CN102931420A - Carbon/resin composite material and application thereof - Google Patents
Carbon/resin composite material and application thereof Download PDFInfo
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Abstract
The invention relates to a carbon/resin composite material and application thereof. The carbon/resin composite material is manufactured by that a pre-finished product is manufactured through pressurization and solidification, and then the pre-finished product is solidified through constant pressure and high temperature to obtain the carbon/resin composite material. The total weight of used raw materials is used as 100wt% calculation reference, a carbon material occupies 70wt%-90wt%, and the carbon material is a mixture formed by natural graphite, expanded graphite and carbon black. The carbon/resin composite material can be used as bipolar plates of a proton exchange membrane fuel cell. The carbon/resin composite material overcomes the defect that a traditional mould pressing method is long in processing cycle and an injection molding method is poor in product performance and is particularly suitable for large-scale production.
Description
Technical field
The present invention relates to a kind of carbon element/resin composite materials and uses thereof, specifically, relate to a kind of composite material that comprises graphite, expanded graphite, carbon black and resin and uses thereof.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) but have that high, the pollution-free room temperature of energy conversion efficiency starts fast, the life-span is long and the power density high, all have broad application prospects at aspects such as stationary electric power plant, electric motor car, military special type power supply, movable power sources, especially the driving power of electric motor car, and be considered to third generation dynamical system after steam engine and internal combustion engine.Its research has been become a focus in electrochemistry and the energy science field, and many developed countries and company are paid much attention to its development, and invest heavily in this technology.
Bipolar plates is the significant components of Proton Exchange Membrane Fuel Cells, and also being affects battery performance, especially affects a key factor of power of battery density and manufacturing cost.Difference according to the preparation material often is divided into graphite bi-polar plate with bipolar plates, metal double polar plates and composite material double pole plate.
Common graphite is the bipolar plate material of early development and utilization, its bipolar plates quality of making is light, corrosion resistance and good, conductivity are stronger, but the property of graphite own is crisp, has caused certain difficulty to assembling product, and easily produces 15% left and right sides pore in the manufacture process.Simultaneously, graphite sheet manufacturing and flow field processing technology more complicated cause manufacturing cost expensive.
Metal double polar plates has good conductivity, thermal conductivity, machining property, compactness etc., satisfy the requirement of batch production, but metal material density is high, perishable, the metal ion of dissolved rear generation is diffused into the proton exchange rete at work, will increase the resistance of the bipolar plates that is corroded, reduce power output and the useful life of fuel cell.
Composite material double pole plate, particularly resin-based carbon composite bipolar plates are the developing direction of pem cell bipolar plates.At present, resin-based carbon composite dual polar plates of proton exchange membrane fuel cell generally uses a kind of to two kinds of packing materials, and its electricity and mechanical property are all lower; Adopt multi-component filler as raw material in the individual material, but used filler is expensive, is difficult for obtaining.Aspect of performance, composite plate are faced with inevitable contradiction difficult point between intensity and the conductivity, namely improve intensity, and needing increases resin content, and this will inevitably cause the decline of composite plate electrical property, otherwise then mechanical strength is not enough.The processing technology of existing composite material dual polar plates of proton exchange membrane fuel cell is difficult to satisfy simultaneously the short and good requirement of properties of product of process-cycle.Therefore, overcoming the contradiction that mutually restricts between these problems is to improve the key of composite plate performance.
Maximum problem is: the conventional moulded method process-cycle is long, and the injection moulding properties of product are poor, and processing method commonly used all is not suitable for large-scale production at present.
US.Pat.No.4,301,222 (Emannelson et al) have disclosed a kind of bipolar plates that each 50% mixed injection molding of pure graphite powder and charing thermosetting phenolic resin is become, and then carry out aftertreatment technology and make its complete graphitization.The gained graphite cake is better than pure graphite cake in aspect performances such as mechanical strength, weight savings, finishes in condition more than 2000 ℃ but its shortcoming is graphitization, and processing cost is very high.
