CN105778497B - A kind of bacteria cellulose/manganese dioxide/composite polypyrrole film and preparation method thereof - Google Patents

A kind of bacteria cellulose/manganese dioxide/composite polypyrrole film and preparation method thereof Download PDF

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Publication number
CN105778497B
CN105778497B CN201610262358.0A CN201610262358A CN105778497B CN 105778497 B CN105778497 B CN 105778497B CN 201610262358 A CN201610262358 A CN 201610262358A CN 105778497 B CN105778497 B CN 105778497B
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bacteria cellulose
manganese dioxide
polypyrrole
composite
film
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CN105778497A (en
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孙东平
顾焱
自强
孙汴京
朱春林
杨加志
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Nanjing University of Science and Technology
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Nanjing University of Science and Technology
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00Compounds of manganese
    • C01G45/02Oxides; Hydroxides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0605Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0611Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/16Applications used for films

Abstract

The invention discloses a kind of bacteria cellulose/manganese dioxide/composite polypyrrole film and preparation method thereof.Described composite membrane is soaked, after the pretreatment that cleans by cotton-shaped bacteria cellulose through alkali, obtains manganese dioxide and polypyrrole after adding potassium permanganate and the oxidized reduction of pyrroles, final filter is made.The present invention prepares the polypyrrole of film forming, low toxicity evil using air stability is good, is easy to electrochemistry, the manganese dioxide of good capacitive properties is shown in the aqueous electrolyte of neutrality, under wider potential window, and the progress of high-strength material bacteria cellulose is compound, method is simple and easy.Polypyrrole is supported on bacteria cellulose, enhances the electric conductivity of film, while the capacitive properties that manganese dioxide is good, further increases the electrical properties of composite membrane.Bacteria cellulose/manganese dioxide/composite polypyrrole film of the present invention can be applied in the fields such as lithium ion battery negative material, ultracapacitor, electronic device and biology sensor covering material.

