CN1697218A - Bipolar plate composed of aromatic polythioether/Nano graphite, and preparation method - Google Patents
Bipolar plate composed of aromatic polythioether/Nano graphite, and preparation method Download PDFInfo
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- CN1697218A CN1697218A CNA2005100348913A CN200510034891A CN1697218A CN 1697218 A CN1697218 A CN 1697218A CN A2005100348913 A CNA2005100348913 A CN A2005100348913A CN 200510034891 A CN200510034891 A CN 200510034891A CN 1697218 A CN1697218 A CN 1697218A
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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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Abstract
In present technique, although aromatic poly-disulfide possesses fine degradability anti environments and other excellent performance, but it is difficult to be dissolved and melted so that its application is limited. Using cyclic oligomer of aromatic disulfide to synthesize aromatic poly-disulfide solves the said the problem. The invention discloses method for fabricating bipolar plate from cyclic oligomer of aromatic disulfide and expandable graphite. Using expandable graphite in low cost as filler to fill to oligomer of aromatic disulfide in heat ring opening polymerization produces precursor body of Nano composite material. Then, bipolar plate of fuel cell is made from the precursor body. Advantages of the bipolar plate are: excellent conductivity, good gas barrier property and cracking resistance property etc.
Description
Technical field
The present invention relates to prepare fuel battery double plates and method for making by in-situ ring-opening polymerization and expanded graphite.
Background technology
The poly-double thioether of fragrance has good anti-environment degradable, good cryogenic property, and low moisture-vapor transmission and excellent acid-proof alkaline, however because being difficult to dissolving, it also is difficult to fusion, limited its application.We find to utilize in-situ ring-opening polymerization to come the poly-double thioether of synthesizing fragrant to solve this difficult problem [Synthesis of cocyclic (arylene disulfide) oligomers and Their Adhesion Properties as Heating-melt Adhesive.Y.Z.Meng, S.C.Tjong and A.S.Hay
Polymer, 2001,42/12,5215-5224; Crosslinking of poly (arylenedisulfide) s and poly (arylene sulfane) s derived from cyclic (arylene disulfide) oligomer, Y.Z.Meng, A.S.Hay J.Appl.Polym.Sci.1999,74, p.3069-3077].
In-situ ring-opening polymerization possesses following characteristics:
1. be made up of the different ring homology thing of a series of degree of polymerization, ring strain is little.
2. under certain heat, light or initator effect, can carry out ring-opening polymerisation, need not any catalyst in the polymerization process does not have the small molecule by-product generation yet.
3. dissolubility is good.Most in-situ ring-opening polymerizations dissolves in and resembles oxolane (THF), in dimethyl formamide (DMF) the isopolarity organic solvent.
4. melting viscosity is low, easy-formation processing.
It can only need be heated to not adding any catalyst under the situation of uniform temperature carries out melt free radical ring-opening polymerization, thereby make processing more convenient, product can not cause because of containing the situation that initator impurity makes the product property variation because of adding initator yet.
Utilize the These characteristics of in-situ ring-opening polymerization, we have prepared high performance resin/graphite nanometer composite material [Facile synthesis of exfoliated and highly conductive poly (arylenedisulfide)/graphite nanocomposites.X.S.Du, M.Xiao, Y.Z.Meng, A.S.Hay, Polymer forAdvanced Technologies, 2004; 15:320-323].Graphite is scattered in the polymeric matrix with the limellar stripping less than the thickness of 100 nanometers in polymer, forms nano-graphite lamella conductive network.Because the nano-dispersed of electrically conductive graphite can prepare at the composite material that reaches needed conductivity with minimum graphite (or claiming class graphite).Prepare fuel battery double plates with this composite material following advantage arranged:
1, simple processing type can adopt the method one-shot forming of injection moulding or mold pressing.And carbon-to-carbon base bipolar plates adopts machine-tooled method to make bipolar plates usually, adopts the manual operations of wasting time and energy to be unlikely to cracking or broken to guarantee the thin bipolar plates of crisp, frangible carbon-to-carbon then in the assembling process of fuel cell.
2, light weight, thin thickness.The expanded graphite lamella of nano-dispersed makes a spot of filler just can reach required conductivity.And in traditional process, the graphite filler particles is big, meet the requirements of conductivity, and the consumption of graphite must be big, and graphite and polymeric matrix interaction force are little simultaneously, composite material machinery poor performance, and thickness is difficult to further attenuation.