CN 1440574A (Z Iqbal etc.) provides a kind of nano composite material for fuel battery double plates.Used nanotube-shaped fiber in described nanocomposites, this material price is expensive and originate lessly, and used nanotube-shaped fiber carries out annealing in process under 3000 ℃, improved processing cost, is not suitable for the batch production of product.
CN 101101994A (Shen Chunhui etc.) discloses a kind of expansion graphite base compound material dual-pole board and preparation method thereof, and described bipolar plates is mainly by forming through the pretreated expanded graphite of thermoplastic resin and carbon cloth or carbon paper mold pressing.Although prepared bipolar plates has better mechanics and electric property, but carbon cloth or carbon paper need to process through 200 ℃ of lower 1-2 hours, need to be molded into plate to expanded graphite, again with carbon cloth or carbon paper together mold pressing make bipolar plates, and under pressurize, naturally cool to room temperature, its complicated process of preparation, the process-cycle is long, is not suitable for the batch production of product.
CN 101132067A (Li Aiju etc.) also discloses a kind of fuel battery double plates composite material and preparation technology thereof, and it mainly adopts the carbon nano-tube through surface preparation to strengthen phenolic resin/graphite based fuel-cell double.The major defect of this technique is; the carbon nano-tube treatment process is comparatively complicated; need under ferrous ion, hydrogen peroxide, fixed pH value and specific wavelength ultraviolet light, to process 1 hour to 5 hours; that molding pressure requires is high (needs 10MPa～40MPa); long (the dwell time 40min～120min), be not suitable for large-scale production of process cycle.
Summary of the invention
The problem that exists in order to solve prior art, the present invention provides a kind of composite material that comprises graphite, expanded graphite, carbon black and resin on a large amount of experimental study bases.Composite material provided by the present invention has better mechanics and electric property, can be used as the application of dual polar plates of proton exchange membrane fuel cell.
One object of the present invention is, a kind of carbon element/resin composite materials of novelty is provided, and described carbon element/resin composite materials is made by the preparation method who comprises the steps:
The raw material cure under pressure moulding that (1) will be comprised of carbon materials and " resin matrix " (term " resin matrix " refers to comprise the mixture of thermosetting resin and curing agent) obtains preform; With
(2) under normal pressure (1 atmospheric pressure) condition, the preform that will be obtained by step (1) obtains object (carbon element/resin composite materials of the present invention) through hot curing;
Wherein, as calculating benchmark, carbon materials accounts for 70wt%～90wt%, the mixture that described carbon materials is comprised of graphite, expanded graphite and carbon black take the total weight of raw materials as 100wt%;
In step (1), minimum pressure is for can guarantee that the molten state thermosetting resin is full of the pressure of dies cavity, and maximum pressure is not higher than makes the destroyed critical pressure of carbon materials structure; Minimum temperature is higher than used thermosetting resin cured temperature, and maximum temperature is not higher than the temperature can make the melting heat thermosetting resin stop to flow at 1 minute; Shortest time is the time (the better shortest time is the time that used thermosetting resin stops to flow) of the complete melt impregnation carbon packing of used thermosetting resin;
The conductivity of prepared carbon element/resin composite materials is 150S/cm～250S/cm (23 ℃), and bending strength is 30MPa～45MPa (23 ℃), and density is 1.45g/cm
3～1.70g/cm
3(23 ℃).
Another object of the present invention is, discloses a kind of purposes of above-mentioned carbon element/resin composite materials, and described carbon element/resin composite materials is as the application of the bipolar plates of Proton Exchange Membrane Fuel Cells.
Compared with prior art, the outstanding advantages of carbon element/resin composite materials provided by the present invention is, raw material is inexpensive, manufacturing cycle is short and be suitable for large-scale production.In brief, carbon element/resin composite materials provided by the present invention has more commercial value.
Embodiment
In the present invention, used graphite (native graphite or Delanium), expanded graphite and carbon black all be commonly use, the cheap and conductive filling material that is easy to get.
