CN102694139A - Bacterial cellulose-Nafion sandwich proton exchange membrane and preparation and application thereof - Google Patents
Bacterial cellulose-Nafion sandwich proton exchange membrane and preparation and application thereof Download PDFInfo
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- CN102694139A CN102694139A CN2012101624446A CN201210162444A CN102694139A CN 102694139 A CN102694139 A CN 102694139A CN 2012101624446 A CN2012101624446 A CN 2012101624446A CN 201210162444 A CN201210162444 A CN 201210162444A CN 102694139 A CN102694139 A CN 102694139A
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- 239000012528 membrane Substances 0.000 title claims abstract description 72
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- 230000001580 bacterial effect Effects 0.000 title abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 87
- 238000001035 drying Methods 0.000 claims abstract description 23
- 239000000446 fuel Substances 0.000 claims abstract description 17
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 10
- 241000894006 Bacteria Species 0.000 claims description 137
- 239000001913 cellulose Substances 0.000 claims description 106
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- 239000002131 composite material Substances 0.000 claims description 49
- 238000012545 processing Methods 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
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- 239000001963 growth medium Substances 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 10
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- 239000007864 aqueous solution Substances 0.000 claims description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 238000007654 immersion Methods 0.000 claims description 5
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- 239000002253 acid Substances 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 230000001788 irregular Effects 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 206010013786 Dry skin Diseases 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 235000010338 boric acid Nutrition 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229940072033 potash Drugs 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000004334 sorbic acid Substances 0.000 claims description 2
- 235000010199 sorbic acid Nutrition 0.000 claims description 2
- 229940075582 sorbic acid Drugs 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims 1
- 230000035699 permeability Effects 0.000 abstract description 13
- 238000009835 boiling Methods 0.000 abstract description 11
- 229920002749 Bacterial cellulose Polymers 0.000 abstract description 9
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- 238000005406 washing Methods 0.000 abstract description 2
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- 238000010521 absorption reaction Methods 0.000 description 30
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- 239000004033 plastic Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 4
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001875 compounds Chemical group 0.000 description 3
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- 239000002184 metal Substances 0.000 description 2
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- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Separation Using Semi-Permeable Membranes (AREA)
- Apparatus Associated With Microorganisms And Enzymes (AREA)
Abstract
The invention relates to a bacterial cellulose-Nafion sandwich proton exchange membrane. The sandwich proton exchange membrane is in a BC-Nafion-BC or Nafion-BC-Nafion structure. The preparation comprises the following steps: soda boiling and washing the bacterial cellulose membrane to acquire a gel-like bacterial cellulose membrane; stacking the gel-like bacterial cellulose membrane, the treated Nafion membrane and the gel-like bacterial cellulose membrane in sequence, or stacking the treated Nafion membrane, the gel-like bacterial cellulose membrane and the treated Nafion membrane in sequence, or drying and soaking the gel-like bacterial cellulose membrane in a Nafion solution, drying the soaked bacterial cellulose membrane; and finally toughening the dried bacterial cellulose membrane. According to the invention, the sandwich proton exchange membrane has lower methanol permeability, higher proton conductivity and high thermal stability, and a good application prospect in a methanol fuel cell. The preparation process is simple and easy, and has little pollution to the environment.
Description
Technical field
The invention belongs to PEM and preparation thereof and application, the sandwich PEM of particularly a kind of bacteria cellulose-Nafion and preparation and application.
Background technology
DMFC (DMFC) is a types of fuel cells newly developed in recent years.It acts as a fuel with methanol aqueous solution, and methyl alcohol oxidation under the effect of anode catalyst generates CO
2, discharging electronics and proton simultaneously, both conduct to negative electrode through external circuit and film respectively.At negative electrode by O
2Electrochemical reduction consumes the electronics that passes over from external circuit, and combines to generate water with proton.Electronics through loading to the transmission of negative electrode, is realized the conversion of chemical energy to electrical energy from anode.It is abundant that DMFC has the methanol fuel source, low price, and theoretical specific energy density is high; Be easy to carry and store, simple in structure, volume is little; Light weight, advantage such as convenient, flexible is particularly suitable for being applied to compact power; For example notebook computer, mobile phone, video camera, small-sized independent current sources such as remote districts, island desert, and the particular power source of using in the military field etc.The PEM that is adopted among the DMFC at present remains perfluoro sulfonic acid membrane, like
series membranes of Dupond company.Yet, high cost (about US$3000kg
-1), produce the poisonous and hazardous intermediate product of environment in the synthetic difficulty, manufacture process, and the high methanol permeability that when be used for DMFC, exists and the loss that contains the Ru catalyst have greatly restricted its application.Therefore, development of new low cost, high proton conductivity, low methanol permeability, eco-friendly PEM become the focus and the important directions of DMFC research.