Description

A kind of bacteria cellulose/manganese dioxide/composite polypyrrole film and preparation method thereof
Technical field
The present invention relates to a kind of bacteria cellulose/manganese dioxide/composite polypyrrole film and preparation method thereof, belong to material system Standby technical field.
Background technology
Cellulose is mainly derived from the photosynthesis of plant, artificial synthesized and bacterial fermentation.Photosynthesis of plant synthesis Cellulose need to could be applied with lignin and hemicellulose impurity through the pretreatment of complexity.Artificial synthesized cellulose is due to it The degree of polymerization is relatively low, and utilization rate is low.Bacteria cellulose (BC) is bacterial secretory thing, is formed by simple glucose polycondensation, its fiber Content and the degree of polymerization are all higher, and without impurity such as lignin.
In recent years, various methods are used for compound, such as doping, Surface coating and training in situ of bacteria cellulose and conductive materials Support.(Haihua Wang, the etc.Preparation and characterization of polypyrrole/ of document 1 cell-ulose fiber conductive composites doped with cationic polyacrylate of different charge density.Cellulose,2015,22:3305-33) report a kind of with cation polypropylene acid Ester is as dopant, FeCl3As oxidant, by the method together with polypyrrole and cellulose doping, prepared micron order Composite has good electric conductivity, but operating condition is difficult to control, and Compound Degree is not high, and the intensity of material is not good enough, system Energy loss is larger during standby.Chinese patent 201310280034.6 discloses a kind of polypyrrole PPy nano-celluloses NCCs The preparation method of compound film electrode material, by plant cellulose successively in NaOH, NaClO and H2SO4Heated in solution, by electricity Composite membrane is made in solution reaction, but this method uses plant cellulose, and pretreatment is numerous and diverse, need to repeatedly heat, be electrolysed, high energy consumption, Influence factor is more, is not easy to manipulate.Chinese patent application 201510323596.3 disclose it is a kind of for sodium-ion battery two Manganese oxide/nitrating carbon fiber anode material and preparation method thereof, bacteria cellulose add Gao Meng after heat treatment is carbonized Sour potassium and nitrogen-containing compound, obtain the conductive composite film containing manganese dioxide, but manganese dioxide is only attached to bacteria cellulose Surface, fail to produce covered effect, while the bacteria cellulose being carbonized loses original intensity, film is easily broken.
In summary, existing cellulose conductive composite film conductive effect is undesirable, and doping is not easy in recombination process Regulation and control, while it is poor mechanical strength to be present, the problems such as being unsuitable for later stage application, therefore develop that a kind of doping effect is good, mechanical strength Excellent composite membrane is very necessary.
The content of the invention
For deficiency of the prior art, the invention provides a kind of bacteria cellulose/manganese dioxide/composite polypyrrole film And preparation method thereof, manganese dioxide and polypyrrole are dispersed in cotton-shaped bacteria cellulose matrix in the composite membrane, are improved The stability and resistance homogeneity of the electric conductivity of composite membrane, maintain the mechanical strength of cotton-shaped bacteria cellulose matrix.
Technical scheme is as follows:
A kind of bacteria cellulose/manganese dioxide/composite polypyrrole film, described composite membrane pass through with cotton-shaped bacteria cellulose For matrix, soaked, after the pretreatment that cleans through alkali, add liquor potassic permanganate and oxidizable pyrrole is reduced into manganese dioxide and poly- pyrrole Cough up, it is final filter after be made, polypyrrole in described composite membrane, that manganese dioxide is dispersed in bacteria cellulose is nanofiber-based In body, potassium permanganate and the mass ratio of pyrroles are 1 in described composite membrane:2~10, the quality of bacteria cellulose and potassium permanganate Than for 1:10~20.
In above-mentioned composite membrane, polypyrrole stability is good, is easy to electrochemistry prepares film forming and low toxicity evil, and manganese dioxide is in neutrality Aqueous electrolyte in, show good capacitive properties under wider potential window, composite membrane have preferable hydrophily with And mechanical strength.
A kind of preparation method of bacteria cellulose/manganese dioxide/composite polypyrrole film, using cotton-shaped bacteria cellulose, Alkali process is decolourized, potassium permanganate and pyrroles, potassium permanganate and pyrroles's oxygen are added in the pretreated cotton-shaped bacteria cellulose that cleans Change is reduced into manganese dioxide and polypyrrole, and ultrasonic agitation is sufficiently mixed bacteria cellulose, manganese dioxide and polypyrrole, finally taken out Film forming is filtered, is comprised the following steps that:
Step 1, cotton-shaped bacteria cellulose is dried after alkali process is decolourized, cleaned;
Step 2, it is 1 by potassium permanganate and the mass ratio of pyrroles:2~10, the mass ratio of bacteria cellulose and potassium permanganate For 1:10~20 add pyrroles and the bacteria cellulose dried in the liquor potassic permanganate that mass concentration is 0.2%~1%, surpass Sound stirring reaction, it is sufficiently mixed bacteria cellulose, manganese dioxide and polypyrrole;
Step 3, the mixed liquor obtained by step 2 is filtered under diminished pressure, bacteria cellulose/manganese dioxide/polypyrrole is made Composite membrane.
In step 1, described bacteria cellulose film is by after gluconobacter sp dynamic fermentation, sterilized, removal of impurities and decolouring The obtained cotton-shaped bacteria cellulose of solid-state, described drying time are 2~5h.
In step 2, described ultrasonic time is 20~30min.
In step 3, used filtering surface density is 10~15g/m2
The present invention is fine with the film-form bacterium of static culture by the use of dispersed preferably cotton-shaped bacteria cellulose as raw material Dimension element is compared, and the cotton-shaped bacteria cellulose possesses bigger specific surface area, and it is compound more uniformly tight with manganese dioxide, polypyrrole It is close, it is difficult for drop-off after compound;Using potassium permanganate oxidation, reduzate manganese dioxide is directly carried in matrix.In composite membrane, Manganese dioxide is coated by polypyrrole, causes monolithic membrane to have electrically conductive property, two panels film is simultaneously in use, can realize good again Capacitive properties.The nitrogen-containing functional group that bacteria cellulose and polypyrrole surface are enriched in composite membrane causes polypyrrole as crosslinking Agent provides more tie points for the connection of cellulose, so as to improve the intensity of cellulose membrane matrix.Polypyrrole, titanium dioxide Manganese is dispersed in bacteria cellulose film matrix, and this design feature make it that the electric conductivity of fiber is more stable, and resistance is more Uniformly.Composite membrane has tridimensional nano net structure, and fibre diameter is homogeneous, and has adjustability, good biocompatibility, can apply In lithium ion battery negative material, ultracapacitor, organizational project and biology sensor covering material.
Brief description of the drawings
Fig. 1 is thin made from regenerated cellulose/manganese dioxide/composite polypyrrole film, membranaceous bacteria cellulose and embodiment 1 The infrared figure of fungin/manganese dioxide/composite polypyrrole film.
Fig. 2 is bacteria cellulose/manganese dioxide/composite polypyrrole film (b) made from bacteria cellulose (a) and embodiment 2 SEM figure.
Fig. 3 is that bacteria cellulose/manganese dioxide/composite polypyrrole film that embodiment 3 obtains carries out charge-discharge test result Figure.
Fig. 4 is the cyclic voltammetry curve figure for bacteria cellulose/manganese dioxide/composite polypyrrole film that embodiment 4 obtains.
Fig. 5 is different KMnO4Bacteria cellulose/manganese dioxide of content/composite polypyrrole film mechanical strength test curve Figure.
Embodiment
The invention will be further described with accompanying drawing with reference to embodiments.
Embodiment 1
Crude product bacteria cellulose obtained by dynamic fermentation is put into 1mol/L NaOH and boiled 60 minutes, is washed with deionized water Only until cellulose becomes white, dry 2 hours.
It is to add pyrroles 2g in 0.2% liquor potassic permanganate in 500ml mass concentration, is stirred, during this, pyrrole Cough up and polymerize to form polypyrrole by potassium permanganate oxidation, potassium permanganate is reduced into manganese dioxide.Added into above-mentioned mixed liquor dry Dry bacteria cellulose 0.1g, ultrasonic agitation mixing 20min, finally give well mixed bacteria cellulose/manganese dioxide/poly- Pyrroles's mixed liquor.Mixed liquor is finally subjected to negative pressure filtration, filtering surface density is 10g/m2, filtered with 75% alcohol flushing gained Cake until filtrate become colorless it is transparent, and pH in neutrality, finally be made bacteria cellulose/manganese dioxide/composite polypyrrole film.
Bacteria cellulose/the manganese dioxide obtained to embodiment 1/composite polypyrrole film carries out IR Characterization, as a result such as Fig. 1 It is shown.In Fig. 1, BC represents bacteria cellulose, and RBC represents regenerated cellulose, and PPy represents polypyrrole.It is it can be seen that thin In the infrared peak of fungin/manganese dioxide/polypyrrole, compared with simple bacteria cellulose, in 3417cm-1Place C-O is flexible to shake Dynamic peak broaden and respective strengths change show that the hydrogen bond in BC is interfered, it is shown that it is strong between BC and manganese dioxide Strong interaction.Meanwhile compared with simple BC, composite membrane is in 1300cm-1There are obvious C-N stretching vibration peaks in left and right, says Bright BC has loaded the interaction between polypyrrole and polypyrrole and BC.With regenerated cellulose (wood fibre under similarity condition Element dissolving gained) it is matrix, composite manganese dioxide and polypyrrole obtain regenerated cellulose/manganese dioxide/composite polypyrrole film, its Infared spectrum and simple BC are close, illustrate that the composite effect of regenerated cellulose is bad.