Used native graphite preferably has the native graphite of sclay texture, and its thickness is 0.02mm～0.05mm, and the scale draw ratio is 1～4; Used Delanium preferably has the Delanium of spherical structure.The present inventor finds: the bending strength of carbon element/resin composite materials provided by the present invention reduces with the particle diameter of used graphite and increases, and with particle diameter different " admixed graphite " (term " admixed graphite " refers to: the graphite that is mixed by the graphite of two or more different-grain diameter) substitute the graphite of single particle size, conductivity and the bending strength of the carbon element/resin composite materials of gained are better.
Used expanded graphite can be made through methods such as electrochemical process, chemical oxidization method, microwave method, explosion method or air plllutant methods by expansible graphite, and it is the vermicular texture of porosity and looseness.The present invention does not have specific (special) requirements to the expanding volume of used expanded graphite.
Used carbon black is the spherical shape structure of Nano grade, and it can be conductive channel black, conductive furnace black, extra conductive furnace black, high electric conductivity furnace black or acetylene carbon black.Used carbon black can be surface treated, also can be not surface treated, and carbon black also can pass through graphitization processing, to the particle diameter no requirement (NR) of carbon black.
This three of above-mentioned graphite, expanded graphite and carbon black can effectively cooperate on structure and consists of good three-dimensional conductive network and lower porosity, and there is active group on the expanded graphite surface, has strengthened the adhesion with resin, has improved the mechanical property of goods.
The hard high order cohesion structure of the higher order structure of expanded graphite particles itself and carbon black particle makes and forms a plurality of electric networks between the conductivity particle filled composite.And along with the increase of graphite particle diameter, the particle filled composite Contact increases, and conductivity improves.Simultaneously, the sclay texture of natural flake graphite is orientated under ambient pressure, is conducive to form conductive network, and the natural flake graphite of orientation can improve the gas barrier property of bipolar plates; Delanium is sandwich construction, and complex structure, different-grain diameter graphite and multiple carbon materials are used in combination and can effectively improve the high shortcoming of its voidage.
When graphite and expanded graphite used as the conductivity filler simultaneously, the bending strength of the composite material of gained can reduce (than only filling graphite), and possible cause is: the expanded graphite vesicular structure causes existing in the composite material small pore; When using graphite, expanded graphite and carbon black as the conductivity filler, the bending strength of the composite material of gained can increase, this may be because nano level carbon black penetrates in the expanded graphite vesicular structure and stops up pore, and because pressure, the vesicular structure locking is suppressed, specific area increases, and the bonded area of graphite and resin increases; When using graphite and carbon black as the conductivity packing material, the bending strength of the composite material of gained can increase, but Conductivity Ratio uses graphite, expanded graphite and carbon black low.In preferred technical scheme of the present invention, take the total weight of raw material (being formed by graphite, expanded graphite, carbon black and " resin matrix ") as 100wt%, graphite accounts for 40wt%～70wt%, expanded graphite accounts for 3wt%～10wt%, carbon black accounts for 5wt%～25wt%, and " resin matrix " accounts for 10wt%～30wt%.
The present inventor finds through experiment: adopt the graphite of two kinds of different-grain diameters to mix prepared composite material, than using the standby composite material of single particle size graphite-made, both density is close, but the former conductivity and bending strength are better.And to the requirement as the composite material of dual polar plates of proton exchange membrane fuel cell be: high conductivity and high bending strength.Therefore, the present invention advises using the mixture (" admixed graphite ") of the graphite of different-grain diameter.Experimental result shows, under the identical condition of other condition, adopt the electricity of carbon element/resin composite materials of " admixed graphite " and mechanical property to be better than adopting electricity and the mechanical property of the carbon element/resin composite materials of single particle size graphite, but disproportional requirement between the graphite of two or more different-grain diameter.