(Bacterial Cellulose is one type of cellulose that is formed by microbial fermentation BC) to bacteria cellulose, is applied to aspects such as food, medicine, papermaking, sound equipment and textile industry mainly as a kind of biomaterial.Yet; Bacteria cellulose film has special three-dimensional manometer network configuration, ultra-fine silk ribbon and Heat stability is good and characteristics such as the high and low gas permeability of mechanical strength, high-hydroscopicity, makes bacteria cellulose film on Proton Exchange Membrane Fuel Cells, have fine application prospect.American scholar has been carried out preliminary discussion to it, and result of study shows that bacteria cellulose film uses and have unique advantage aspect fuel cell.Yet the proton conductivity of bacteria cellulose film is lower, need carry out modification and improve its proton conductivity.Simultaneously, existing research shows that bacteria cellulose film can be used for the mixture that infiltration evaporation separates alcohols and water, proves that it has alcohol-resistant performance.
Summary of the invention
Technical problem to be solved by this invention provides the sandwich PEM of a kind of bacteria cellulose-Nafion and preparation and application; The sandwich composite membrane of bacteria cellulose-Nafion of the present invention has higher proton conductivity, thermal stability, low methanol permeability preferably; Be a kind of sandwich structure compound proton exchange membrane of novel low-cost, be particularly suitable for methyl alcohol, ethanol etc. and be the fuel liquid battery of fuel that preparation is simple for this; With low cost, environmental pollution is little.
The sandwich PEM of a kind of bacteria cellulose-Nafion of the present invention, this sandwich PEM are BC-Nafion-BC structure or Nafion-BC-Nafion structure.
The preparation method of the sandwich PEM of a kind of bacteria cellulose-Nafion of the present invention comprises:
(1) bacteria cellulose film is used deionized water rinsing; Remove impurity such as residual culture medium; Under 70-100 ℃, place the alkaline solution of mass concentration 0.1-5% to handle 0.5-4h then; It is translucent to become white until bacteria cellulose film, uses acid solution and the washed with de-ionized water (or using washed with de-ionized water separately) of mass concentration 0.1-3% again, in deionized water, boils 0.5-2h then; Till using deionized water rinsing to bacteria cellulose film pH value as neutrality again, obtain gelatinous bacteria cellulose film; Simultaneously, get the above-mentioned leachate that boils and measure it,, then repeat to boil and wash until boiling leachate till 280nm does not have remarkable absorption if absorption value is not less than 0.05 in the absorption value of 280nm; The bacteria cellulose film that purification process is good places deionized water, seals 4 ° of C and preserves;
(2) the Nafion film is boiled with the dilute sulfuric acid of the hydrogen peroxide solution of mass concentration 3%, deionized water, 1mol/L and deionized water successively handle 1h, the Nafion film that obtains handling places deionized water to preserve;
(3) the Nafion film with above-mentioned processing is cut into the shape slightly littler than gelatinous bacteria cellulose film, the Nafion film of on the container of Teflon coating, stack gelatinous bacteria cellulose film successively then, handling and gelatinous bacteria cellulose film; When stacking, should notice that the Nafion film and the gelatinous bacteria cellulose film of both sides up and down fit tightly, and prevent the generation of bubble; Drying and forming-film then promptly obtains the sandwich composite membrane of bacteria cellulose-Nafion of BC-Nafion-BC structure;
Perhaps the Nafion film with above-mentioned processing is cut into the shape slightly littler than gelatinous bacteria cellulose film, the Nafion film that on the container of Teflon coating, stacks the Nafion film of handling, gelatinous bacteria cellulose film successively and handled then; When stacking, should notice that the Nafion film and the gelatinous bacteria cellulose film of both sides up and down fit tightly, and prevent the generation of bubble; Drying and forming-film then promptly obtains the sandwich composite membrane of bacteria cellulose-Nafion of Nafion-BC-Nafion structure;
Perhaps, obtain the bacteria cellulose dry film with after the gelatinous bacteria cellulose film drying; After the irregular part in described bacteria cellulose dry film edge reduced; Be soaked in 5-15min in the Nafion solution of mass concentration 0.1-20%; Then in 90-110 ° of C baking 10-30min; Repeat step 1-9 time of above-mentioned immersion oven dry again, promptly obtain the sandwich composite membrane of bacteria cellulose-Nafion of Nafion-BC-Nafion structure; Sandwich composite membrane promptly obtains the sandwich composite membrane of malleableize in 110-130 ° of C patent 1-2h.
Alkaline solution described in the step (1) is the aqueous solution of NaOH, potassium hydroxide, potash or sodium carbonate.