3, in-situ ring-opening polymerization can be depolymerized to encircle and obtain by the poly-double thioether of fragrance, that is to say that the polymer in the bipolar plates of making can recycling [Novel Synthesis of Macrocyclic Aromatic DisulfideOligomers by Cyclodepolymerization of Aromatic Disulfide Polymers.Z.A.Liang, Y.Z.Meng, L.Li, X.S.Du, A.S.Hay.Macromolecules.2004,37 (16): 5837-5840.].
Summary of the invention
At the deficiencies in the prior art and problem, the purpose of this invention is to provide a kind of fuel battery double plates and method for making by in-situ ring-opening polymerization and expanded graphite preparation.
The present invention utilizes cheap expanded graphite to be filler, the in-situ ring-opening polymerization of filling thermal-ring-opening polymerization produces a kind of nano composite material presoma, and make fuel battery double plates with this nano composite material presoma, this bipolar plates has good conductivity, low manufacturing cost, simple processability, and have good gas-barrier properties energy and anti-cracking performance.
Nano composite material presoma of the present invention is by 30 ~ 50wt% in-situ ring-opening polymerization, and 50 ~ 70wt% expanded graphite is formed.
The structure of the in-situ ring-opening polymerization in the described nano composite material presoma is suc as formula shown in the I:
n＝1，2，......5
Ar is selected from following group among the formula I:
Or
Usually, the melting range of the in-situ ring-opening polymerization in the nano composite material presoma of the invention described above is 100 ℃-250 ℃.
Expanded graphite in the nano composite material presoma of the present invention can have different particle sizes, and the mean size of preferred particle is 10 μ m ~ 1000 μ m.
The described nano composite material presoma of the invention described above can prepare by the following method: in-situ ring-opening polymerization and expanded graphite are carried out solwution method mix in solvent, remove then and desolvate, promptly obtain required nano composite material presoma; Used solvent can be chloroform or carrene, or intensive polar solvent such as dimethyl formamide (DMF), N, N '-dimethylacetylamide (DMAc) or N-methyl pyrrolidone (NMP).
Usually, the consumption of solvent is advisable for soaking into filler (expanded graphite) fully.
The present invention is to provide a kind of fuel battery double plates of making by above-mentioned nano composite material presoma---have the Nano graphite bipolar plates in flow field.
This fuel battery double plates thickness generally can be 2-5mm, and preferred thickness range is 2-4mm.
The preparation method of above-mentioned fuel battery double plates comprises the steps: the nano composite material presoma of above-mentioned method for making gained molded by needed shape, then, (be generally 150 ℃-230 ℃ 100 ℃ of-250 ℃ of temperature, and be preferably 180 ℃-210 ℃), 1MPa-25MPa pressure (is generally 5MPa-20MPa, and be preferably 10MPa-20Mpa) condition under thermal-ring-opening polymerization 20 ~ 30min, make required bipolar plates.
Described molded method can be common injection molding or die pressing.
In-situ ring-opening polymerization of the present invention is under the prerequisite of not using any catalyst, only need be heated to suitable temperature ring-opening polymerisation can take place, in-situ ring-opening polymerization approach of ring-opening polymerisation and recovery under the situation of heating is shown below:
Ar in the formula can be:
Or
The present invention utilizes the easy dissolubility of in-situ ring-opening polymerization, low melting viscosity, the characteristics such as original position ring-opening polymerisation straight forming that no small molecule by-product is emitted, it is nano combined that target molecule and graphite are carried out, can be under suitable temperature and pressure condition by the original position ring-opening polymerization, be no more than in 30 minutes, obtain the Nano graphite composite dual-electrode plates in die for molding, it is very convenient to process, and has overcome direct use polymeric matrix itself and has prepared the processing forming that is difficult for that composite material had.
Bipolar plates provided by the present invention has thin thickness, low density, (its bending strength is about 30-35Mpa to the performance of cracking resistance, that is to say when the suffered stress of bipolar plates is no more than this scope, its intensity is enough to avoid cracking), can improve processing characteristics, have low manufacturing cost simultaneously, and improve its conductivity (its resistivity is not higher than 0.01 Ω .cm).In addition, the used fragrant double thioether polymer of the present invention has the high-resistance to environment degradable, is inactive in corrosive fuel cell environment, thereby helps reducing ion permeability.Moreover, in-situ ring-opening polymerization melting viscosity in this nano composite material presoma is low, it can only need be heated to not adding any catalyst under the situation of uniform temperature carries out melt free radical ring-opening polymerization, thereby help improving the processing characteristics of this nano composite material presoma under moderate temperature and pressure condition, make processing more convenient.