Used " resin matrix " is the mixture that comprises thermosetting resin and curing agent.Take the total weight of " resin matrix " as 100wt%, curing agent accounts for 7wt%～10wt%.
Wherein, described thermosetting resin preferably comprises the phenolic resins take phenolic compound and aldehyde compound as monomer at least.In addition, described thermosetting resin can pass through epoxy resin, unsaturated polyester (UP) etc. and carries out modification;
Described curing agent is amine curing agent, and it can be selected from the mixture of the arylamine such as aniline, hexa and melamine or fatty amine one or two or more kinds (containing two kinds).
There is the contradiction that is difficult to be in harmonious proportion between process time and the properties of product for existing in the prior art, the present invention adopts two-step method, at pressurization precuring formative stage (hereinafter to be referred as " step (1) "), being about to temperature is controlled at more than the used thermosetting resin cured temperature, carry out short time press molding and precuring, cooling and demolding makes preform.In " step (1) ", product molding but solidify and insufficient.
Constant-pressure and high-temperature cure stage (hereinafter to be referred as " step (2) ") is namely under normal pressure (1 atmospheric pressure) condition and more than the curing temperature, after will further being solidified by " step (1) " prepared preform, get carbon element/resin composite materials of the present invention.Prepared carbon element/resin composite materials can be (the implementing in " step (1) ") that runner is arranged, and also can bore the runner at quarter the later stage.
Find through experiment: in " step (1) ", pressure can not be too low, because the processing temperature in this stage is higher than thermosetting resin cured temperature, operating pressure is crossed and lowly can be caused resin melting to flow not fully and solidify, make the inner hole that produces of prefabrication, affect performance.Therefore, the minimum pressure of " step (1) " is full of the pressure of dies cavity for guaranteeing the molten state thermosetting resin, and maximum pressure should not be higher than and cause the destroyed critical pressure of carbon materials structure, and design parameter is decided on used carbon materials.Therefore, in another optimal technical scheme of the present invention, pressure is 1MPa～10MPa in " step (1) ".
In addition, in " step (1) ", mold pressing is held time too short or temperature is crossed when hanging down, and thermosetting resin can't be finished the vesicular structure infiltration to expanded graphite, and simultaneously precuring is not enough.On the contrary, when molding temperature was too high, the molten state thermosetting resin easily solidified, and lost flowability, and was difficult to the infiltration of expanded graphite porousness structure.According to experimental result, the minimum temperature of " step (1) " should be higher than thermosetting resin melt-flow temperature (better temperature is to be higher than thermosetting resin cured temperature), but should be not too high in order to avoid the temperature that the molten state thermosetting resin loses flowability before not having the thorough impregnation carbon packing (being that maximum temperature is not higher than the temperature can make the melting heat thermosetting resin stop to flow at 1 minute).The shortest time of " step (1) " is the complete required time of melt impregnation carbon packing of used thermosetting resin, and maximum duration can change according to producing actual needs.Therefore, in another optimal technical scheme of the present invention, in " step (1) ", the temperature of pressurization precuring moulding should be set as be higher than used thermosetting resin 10 ℃～20 ℃ of curing temperatures (in other words, the temperature of pressurization precuring moulding is A+ (10 ℃～20 ℃), wherein A is the curing temperature of used thermosetting resin, and is lower same), and pressurization precuring moulding total time is 0.5 minute～5 minutes.