Embodiment 2
Crude product bacteria cellulose obtained by dynamic fermentation is put into 1mol/L NaOH and boiled 60 minutes, is washed with deionized water Only until cellulose becomes white, dry 4 hours.
Pyrroles 5g is added in the liquor potassic permanganate that 200ml mass concentrations are 0.5%, is stirred, during this, pyrrole Cough up and polymerize to form polypyrrole by potassium permanganate oxidation, potassium permanganate is reduced into manganese dioxide.Added into above-mentioned mixed liquor dry Dry bacteria cellulose 0.07g, ultrasonic agitation mixing 25min, finally give well mixed bacteria cellulose/manganese dioxide/ Polypyrrole mixed liquor.Mixed liquor is finally subjected to negative pressure filtration, filtering surface density is 15g/m2, with 75% alcohol flushing gained Filter cake until filtrate become colorless it is transparent, and pH in neutrality, finally be made bacteria cellulose/manganese dioxide/composite polypyrrole film.
Original BC and composite membrane microscopic appearance are observed under ESEM, as a result as shown in Fig. 2 wherein a is original BC Shape appearance figure, b are bacteria cellulose/manganese dioxide/composite polypyrrole film shape appearance figure.Show that original BC films surface can see that in figure Obvious bacteria cellulose texture, bacteria cellulose/manganese dioxide/composite polypyrrole film surface is by one layer of fine and close polypyrrole film Covered, the surface of polypyrrole film is uniformly coated with the manganese dioxide particle of aggregation.
Embodiment 3
Crude product bacteria cellulose obtained by dynamic fermentation is put into 1mol/L NaOH and boiled 60 minutes, is washed with deionized water Only until cellulose becomes white, dry 5 hours.
Pyrroles 10g is added in 100ml mass concentrations are 1% liquor potassic permanganate, is stirred, during this, pyrroles It is polymerize to form polypyrrole by potassium permanganate oxidation, potassium permanganate is reduced into manganese dioxide.Drying is added into above-mentioned mixed liquor Bacteria cellulose 0.05g, ultrasonic agitation mixing 20min, finally give well mixed bacteria cellulose/manganese dioxide/poly- Pyrroles's mixed liquor.Mixed liquor is finally subjected to negative pressure filtration, filtering surface density is 10g/m2, filtered with 75% alcohol flushing gained Cake until filtrate become colorless it is transparent, and pH in neutrality, finally be made bacteria cellulose/manganese dioxide/composite polypyrrole film.
Charge-discharge test is carried out to obtained bacteria cellulose/manganese dioxide/composite polypyrrole film, detects its electrical property Matter, as a result as shown in figure 3, shown in charge-discharge test figure, as a result show that the composite membrane has larger initial capacitance.
Embodiment 4
Crude product bacteria cellulose obtained by dynamic fermentation is put into 1mol/L NaOH and boiled 60 minutes, is washed with deionized water Only until cellulose becomes white, dry 2 hours.
Pyrroles 4g is added in the liquor potassic permanganate that 200ml mass concentrations are 0.5%, is stirred, during this, pyrrole Cough up and polymerize to form polypyrrole by potassium permanganate oxidation, potassium permanganate is reduced into manganese dioxide.Added into above-mentioned mixed liquor dry Dry gained bacteria cellulose 0.1g, ultrasonic agitation mixing 30min, finally give well mixed bacteria cellulose/manganese dioxide/ Polypyrrole mixed liquor.Mixed liquor is finally subjected to negative pressure filtration, filtering surface density is 15g/m2, with 75% alcohol flushing gained Filter cake until filtrate become colorless it is transparent, and pH in neutrality, finally be made bacteria cellulose/manganese dioxide/composite polypyrrole film.
Gained composite membrane is subjected to cyclic voltammetry, as a result as shown in Figure 4.It can be seen that display window compared with Greatly, and overall shape is close to rectangle, illustrates that composite membrane electrochemical properties are stable.
Change KMnO in composite membrane4Content, gained composite membrane is subjected to mechanical strength test, as a result as shown in Figure 5.From figure In as can be seen that composite membrane elongation at break and tensile strength with KMnO4The increase of content is in a slight decrease, but reduces Degree unobvious.When potassium permanganate incorporation is 1.0g, composite membrane tensile strength is 13.88MPa, and elongation at break is 25.1%, illustrate that the preparation method of the present invention can be very good to keep the original mechanical strength of bacteria cellulose.