Acid solution described in the step (1) is acetic acid, citric acid, oxalic acid, the aqueous solution of benzoic acid, sorbic acid, malic acid, formic acid, boric acid, carbonic acid, silicic acid, sulfurous acid or phosphoric acid.
The said Nafion film of step (3) is business-like Nafion115 film, Nafion212 film or Nafion117 film (Dupond company of Du Pont).
The mode that gelatinous bacteria cellulose film is dry described in the step (3) is oven dry, air-dry or freeze-drying, and remaining drying mode is that room temperature is dried, air-dry or 60 ° of following low temperature dryings of C.
The sandwich PEM of a kind of bacteria cellulose-Nafion of the present invention is applied to hydrogen oxygen fuel cell or is in the fuel liquid battery of fuel with methyl alcohol or ethanol.
The sandwich composite fuel cell PEM of a kind of bacteria cellulose-Nafion of the present invention; Comprise: get the bacteria cellulose film of gathering in the crops behind the bacterial fermentation; After processing such as soda boiling and washing are removed remaining fermentation medium and bacterial cell and obtained purifying cellulose, place that drying obtains the bacteria cellulose dry film on the plate; With the Nafion film successively with 3% hydrogen peroxide solution, deionized water, 1mol/L dilute sulfuric acid and deionized water boil handle 1h after, be cut into the shape slightly littler than gel bacteria cellulose film; On plate, stack gel bacteria cellulose film, Nafion film and gel bacteria cellulose film successively, drying and forming-film then promptly obtains the sandwich composite membrane of bacteria cellulose-Nafion of BC-Nafion-BC structure; Perhaps on plate, stack Nafion film, gel bacteria cellulose film and Nafion film successively, drying and forming-film then promptly obtains the sandwich composite membrane of bacteria cellulose-Nafion of Nafion-BC-Nafion structure; Perhaps get bacteria cellulose dry film (oven dry, air-dry or freeze-drying), it is soaked in the 0.1-20%Nafion solution, takes out 90-110 ° of C oven dry 10-30min, repeat step 1-9 time that above-mentioned immersion dries again.Then above composite membrane is placed under the uniform temperature and dry malleableize, promptly obtain bacteria cellulose-sandwich composite membrane of Nafion malleableize.
The present invention mixes bacteria cellulose with Nafion, in conjunction with the high proton conductivity of Nafion and the alcohol-resistant performance of bacteria cellulose, be applicable to the proton exchange composite membrane of DMFC with preparation.
Beneficial effect
(1) the sandwich composite membrane of bacteria cellulose-Nafion of the present invention has higher proton conductivity, thermal stability, low methanol permeability preferably; Be a kind of sandwich structure compound proton exchange membrane of novel low-cost, be particularly suitable for methyl alcohol, ethanol etc. and be the fuel liquid battery of fuel;
(2) of the present invention preparation is simple, and with low cost, environmental pollution is little.
Description of drawings
Fig. 1 is the ac impedance spectroscopy (Nyquist figure) of the sandwich composite membrane of BC-Nafion115-BC in the embodiment of the invention 1;
Fig. 2 is the ac impedance spectroscopy (Nyquist figure) of the sandwich composite membrane of BC-Nafion212-BC in the embodiment of the invention 2;
Fig. 3 is the methanol permeability testing apparatus figure in the embodiment of the invention 4;
Fig. 4 is the methanol concentration-time changing curve of the sandwich composite membrane of BC-Nafion115-BC in the embodiment of the invention 4;
Fig. 5 is the sandwich composite membrane of the BC-Nafion115-BC in the embodiment of the invention 5 surface SEM Electronic Speculum figure;
Fig. 6 is the sandwich composite membrane section S of the BC-Nafion115-BC in the embodiment of the invention 5 EM Electronic Speculum figure;
Fig. 7 is the sandwich composite membrane of the BC-Nafion212-BC in the embodiment of the invention 6 surface SEM Electronic Speculum figure;
Fig. 8 is the sandwich composite membrane section S of the BC-Nafion212-BC in the embodiment of the invention 6 EM Electronic Speculum figure;
Fig. 9 is the ac impedance spectroscopy (Nyquist figure) of the sandwich composite membrane of individual layer Nafion-BC-Nafion in the embodiment of the invention 7;
Figure 10 is the ac impedance spectroscopy (Nyquist figure) of the sandwich composite membrane of double-deck Nafion-BC-Nafion in the embodiment of the invention 8.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
(1) gets bacteria cellulose film; Use deionized water rinsing, remove impurity such as residual culture medium, place 80 ° of C water bath processing of sodium hydroxide solution 2h of mass percent 1% then; It is translucent to become white until bacteria cellulose film; Use washed with de-ionized water again, place deionized water to boil 1h, till taking-up uses deionized water rinsing to bacteria cellulose film surface p H value as neutrality.Simultaneously, get the above-mentioned leachate that boils and measure its 280nm absorption value, if absorption value is not less than 0.05, the step that then repeats to boil and wash is till boiling leachate 280nm and not having remarkable absorption;
(2) the Nafion115 film is boiled processing 1h with 3% hydrogen peroxide solution, deionized water, 1mol/L dilute sulfuric acid and deionized water successively, place deionized water to preserve.