In fact, " step (1) " has comprised two physical processes: the used resin melted by heating of the first flows, and dipping carbon packing and be full of the process of mould, and it two is thermosetting resin precuring processes.Therefore, in concrete operations, " step (1) " can finish under same pressure, temperature and time process conditions, also can for above-mentioned two physical processes arrange respectively process conditions (namely flow in the thermosetting resin melted by heating, and dipping carbon packing and being full of in the process of mould, pressure is 1MPa～10MPa, Temperature Setting (can be expressed as A+ (10 ℃～20 ℃) equally for being higher than 10 ℃～20 ℃ of used thermosetting resin cured temperature, wherein A is the curing temperature of used thermosetting resin), the time is 0.1 minute～2 minutes; In thermosetting resin precuring process, pressure is 1MPa～10MPa, Temperature Setting (can be expressed as A+ (10 ℃～20 ℃) equally for being higher than 10 ℃～20 ℃ of used thermosetting resin cured temperature, wherein A is the curing temperature of used thermosetting resin), the time is 0.1 minute～3 minutes).These two processes are finished in single stepping, and the minimum time of this operation is to be advisable in 0.5 minute; The concrete time of our these two processes all is since 0.1 minute, but the time of two processes comprehensively will guarantee minimum 0.5 minute.
Determining of extrusion forming phases-time is flowability according to used resin, and resin can well the impregnated carbon cellulosic material and is full of mould in this is interval, and resin still has certain fluidity in this time range, can fully not solidify; Determining of pressurization pre-cure phase time is minimum curing time according to resin, and in this time range, resin solidification and typing lose flowability, and can not deform when regelate.
" step (2) " (being that constant-pressure and high-temperature solidifies) carried out hot setting and got final product under condition of normal pressure.No matter be in " step (1) " or " step (2) ", the establishment of the curing temperature of used resin all can obtain by best curing temperature shown in the DSC curve of used resin or by the hot plate gel test.
DSC curve such as used certain phenolic resins shows that its curing temperature is about 150 ℃ (exothermic peak), and then in " step (1) ", processing temperature should be set as 160 ℃～170 ℃; And in " step (2) ", processing temperature should be set as 150 ℃～170 ℃, and be 60 minutes～180 minutes curing time.
As shown from the above technical solution, the present invention has overcome the shortcoming of single carbon packing goods electric property and mechanical property deficiency, and the conventional moulded method process-cycle is long and the poor shortcoming of injection moulding properties of product, can make at several minutes the composite material preform of function admirable.After can stacking at a certain distance, many preforms at the constant-pressure and high-temperature baking-curing, implement batch production; Also can enter constant-pressure and high-temperature baking-curing streamline, implement to produce continuously.So, the present invention is more suitable in large-scale production.
Below by embodiment the present invention is further set forth, its purpose only is better to understand content of the present invention, and unrestricted protection scope of the present invention.
In the following example, used carbon black is XPB348 (Evonik Degussa GmbH's product), the used phenolic resins trade mark is 206 (Shanghai addition chemical industry Co., Ltd products), wherein comprise curing agent, artificial, native graphite and expansible graphite are provided by Shanghai one sail graphite Co., Ltd.
The conductivity of composite plate records by four-point method.Sample in preparation is wherein simultaneously got 4 points that spacing is 15mm.(Keithley6487picoame ter/Voltage source) passes into direct current with DC power supply, records material resistance with PZ158 type DC digital formula potentiometer.Conductance is calculated with following formula:
In the formula, σ-conductance, S/cm; B, h-specimen width, thickness, cm; The L-electrode spacing, cm; The I-electric current, mA; V-voltage, mV.
Material surface resistance (ρ) is the inverse of conductance.
Bending strength is to utilize the test of SANS type universal testing machine.Bend test is general to adopt load simply supported beams at 3, is about to sample and is placed on two fulcrums, and the sample between two fulcrums applies concentrfated load, makes sample deformation until the intensity when destroying, and computing formula is as follows:
In the formula, σ
f-bending strength, MPa; The P-breaking load, N; The 1-span, cm; B, h-specimen width, thickness, cm.
The experiment span is 30mm, and the decrease speed of pressure head is 2mm/min, and on-load pressure begins record during greater than 1N.