Claims (5)

1. a kind of bacteria cellulose/manganese dioxide/composite polypyrrole film, it is characterised in that described composite membrane passes through with cotton-shaped Bacteria cellulose is matrix, is soaked, after the pretreatment that cleans through alkali, adds liquor potassic permanganate and oxidizable pyrrole is reduced into titanium dioxide Manganese and polypyrrole, it is made after finally filtering, polypyrrole, manganese dioxide are dispersed in bacteria cellulose and received in described composite membrane In rice fibrous matrix, potassium permanganate and the mass ratio of pyrroles are 1 in described composite membrane:2~10, bacteria cellulose and permanganic acid The mass ratio of potassium is 1:10~20.
2. the preparation method of bacteria cellulose/manganese dioxide/composite polypyrrole film according to claim 1, its feature exist In comprising the following steps that:
Step 1, cotton-shaped bacteria cellulose is dried after alkali process is decolourized, cleaned;
Step 2, it is 1 by potassium permanganate and the mass ratio of pyrroles:2~10, the mass ratio of bacteria cellulose and potassium permanganate is 1: 10~20 add pyrroles and the bacteria cellulose dried in the liquor potassic permanganate that mass concentration is 0.2%~1%, and ultrasound is stirred Reaction is mixed, is sufficiently mixed bacteria cellulose, manganese dioxide and polypyrrole;
Step 3, the mixed liquor obtained by step 2 is filtered under diminished pressure, it is compound that bacteria cellulose/manganese dioxide/polypyrrole is made Film.
3. the preparation method of bacteria cellulose/manganese dioxide/composite polypyrrole film according to claim 2, its feature exist In in step 1, described cotton-shaped bacteria cellulose is by being made after gluconobacter sp dynamic fermentation, sterilized, removal of impurities and decolouring The cotton-shaped bacteria cellulose of solid-state, described drying time is 2~5h.
4. the preparation method of bacteria cellulose/manganese dioxide/composite polypyrrole film according to claim 2, its feature exist In in step 2, described ultrasonic time is 20~30min.
5. the preparation method of bacteria cellulose/manganese dioxide/composite polypyrrole film according to claim 2, its feature exist In in step 3, used filtering surface density is 10~15g/m2
CN201610262358.0A 2016-04-25 2016-04-25 A kind of bacteria cellulose/manganese dioxide/composite polypyrrole film and preparation method thereof Expired - Fee Related CN105778497B (en)

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CN108772050B (en) * 2018-04-27 2021-03-23 长安大学 Adsorbent, preparation method and application thereof
CN109384953A (en) * 2018-09-26 2019-02-26 德清舒华泡沫座椅有限公司 A kind of bacteria cellulose sponges of conductive modified

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Publication number Priority date Publication date Assignee Title
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CN103014888A (en) * 2012-10-25 2013-04-03 中原工学院 Preparation method of bacterial cellulose based power generation fibers and yarns
CN104993111A (en) * 2015-06-12 2015-10-21 中南大学 Manganese dioxide/nitrating carbon fiber cathode composite material for sodium-ion battery and preparing method thereof
CN105070527A (en) * 2015-08-27 2015-11-18 桂林理工大学 Preparation method of graphene/polypyrrole/manganese-dioxide three-element composite electrode material
CN105428080A (en) * 2015-12-25 2016-03-23 哈尔滨工业大学 Preparation method for bacterial cellulose based polypyrrole/graphene flexible electrode material and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102219997A (en) * 2011-04-29 2011-10-19 南京理工大学 Method for preparing polypyrrole coated bacterial cellulose nanometer electric-conduction composite material by utilizing bacterial cellulose as template
CN103014888A (en) * 2012-10-25 2013-04-03 中原工学院 Preparation method of bacterial cellulose based power generation fibers and yarns
CN104993111A (en) * 2015-06-12 2015-10-21 中南大学 Manganese dioxide/nitrating carbon fiber cathode composite material for sodium-ion battery and preparing method thereof
CN105070527A (en) * 2015-08-27 2015-11-18 桂林理工大学 Preparation method of graphene/polypyrrole/manganese-dioxide three-element composite electrode material
CN105428080A (en) * 2015-12-25 2016-03-23 哈尔滨工业大学 Preparation method for bacterial cellulose based polypyrrole/graphene flexible electrode material and application thereof

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