(3) get the Nafion115 film of handling, be cut into the shape slightly littler than gel bacteria cellulose film.On the plastics plate, stack gel bacteria cellulose film, Nafion115 film and gel bacteria cellulose film successively.When stacking, should notice that the Nafion115 film and the gel bacteria cellulose film of both sides up and down fit tightly, and prevent the generation of bubble.The air-dry film forming of room temperature then promptly obtains the sandwich composite membrane of bacteria cellulose-Nafion of BC-Nafion115-BC structure.
Utilize AC impedence method to measure the conductivity of PEM under the room temperature, the i.e. proton conductivity of film then.
Laboratory apparatus: electrochemical workstation CHI760d
Experiment test condition: AC Impedence, frequency scanning scope 1-10
5Hz, amplitude voltage 100mV
Experimental technique:
(1) measures the thickness of modified bacteria cellulose film with micrometer caliper, be recorded as d, the cm of unit;
(2) the sandwich composite membrane of BC-Nafion115-BC is placed the conductivity test module, place 25 ℃ of constant temperature ovens, balance 30min makes the temperature of module and film reach 25 ℃, connects lead, the test AC impedance.Read the impedance R of film according to the AC impedance spectrogram, the Ω of unit, the AC impedance spectrogram is as shown in Figure 1.
(3) according to formula
Wherein l is the distance between the two poles of the earth, and the cm of unit calculates the proton conductivity of membrane, the Scm of unit
-1
Experimental result shows that the thickness of the sandwich composite membrane of BC-Nafion115-BC is 0.018-0.020cm, and AC impedance is 1500-1600 Ω, and proton conductivity can reach 0.01714 ± 0.00006Scm
-1
(1) gets bacteria cellulose film; Use deionized water rinsing, remove impurity such as residual culture medium, place 80 ° of C water bath processing of potassium hydroxide solution 2h of mass percent 1% then; It is translucent to become white until bacteria cellulose film; Use mass concentration 0.1% aqueous acetic acid and washed with de-ionized water again, place deionized water to boil 1h, till taking-up uses deionized water rinsing to bacteria cellulose film surface p H value as neutrality.Simultaneously, get the above-mentioned leachate that boils and measure its 280nm absorption value, if absorption value is not less than 0.05, the step that then repeats to boil and wash is till boiling leachate 280nm and not having remarkable absorption;
(2) the Nafion212 film is boiled processing 1h with 3% hydrogen peroxide solution, deionized water, 1mol/L dilute sulfuric acid and deionized water successively, place deionized water to preserve.
(3) get the Nafion212 film of handling, be cut into the shape slightly littler than gel bacteria cellulose film.On the plastics plate, stack gel bacteria cellulose film, Nafion212 film and gel bacteria cellulose film successively.When stacking, should notice that the Nafion212 film and the gel bacteria cellulose film of both sides up and down fit tightly, and prevent the generation of bubble.Room temperature is dried drying and forming-film then, promptly obtains the sandwich composite membrane of bacteria cellulose-Nafion of BC-Nafion212-BC structure.
Utilize AC impedence method to measure the conductivity of PEM under the room temperature, the i.e. proton conductivity of film.
Laboratory apparatus: electrochemical workstation CHI760d
Experiment test condition: AC Impedence, frequency scanning scope 0.1-10
4Hz, amplitude voltage 100mV
Experimental technique:
(1) measures the thickness of modified bacteria cellulose film with micrometer caliper, be recorded as d, the cm of unit;
(2) the sandwich composite membrane of BC-Nafion212-BC is placed the conductivity test module, place 25 ℃ of constant temperature ovens, balance 30min makes the temperature of module and film reach 25 ℃, connects lead, the test AC impedance.Read the impedance R of film according to the AC impedance spectrogram, the Ω of unit, the AC impedance spectrogram is as shown in Figure 2.