Density according to Archimedes principle measurement obtain.Use electronic balance to measure the temperature of the aerial density of sample, the density in water and water, computing formula is as follows:
In the formula, ρ-sample density, g/cm
3m
oThe aerial quality of-sample, g; The quality of m-sample in water, g; ρ
1The density of-water, g/cm
3ρ
2-atmospheric density, g/cm
3
The density of water is by measuring the temperature of water, and tabling look-up obtains the density of water under this temperature.Atmospheric density at room temperature is 0.0012g/cm
3
Embodiment 1
Two kinds of native graphites and expanded graphite with particle diameter 75 μ m (200 order) and 150 μ m (100 order), carbon black and phenolic resins mix, its quality percentage composition is respectively: 26wt%, 26wt%, 8wt%, 20wt% and 20wt%, room temperature (20 ℃～25 ℃) mixing and ball milling got mixture in 2 hours, the gained mixture is placed flat plate mold, at 5MPa (mold pressing preheating pressure), after keeping under 170 ℃ of (molding temperature) conditions implementing press molding 1 minute (mold pressing warm-up time), boost to again 10MPa (mold pressing precuring pressure), and under this state, keep 3 minutes (mold pressing precuring time) to implement pressurization precuring, cooling, the demoulding (release agent is silicone oil) makes preform; Preform is kept implementing constant-pressure and high-temperature 3 hours (normal pressure curing time) solidify under 150 ℃ of normal pressures (normal pressure curing temperature) condition, obtain object (composite material of the present invention, note by abridging be composite A).
Embodiment 2
Except the molding temperature among the embodiment 1 is changed into 160 ℃, other condition is identical with embodiment 1, obtains composite material B.
Embodiment 3
Except the mold pressing preheating pressure among the embodiment 1 is changed into the 1MPa, other condition is identical with embodiment 1, obtains composite material C.
Embodiment 4
Except the mold pressing precuring pressure among the embodiment 1 is changed into the 8MPa, other condition is identical with embodiment 1, obtains composite material D.
Embodiment 5
Except the mold pressing precuring time among the embodiment 1 was changed into 2 minutes, other condition is identical with embodiment 1, obtains composite material E.
Embodiment 6
Except the mold pressing among the embodiment 1 is changed into 2 minutes warm-up time, other condition is identical with embodiment 1, obtains composite material F.
Embodiment 7
Except the normal pressure among the embodiment 1 is changed into 1 hour curing time, other condition is identical with embodiment 1, obtains composite material G.
Embodiment 8
Except the normal pressure curing temperature among the embodiment 1 is changed into 170 ℃, other condition is identical with embodiment 1, obtains composite material H.
Embodiment 9～12
Except the percentage composition of each component that changes embodiment 1 Raw, other condition is identical with embodiment 1, obtains respectively corresponding composite material, sees table 1 for details.
Table 1
Embodiment 13
Except the mold pressing preheating pressure among the embodiment 1 is changed into the 10MPa, other condition is identical with embodiment 1, obtains composite material M.
Embodiment 14
Except the mold pressing precuring pressure among the embodiment 1 is changed into the 1MPa, other condition is identical with embodiment 1, obtains composite material N.
Embodiment 15-17
Except the kind that changes embodiment 1 Raw, other condition is identical with embodiment 1, obtains respectively corresponding composite material, sees table 2 for details.
Table 2
Comparative Examples 1
With particle diameter 75 μ m (200 order) and 150 μ m (100 order) two kinds of native graphites and expanded graphites, carbon black and phenolic resins mix, its quality percentage composition is respectively: 26wt%, 26wt%, 8wt%, 20wt% and 20wt%, room temperature (0 ℃～35 ℃) mixing and ball milling got mixture in 2 hours, the gained mixture is placed flat plate mold, at 5MPa (mold pressing preheating pressure), kept 1 minute under 170 ℃ of conditions, after boosting to again 10 seconds of 10MPa (mold pressing precuring pressure) pressurize, at once cooling, the demoulding (release agent is silicone oil) makes preform; Preform was kept 3 hours under 150 ℃ of conditions of normal pressure, obtain composite material a.
