carbon fiber composite material of core-shell structure is by carbon fiber structural and the manganese dioxide clad group for being coated on carbon fiber surface
At with MnO2The form of@C core-shell structure exists.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111933456A (en) * | 2020-08-11 | 2020-11-13 | 苏州柯诺思高新材料有限公司 | MnO (MnO)2Preparation method of/carbon fiber composite electrode and capacitor with same |
| CN113193178A (en) * | 2020-12-07 | 2021-07-30 | 北京服装学院 | Preparation method of manganese dioxide nanosheet coated carbon fiber for supplying power to intelligent clothes |
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| WO2015146915A1 (en) * | 2014-03-28 | 2015-10-01 | 国立大学法人大分大学 | Oxygen electrode catalyst and production method therefor |
| CN105097302A (en) * | 2015-09-15 | 2015-11-25 | 江苏苏通碳纤维有限公司 | Activated carbon fibers for supercapacitor and preparation method therefor |
| CN107978463A (en) * | 2017-12-08 | 2018-05-01 | 天津工业大学 | A kind of preparation method of the ultracapacitor compound porous nanofiber of carbon@manganese dioxide |
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- 2018-07-04 CN CN201810725618.2A patent/CN108899519A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103820883A (en) * | 2014-02-24 | 2014-05-28 | 钟春燕 | Preparation method of bacterial cellulose based carbon nanofibers |
| WO2015146915A1 (en) * | 2014-03-28 | 2015-10-01 | 国立大学法人大分大学 | Oxygen electrode catalyst and production method therefor |
| CN105097302A (en) * | 2015-09-15 | 2015-11-25 | 江苏苏通碳纤维有限公司 | Activated carbon fibers for supercapacitor and preparation method therefor |
| CN107978463A (en) * | 2017-12-08 | 2018-05-01 | 天津工业大学 | A kind of preparation method of the ultracapacitor compound porous nanofiber of carbon@manganese dioxide |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111933456A (en) * | 2020-08-11 | 2020-11-13 | 苏州柯诺思高新材料有限公司 | MnO (MnO)2Preparation method of/carbon fiber composite electrode and capacitor with same |
| CN113193178A (en) * | 2020-12-07 | 2021-07-30 | 北京服装学院 | Preparation method of manganese dioxide nanosheet coated carbon fiber for supplying power to intelligent clothes |
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