(3) according to formula
Wherein l is the distance between the two poles of the earth, and the cm of unit calculates the proton conductivity of membrane, the Scm of unit
-1
Experimental result shows that the thickness of the sandwich composite membrane of BC-Nafion212-BC is 0.0118cm, and AC impedance is 6500 Ω, and proton conductivity can reach 0.00652Scm
-1
(1) gets bacteria cellulose film; Use deionized water rinsing, remove impurity such as residual culture medium, place 95 ° of C water bath processing of solution of potassium carbonate 1h of mass percent 5% then; It is translucent to become white until bacteria cellulose film; Use mass concentration 0.1% phosphate aqueous solution and washed with de-ionized water again, place deionized water to boil 2h, till taking-up uses deionized water rinsing to bacteria cellulose film surface p H value as neutrality.Simultaneously, get the above-mentioned leachate that boils and measure its 280nm absorption value, if absorption value is not less than 0.05, the step that then repeats to boil and wash is till boiling leachate 280nm and not having remarkable absorption;
(2) Nafion115 film and Nafion212 film are boiled processing 1h with 3% hydrogen peroxide solution, deionized water, 1mol/L dilute sulfuric acid and deionized water successively, place deionized water to preserve.
(3) get Nafion115 film or the Nafion212 film of handling, be cut into the shape slightly littler than gel bacteria cellulose film.On the plastics plate, stack gel bacteria cellulose film, Nafion film and gel bacteria cellulose film successively.When stacking, should notice that the Nafion film and the gel bacteria cellulose film of both sides up and down fit tightly, and prevent the generation of bubble.60 ° of following low temperature drying drying and forming-films of C then promptly obtain the sandwich composite membrane of bacteria cellulose-Nafion of BC-Nafion-BC structure.
The sandwich composite membrane of BC-Nafion115-BC, the sandwich composite membrane of BC-Nafion212-BC and Nafion115 film were soaked in deionized water 3 days, take out its quality of mensuration and be designated as W
WetIn vacuum drying chamber, 60 ° of C dried overnight in the vacuum are taken out weighing and are designated as W then
Dry, calculate the water absorption rate WU of film, the gg of unit then according to following formula
-1: WU=(W
Wet-W
Dry)/W
Dry
Experimental result shows that the water absorption rate of the sandwich composite membrane of BC-Nafion115-BC is 0.283 ± 0.061gg
-1The sandwich composite membrane of BC-Nafion212-BC is 0.342 ± 0.016g g
-1The water absorption rate of Nafion115 film is 0.243 ± 0.102gg
-1
(1) gets bacteria cellulose film; Use deionized water rinsing, remove impurity such as residual culture medium, place 90 ° of C water bath processing of sodium carbonate liquor 2h of mass percent 5% then; It is translucent to become white until bacteria cellulose film; Use mass concentration 0.5% aqueous citric acid solution and washed with de-ionized water again, place deionized water to boil 2h, till taking-up uses deionized water rinsing to bacteria cellulose film surface p H value as neutrality.Simultaneously, get the above-mentioned leachate that boils and measure its 280nm absorption value, if absorption value is not less than 0.05, the step that then repeats to boil and wash is till boiling leachate 280nm and not having remarkable absorption;
(2) the Nafion115 film is boiled processing 1h with 3% hydrogen peroxide solution, deionized water, 1mol/L dilute sulfuric acid and deionized water successively, place deionized water to preserve.
(3) get the Nafion115 film of handling, be cut into the shape slightly littler than gel bacteria cellulose film.On the plastics plate, stack gel bacteria cellulose film, Nafion115 film and gel bacteria cellulose film successively.When stacking, should notice that the Nafion115 film and the gel bacteria cellulose film of both sides up and down fit tightly, and prevent the generation of bubble.Drying and forming-film then promptly obtains the sandwich composite membrane of bacteria cellulose-Nafion of BC-Nafion115-BC structure.
Adopt the barrier film diffusion method to measure methanol permeability, to characterize alcohol-resistant performance.Methanol permeability is low more, and alcohol-resistant performance is good more.
Laboratory apparatus: diffusion cell, magnetic agitation, thermostat water bath, gas chromatograph
GC conditions: Porapak Q packed column, 80-100 order, 2m * 3mm * 2mm, 150 ° of C of column temperature; Fid detector, 250 ° of C of detector temperature; 1 μ L sample size, 200 ° of C of injector temperature; Nitrogen is done carrier gas, flow 15mLmin
-1
Experimental technique:
(1) be assembled into the methanol permeability testing apparatus according to Fig. 3, it is 25 ° of C that the water bath with thermostatic control temperature is set.
(2) the sandwich composite membrane of BC-Nafion115-BC is clipped in the middle of two diffusion cells, clamps with the polytetrafluoroethylene flange.After treating that bath temperature is stable, diffusion cell is put into water-bath.In the A chamber, add the methanol aqueous solution of 300mL 1M rapidly, in the B chamber, add the 300mL deionized water, pick up counting then.