Comparative Examples 2
With particle diameter 75 μ m (200 order) and 150 μ m (100 order) two kinds of native graphites and expanded graphites, carbon black and phenolic resins mix, its quality percentage composition is respectively: 26wt%, 26wt%, 8wt%, 20wt% and 20wt%, room temperature (0 ℃～35 ℃) mixing and ball milling got mixture in 2 hours, the gained mixture is placed flat plate mold, at 5MPa (mold pressing preheating pressure), kept 1 minute under 170 ℃ of conditions, boost to again 10MPa (mold pressing precuring pressure), and under this state, kept 3 minutes, cooling, the demoulding (release agent is silicone oil) makes composite material b.
Comparative Examples 3
Particle diameter 75 μ m (200 order) and two kinds of native graphites of 150 μ m (100 order) are mixed with carbon black and phenolic resins, its quality percentage composition is respectively: 30wt%, 30wt%, 20wt% and 20wt%, room temperature (20 ℃～25 ℃) mixing and ball milling got mixture in 2 hours, the gained mixture is placed flat plate mold, at 5MPa (mold pressing preheating pressure), kept 1 minute under 170 ℃ of conditions, boost to again 10MPa (mold pressing precuring pressure), and under this state, kept 3 minutes, cooling, the demoulding (release agent is silicone oil) makes preform; Preform was kept 3 hours under 150 ℃ of conditions of normal pressure, obtain composite material c.
Comparative Examples 4
Except the two kinds of native graphites that use among the embodiment 1 being changed into single the kind the 150 μ m native graphites, other condition is identical with embodiment 1, obtains composite material d.
Comparative Examples 5
Except the two kinds of native graphites that use among the embodiment 1 being changed into single the kind the 106 μ m Delaniums, other condition is identical with embodiment 1, obtains composite material e.
Under identical test condition, mechanics, electric property and the density of test compound materials A～Q and composite material a～e the results are shown in Table 3 respectively.Can be seen by table 3 result, the mechanics of composite A～Q, electric property and density all meet the instructions for use of fuel battery double plates, and have at least one not satisfy instructions for use in the mechanics of composite material a～e, electric property and three indexs of density.
Table 3
Claims (9)
1. a carbon element/resin composite materials is characterized in that, described carbon element/resin composite materials is made by the preparation method who comprises the steps:
The raw material cure under pressure moulding that (1) will be comprised of carbon materials and " resin matrix " obtains preform; With
(2) under condition of normal pressure, the preform that will be obtained by step (1) obtains object through hot curing;
Wherein, as calculating benchmark, carbon materials accounts for 70wt%～90wt%, the mixture that described carbon materials is comprised of graphite, expanded graphite and carbon black take the total weight of raw materials as 100wt%; Described " resin matrix " is the mixture that comprises thermosetting resin and curing agent;
In step (1), minimum pressure is for can guarantee that the molten state thermosetting resin is full of the pressure of dies cavity, and maximum pressure is not higher than makes the destroyed critical pressure of carbon materials structure; Minimum temperature is higher than the curing temperature of used thermosetting resin, and maximum temperature is not higher than the temperature can make the melting heat thermosetting resin stop to flow at 1 minute; Shortest time is the complete required time of melt impregnation carbon packing of used thermosetting resin;
In step (2), temperature is not higher than 20 ℃ of used thermosetting resin cured temperature;
The conductivity of prepared carbon element/resin composite materials is 150S/cm～250S/cm (23 ℃), and bending strength is 30MPa～45MPa (23 ℃), and density is 1.45g/cm
3～1.70g/cm
3(23 ℃).
2. carbon element/resin composite materials as claimed in claim 1 is characterized in that, wherein take the total weight of described raw material as 100wt%, graphite accounts for 40wt%～70wt%, expanded graphite accounts for 3wt%～10wt%, and carbon black accounts for 5wt%～25wt%, and " resin matrix " accounts for 10wt%～30wt%.
3. carbon element/resin composite materials as claimed in claim 1 or 2 is characterized in that, wherein said graphite mixes " admixed graphite " by two or more different-grain diameter graphite.