Nano composite material presoma of the present invention, thereby obtain compound by the ring-opening polymerisation under the situation of heating of the in-situ ring-opening polymerization in the hole that is adsorbed on expanded graphite, we find that the lamella of graphite is that form with nanostructure is present in the compound.So the amount of filler is fewer in this nano composite material presoma, thereby make the fuel battery double plates that is prepared by the nano composite material presoma have lower density and do not lose its conductivity, special nanostructure is given bipolar plates good gas-barrier properties energy again.Moreover, be a kind of callable material by the poly-double thioether of the resulting polymer fragrance of in-situ ring-opening polymerization ring-opening polymerisation under the situation of heating.So with this composition is that the preparation material of fuel battery double plates will be made outstanding contributions to environmental protection.
Embodiment
The invention will be further described by the following examples:
Embodiment 1: the preparation of nano composite material presoma
The in-situ ring-opening polymerization of ormal weight is dissolved in chloroform (perhaps carrene, dimethyl formamide, N, N '-dimethylacetylamide or N-methyl pyrrolidone) in, the expanded graphite that under churned mechanically situation, adds ormal weight, dispersed with stirring 30 minutes.With resulting wet nano composite material presoma removal of solvent under reduced pressure, be lower than the 3wt% of said composition until solvent, again said composition is placed in 65 ℃ the stove and be dried to weight, obtain the composition of homogeneous.
All prepare at the nano composite material presoma described in the embodiment 2 ~ 7 according to the method for example 1
Embodiment 2: ring-type diphenyl ether double thioether based nano composite material presoma
Preparation method according to above-mentioned nano composite material presoma prepares 200g ring-type diphenyl ether double thioether based nano composite material presoma in batches, and this nano composite material presoma comprises 30wt% ring-type diphenyl ether double thioether and 70wt% expanded graphite.
Embodiment 3: ring-type diphenyl sulphone (DPS) double thioether based nano composite material presoma
Preparation method according to above-mentioned nano composite material presoma prepares 200g ring-type diphenyl sulphone (DPS) double thioether based nano composite material presoma in batches, and this nano composite material presoma comprises 35wt% ring-type diphenyl sulphone (DPS) double thioether and 65wt% expanded graphite.
Embodiment 4: ring-type biphenyl double thioether based nano composite material presoma
Preparation method according to above-mentioned nano composite material presoma prepares 200g ring-type biphenyl double thioether based nano composite material presoma in batches, and this nano composite material presoma comprises 50wt% ring-type biphenyl double thioether and 50wt% expanded graphite.
Embodiment 5: ring-type diphenyl sulfide double thioether based nano composite material presoma
Preparation method according to above-mentioned nano composite material presoma prepares 200g ring-type diphenyl sulfide double thioether based nano composite material presoma in batches, and this nano composite material presoma comprises 40wt% ring-type diphenyl sulfide double thioether and 60wt% expanded graphite.
Embodiment 6: ring-type benzophenone double thioether based nano composite material presoma
Preparation method according to above-mentioned nano composite material presoma prepares 200g ring-type benzophenone double thioether based nano composite material presoma in batches, and this nano composite material presoma comprises 45wt% ring-type benzophenone double thioether and 55wt% expanded graphite.
Embodiment 7: ring-type hexichol isopropyl double thioether based nano composite material presoma
Preparation method according to above-mentioned nano composite material presoma prepares 200g ring-type hexichol isopropyl double thioether based nano composite material presoma in batches, and this nano composite material presoma comprises 37wt% ring-type hexichol isopropyl double thioether and 63wt% expanded graphite.