(3) open magnetic stirring apparatus, identical rotating speed is set in the diffusion cell both sides.Every separated 20min gets the sample of 200 μ L from the B chamber, be 200min total diffusion time.
(4) will obtain in the methyl alcohol diffusion samples inject gas chromatograph, according to above-mentioned condition test methanol concentration.
(5) with B chamber methanol concentration to mapping diffusion time, obtain methanol concentration as shown in Figure 4 change curve in time, obtain slope S after the linear regression, again through following formula methanol permeability (P) everywhere:
V wherein
BBe the liquor capacity (mL) of accepting pond B, the l thickness (cm) of wet film that is film in the methanol aqueous solution of certain solution behind the immersion treatment 12h adopts digimatic micrometer to measure, and A is the sectional area (cm of diffusion cell
2), c
ABe the initial concentration (mmol/L) of A side methyl alcohol, S is a slope (mmol/s) of accepting methanol concentration variation straight line among the B of pond, and P is the methanol permeability (cm of film
2/ s).
Experimental result shows the sandwich compound thickness 0.0183cm of BC-Nafion115-BC, and the methanol permeability that calculates is 9.65 * 10
-7Cm
2/ s.
(1) gets bacteria cellulose film; Use deionized water rinsing, remove impurity such as residual culture medium, place 90 ° of C water bath processing of sodium hydroxide solution 1h of mass percent 1% then; It is translucent to become white until bacteria cellulose film; Use washed with de-ionized water again, place deionized water to boil 1h, till taking-up uses deionized water rinsing to bacteria cellulose film surface p H value as neutrality.Simultaneously, get the above-mentioned leachate that boils and measure its 280nm absorption value, if absorption value is not less than 0.05, the step that then repeats to boil and wash is till boiling leachate 280nm and not having remarkable absorption;
(2) the Nafion115 film is boiled processing 1h with 3% hydrogen peroxide solution, deionized water, 1mol/L dilute sulfuric acid and deionized water successively, place deionized water to preserve.
(3) get the Nafion115 film of handling, be cut into the shape slightly littler than gel bacteria cellulose film.On the plastics plate, stack gel bacteria cellulose film, Nafion115 film and gel bacteria cellulose film successively.When stacking, should notice that the Nafion115 film and the gel bacteria cellulose film of both sides up and down fit tightly, and prevent the generation of bubble.Drying and forming-film then promptly obtains the sandwich composite membrane of bacteria cellulose-Nafion of BC-Nafion115-BC structure.
Get the sandwich composite membrane of BC-Nafion115-BC and place liquid nitrogen, treat hygral equilibrium after, cast aside disconnectedly with tweezers, obtain smooth cross section.Sample is attached on stage surface and the side, in the vacuum sample is carried out metal spraying and handle.In scanning electron microscopy, take its surface and cross section microstructure at last, as illustrated in Figures 5 and 6.
(1) gets bacteria cellulose film; Use deionized water rinsing, remove impurity such as residual culture medium, place 90 ° of C water bath processing of potassium hydroxide solution 1h of mass percent 1% then; It is translucent to become white until bacteria cellulose film; Use washed with de-ionized water again, place deionized water to boil 2h, till taking-up uses deionized water rinsing to bacteria cellulose film surface p H value as neutrality.Simultaneously, get the above-mentioned leachate that boils and measure its 280nm absorption value, if absorption value is not less than 0.05, the step that then repeats to boil and wash is till boiling leachate 280nm and not having remarkable absorption;
(2) the Nafion212 film is boiled processing 1h with 3% hydrogen peroxide solution, deionized water, 1mol/L dilute sulfuric acid and deionized water successively, place deionized water to preserve.
(3) get the Nafion212 film of handling, be cut into the shape slightly littler than gel bacteria cellulose film.On the plastics plate, stack gel bacteria cellulose film, Nafion212 film and gel bacteria cellulose film successively.When stacking, should notice that the Nafion212 film and the gel bacteria cellulose film of both sides up and down fit tightly, and prevent the generation of bubble.Drying and forming-film then promptly obtains the sandwich composite membrane of bacteria cellulose-Nafion of BC-Nafion212-BC structure.
Get the sandwich composite membrane of BC-Nafion212-BC and place liquid nitrogen, treat hygral equilibrium after, cast aside disconnectedly with tweezers, obtain smooth cross section.Sample is attached on stage surface and the side, in the vacuum sample is carried out metal spraying and handle.In scanning electron microscopy, take its surface and cross section microstructure at last, shown in Fig. 7 and 8.