4. carbon element/resin composite materials as claimed in claim 3 is characterized in that, wherein, take the total weight of used " resin matrix " as 100wt%, curing agent accounts for 7wt%～10wt%.
5. carbon element/resin composite materials as claimed in claim 4 is characterized in that, wherein used thermosetting resin is the phenolic resins that comprises at least take phenolic compound and aldehyde compound as monomer, and used curing agent is amine curing agent.
6. carbon element/resin composite materials as claimed in claim 5 is characterized in that, wherein said amine curing agent is selected from one or two or more kinds mixture of aniline, hexa and melamine.
7. such as the described carbon element/resin composite materials of any one in the claim 1～6, it is characterized in that, in " step (1) ", the temperature of pressurization precuring moulding is 10 ℃～20 ℃ of curing temperatures that are higher than used thermosetting resin, and pressurization precuring moulding total time is 0.5 minute～5 minutes; Or,
Flow in the thermosetting resin melted by heating, and dipping carbon packing and being full of in the process of mould, pressure is 1MPa～10MPa, Temperature Setting is for being higher than 10 ℃～20 ℃ of used thermosetting resin cured temperature, the time is 0.1 minute～2 minutes; In thermosetting resin precuring process, pressure is 1MPa～10MPa, and Temperature Setting is for being higher than 10 ℃～20 ℃ of used thermosetting resin cured temperature, and the time is 0.4 minute～3 minutes.
8. such as the described carbon element/resin composite materials of any one in the claim 1～6, it is characterized in that, " step (2),, in, temperature is A～(A+20 ℃), be 60 minutes～180 minutes curing time; Wherein A is the curing temperature of used thermosetting resin.
9. such as the application of the described carbon element/resin composite materials of any one in the claim 1～8 as the bipolar plates of Proton Exchange Membrane Fuel Cells.
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| CN109713320A (en) * | 2018-12-29 | 2019-05-03 | 绍兴金创意塑化电器有限公司 | A kind of battery pole plates BMC material and preparation method thereof |
| CN109921053A (en) * | 2017-12-13 | 2019-06-21 | 中国科学院大连化学物理研究所 | A kind of preparation method and applications of bipolar plates |
| CN110176608A (en) * | 2019-04-29 | 2019-08-27 | 上海电气集团股份有限公司 | A kind of compound bipolar plates of thermosetting resin base used for all-vanadium redox flow battery and preparation method thereof |
| CN111916782A (en) * | 2020-06-29 | 2020-11-10 | 惠州市杜科新材料有限公司 | Ultrathin graphite composite bipolar plate base material capable of being rapidly cold-pressed and formed and preparation method thereof |
| CN113782751A (en) * | 2021-09-17 | 2021-12-10 | 宁波信远炭材料股份有限公司 | Preparation method of high-flexibility carbon/resin composite material |
| CN114801266A (en) * | 2021-01-19 | 2022-07-29 | 上海神力科技有限公司 | Flexible graphite polar plate processing method, fuel cell and vehicle |
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| CN109921053A (en) * | 2017-12-13 | 2019-06-21 | 中国科学院大连化学物理研究所 | A kind of preparation method and applications of bipolar plates |
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| CN111916782A (en) * | 2020-06-29 | 2020-11-10 | 惠州市杜科新材料有限公司 | Ultrathin graphite composite bipolar plate base material capable of being rapidly cold-pressed and formed and preparation method thereof |
| CN114801266A (en) * | 2021-01-19 | 2022-07-29 | 上海神力科技有限公司 | Flexible graphite polar plate processing method, fuel cell and vehicle |
| CN113782751A (en) * | 2021-09-17 | 2021-12-10 | 宁波信远炭材料股份有限公司 | Preparation method of high-flexibility carbon/resin composite material |
| CN113782751B (en) * | 2021-09-17 | 2023-08-11 | 宁波信远材料科技股份有限公司 | Preparation method of high-flexibility carbon/resin composite material |
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