Embodiment 8: the making of Nano graphite composite dual-electrode plates
Adopt the technology of mold pressing to be molded into the shape of needed bipolar plates the nano composite material presoma of the foregoing description 2, then at 200 ℃, ring-opening polymerisation is 30 minutes under the 20MPa condition, promptly obtains the Nano graphite composite dual-electrode plates.The thickness of bipolar plates is 2mm, and bending strength is 31.7MPa, and resistivity is 0.0097 Ω .cm, and density is 1.48g/cm
3
Embodiment 9: the making of Nano graphite composite dual-electrode plates
Adopt the technology of mold pressing to be molded into the shape of needed bipolar plates the nano composite material presoma of the foregoing description 3, then at 180 ℃, ring-opening polymerisation is 20 minutes under the 15MPa condition, promptly obtains the Nano graphite composite dual-electrode plates.The thickness of bipolar plates is 3mm, and bending strength is 33.0MPa, and resistivity is 0.0095 Ω .cm, and density is 1.48g/cm
3
Embodiment 10: the making of Nano graphite composite dual-electrode plates
Adopt the technology of mold pressing to be molded into the shape of needed bipolar plates the nano composite material presoma of the foregoing description 4, then at 210 ℃, ring-opening polymerisation is 25 minutes under the 10MPa condition, promptly obtains the Nano graphite composite dual-electrode plates.The thickness of bipolar plates is 4mm, and bending strength is 35.0MPa, and resistivity is 0.01 Ω .cm, and density is 1.49g/cm
3The preparation method of cross-lined polymethyl ethylene carbonate.
Claims (6)
1, a kind of poly arylidene thio-ester/Nano graphite composite dual-electrode plates, make by the described method of claim 3, be to utilize cheap expanded graphite to be filler, a kind of nano composite material presoma that the in-situ ring-opening polymerization of filling thermal-ring-opening polymerization is made is made, it is characterized in that fuel battery double plates is the Nano graphite bipolar plates that has the flow field, this fuel battery double plates thickness is 2-5mm,, density is 1.48g/cm
3-1.49g/cm
3, bending strength is that 30-35Mpa, conductivity are not higher than 0.01 Ω .cm, the nano composite material presoma is by 30～50wt% in-situ ring-opening polymerization, 50～70wt% expanded graphite is formed.
2,, it is characterized in that described fuel battery double plates thickness range is 2-4mm according to the poly arylidene thio-ester described in the claim 1/Nano graphite composite dual-electrode plates.
3, the method for making of the poly arylidene thio-ester described in a kind of claim 1/Nano graphite composite dual-electrode plates, the in-situ ring-opening polymerization that utilizes cheap expanded graphite to fill thermal-ring-opening polymerization for filler produces a kind of nano composite material presoma, and make fuel battery double plates with this nano composite material presoma, it is characterized in that concrete method for making comprises the steps:
1), the preparation of nano composite material presoma: in-situ ring-opening polymerization and expanded graphite are carried out solwution method mix in solvent, remove then and desolvate, promptly obtain required nano composite material presoma; Used solvent is chloroform, carrene, intensive polar solvent, and the consumption of solvent is advisable for soaking into the filler expanded graphite fully;
2), the preparation method of fuel battery double plates: nano composite material presoma above-mentioned 1, middle gained is molded by needed shape, then, 100 ℃ of-250 ℃ of temperature, 1MPa-25MPa pressure, condition under thermal-ring-opening polymerization 20～30min, make required bipolar plates.Described molded method can be common injection molding or die pressing.
4, according to the method for making of poly arylidene thio-ester described in the claim 3/Nano graphite composite dual-electrode plates, it is characterized in that step 1), described in intensive polar solvent be dimethyl formamide, N, N '-dimethylacetylamide, or N-methyl pyrrolidone.
5, according to the method for making of poly arylidene thio-ester described in the claim 3/Nano graphite composite dual-electrode plates, it is characterized in that step 2), described in the temperature of thermal-ring-opening polymerization be 150 ℃-230 ℃, especially be 180 ℃-210 ℃; Polymerization pressure is 5MPa-20MPa, especially is 10MPa-20Mpa.
6, according to the method for making of poly arylidene thio-ester described in the claim 3/Nano graphite composite dual-electrode plates, it is characterized in that step 2), described in molded method be injection molding or die pressing.
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| CNB2005100348913A CN1300875C (en) | 2005-05-31 | 2005-05-31 | Bipolar plate composed of aromatic polythioether/Nano graphite, and preparation method |
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| CNB2005100348913A CN1300875C (en) | 2005-05-31 | 2005-05-31 | Bipolar plate composed of aromatic polythioether/Nano graphite, and preparation method |
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| CN1221615C (en) * | 2002-11-19 | 2005-10-05 | 中国科学院广州化学研究所 | Nanometer composite material made from aromatic double thioether cyclic oligomer, preparing method and application thereof |
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