(1) gets bacteria cellulose film; Use deionized water rinsing, remove impurity such as residual culture medium, place 95 ° of C water bath processing of solution of potassium carbonate 2h of mass percent 5% then; It is translucent to become white until bacteria cellulose film; Use washed with de-ionized water again, place deionized water to boil 2h, till taking-up uses deionized water rinsing to bacteria cellulose film surface p H value as neutrality.Simultaneously, get the above-mentioned leachate that boils and measure its 280nm absorption value, if absorption value is not less than 0.05, the step that then repeats to boil and wash is till boiling leachate 280nm and not having remarkable absorption.The bacteria cellulose film that purification process is good places deionized water, and 4 ° of C seal preservation.
(2) gelatinous bacteria cellulose film is placed on the plastics plate, 60 ° of C dryings obtain the bacteria cellulose dry film.
(3) get the bacteria cellulose dry film, reduce the irregular part in edge.It is soaked in 5min in the 5%Nafion solution, takes out 100 ° of C oven dry 10min.Then film is placed 110 ° of C patents of baking oven 1h, promptly obtain the sandwich composite membrane of bacteria cellulose-Nafion of individual layer Nafion-BC-Nafion structure.
Utilize AC impedence method to measure the conductivity of PEM under the room temperature, the i.e. proton conductivity of film.
Laboratory apparatus: electrochemical workstation CHI760d
Experiment test condition: AC Impedence, frequency scanning scope 0.1-10
4Hz, amplitude voltage 100mV
Experimental technique:
(1) measures the thickness of modified bacteria cellulose film with micrometer caliper, be recorded as d, the cm of unit;
(2) the sandwich composite membrane of individual layer Nafion-BC-Nafion is placed the conductivity test module, place 25 ℃ of constant temperature ovens, balance 30min makes the temperature of module and film reach 25 ℃, connects lead, the test AC impedance.Read the impedance R of film according to the AC impedance spectrogram, the Ω of unit, the AC impedance spectrogram is as shown in Figure 9.
(3) according to formula
Wherein l is the distance between the two poles of the earth, and the cm of unit calculates the proton conductivity of membrane, the Scm of unit
-1
Experimental result shows that the thickness of the sandwich composite membrane of individual layer Nafion-BC-Nafion is 0.0018-0.0025cm, and AC impedance is 90-130k Ω, and proton conductivity can reach 0.00206 ± 0.00047Scm
-1
(1) gets bacteria cellulose film; Use deionized water rinsing, remove impurity such as residual culture medium, place 95 ° of C water bath processing of sodium carbonate liquor 2h of mass percent 5% then; It is translucent to become white until bacteria cellulose film; Use washed with de-ionized water again, place deionized water to boil 2h, till taking-up uses deionized water rinsing to bacteria cellulose film surface p H value as neutrality.Simultaneously, get the above-mentioned leachate that boils and measure its 280nm absorption value, if absorption value is not less than 0.05, the step that then repeats to boil and wash is till boiling leachate 280nm and not having remarkable absorption.The bacteria cellulose film that purification process is good places deionized water, and 4 ° of C seal preservation.
(2) gelatinous bacteria cellulose film is placed on the plate of Teflon coating, drying at room temperature or freeze drying obtain the bacteria cellulose dry film.
(3) get the bacteria cellulose dry film, reduce the irregular part in edge.It is soaked in 10min in the 5%Nafion solution; Take out 110 ° of C oven dry 15min; Repeat once the step of above-mentioned immersion oven dry again, then film is placed 110 ° of C patents of baking oven 1h, promptly obtain the sandwich composite membrane of bacteria cellulose-Nafion of double-deck Nafion-BC-Nafion structure.
Utilize AC impedence method to measure the conductivity of PEM under the room temperature, the i.e. proton conductivity of film.
Laboratory apparatus: electrochemical workstation CHI760d
Experiment test condition: AC Impedence, frequency scanning scope 0.1-10
4Hz, amplitude voltage 100mV
Experimental technique:
(1) measures the thickness of modified bacteria cellulose film with micrometer caliper, be recorded as d, the cm of unit;
(2) the sandwich composite membrane of double-deck Nafion-BC-Nafion is placed the conductivity test module, place 25 ℃ of constant temperature ovens, balance 30min makes the temperature of module and film reach 25 ℃, connects lead, the test AC impedance.Read the impedance R of film according to the AC impedance spectrogram, the Ω of unit, the AC impedance spectrogram is shown in figure 10.
(3) according to formula
Wherein l is the distance between the two poles of the earth, and the cm of unit calculates the proton conductivity of membrane, the Scm of unit
-1
Experimental result shows that the thickness of the sandwich composite membrane of double-deck Nafion-BC-Nafion is 0.019-0.021cm, and AC impedance is 16-27k Ω, and proton conductivity can reach 0.0123 ± 0.0047Scm
-1
Claims (7)
1. sandwich PEM of bacteria cellulose-Nafion, this sandwich PEM is BC-Nafion-BC structure or Nafion-BC-Nafion structure.
2. the preparation method of the sandwich PEM of bacteria cellulose-Nafion comprises:
(1) bacteria cellulose film is used deionized water rinsing; Remove impurity such as residual culture medium; Under 70-100 ℃, place the alkaline solution of mass concentration 0.1-5% to handle 0.5-4h then; It is translucent to become white until bacteria cellulose film, again with acid solution and the washed with de-ionized water of mass concentration 0.1-3% or use washed with de-ionized water separately, in deionized water, boils 0.5-2h then; Till using deionized water rinsing to bacteria cellulose film pH value as neutrality again, obtain gelatinous bacteria cellulose film;
(2) the Nafion film is boiled with the dilute sulfuric acid of the hydrogen peroxide solution of mass concentration 3%, deionized water, 1mol/L and deionized water successively handle 1h, the Nafion film that obtains handling;
(3) the Nafion film with above-mentioned processing is cut into the shape littler than gelatinous bacteria cellulose film, the Nafion film of stack gelatinous bacteria cellulose film successively then, handling and gelatinous bacteria cellulose film; Drying and forming-film then promptly obtains the sandwich composite membrane of bacteria cellulose-Nafion of BC-Nafion-BC structure;
Perhaps the Nafion film with above-mentioned processing is cut into the shape littler than gelatinous bacteria cellulose film, the Nafion film that stacks the Nafion film of handling, gelatinous bacteria cellulose film then successively and handled; Drying and forming-film then promptly obtains the sandwich composite membrane of bacteria cellulose-Nafion of Nafion-BC-Nafion structure;
Perhaps, obtain the bacteria cellulose dry film with after the gelatinous bacteria cellulose film drying; After the irregular part in described bacteria cellulose dry film edge reduced; Be soaked in 5-15min in the Nafion solution of mass concentration 0.1-20%; Then in 90-110 ° of C baking 10-30min; Repeat step 1-9 time of above-mentioned immersion oven dry again, promptly obtain the sandwich composite membrane of bacteria cellulose-Nafion of Nafion-BC-Nafion structure;
(4) with the above-mentioned sandwich composite membrane that obtains in 110-130 ° of C patent 1-2h, get final product.
3. the preparation method of the sandwich PEM of a kind of bacteria cellulose-Nafion according to claim 2 is characterized in that: the alkaline solution described in the step (1) is the aqueous solution of NaOH, potassium hydroxide, potash or sodium carbonate.
4. the preparation method of the sandwich PEM of a kind of bacteria cellulose-Nafion according to claim 2; It is characterized in that: the acid solution described in the step (1) is acetic acid, citric acid, oxalic acid, the aqueous solution of benzoic acid, sorbic acid, malic acid, formic acid, boric acid, carbonic acid, silicic acid, sulfurous acid or phosphoric acid.
5. the preparation method of the sandwich PEM of a kind of bacteria cellulose-Nafion according to claim 2 is characterized in that: the said Nafion film of step (3) is business-like Nafion115 film, Nafion212 film or Nafion117 film.
6. the preparation method of the sandwich PEM of a kind of bacteria cellulose-Nafion according to claim 2; It is characterized in that: the mode that gelatinous bacteria cellulose film is dry described in the step (3) is oven dry, air-dry or freeze-drying, and remaining drying mode is that room temperature is dried, air-dry or 60 ° of following low temperature dryings of C.
7. the sandwich PEM of bacteria cellulose-Nafion is applied to hydrogen oxygen fuel cell or is in the fuel liquid battery of fuel with methyl alcohol or ethanol.
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| CN106299429A (en) * | 2016-08-24 | 2017-01-04 | 合肥国轩高科动力能源有限公司 | Alkaline anion exchange composite membrane for fuel cell and preparation method thereof |
| CN106299429B (en) * | 2016-08-24 | 2019-11-01 | 合肥国轩高科动力能源有限公司 | Alkaline anion exchange composite membrane for fuel cell and preparation method thereof |
| CN108395562B (en) * | 2018-05-30 | 2020-11-20 | 陕西科技大学 | Preparation method of high-crystallinity bacterial cellulose powder |
| CN108395562A (en) * | 2018-05-30 | 2018-08-14 | 陕西科技大学 | A kind of preparation method of high-crystallinity bacteria cellulose powder |
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| CN112510235A (en) * | 2020-12-03 | 2021-03-16 | 东华大学 | Polyvinyl alcohol-bacterial cellulose trimmings structure type alkaline anion exchange membrane, preparation and application |
| CN113036194A (en) * | 2021-03-09 | 2021-06-25 | 湖北工程学院 | Preparation method of organic-inorganic composite alkaline polyelectrolyte membrane |
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