CN109244501A - A kind of fuel battery double plates composite material and preparation method and purposes - Google Patents
A kind of fuel battery double plates composite material and preparation method and purposes Download PDFInfo
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- CN109244501A CN109244501A CN201811116196.5A CN201811116196A CN109244501A CN 109244501 A CN109244501 A CN 109244501A CN 201811116196 A CN201811116196 A CN 201811116196A CN 109244501 A CN109244501 A CN 109244501A
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- composite material
- fuel battery
- double plates
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- lanthana
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0226—Composites in the form of mixtures
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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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- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
The present invention provides a kind of fuel battery double plates composite material and preparation method and purposes.The fuel battery double plates composite material includes graphite powder, perovskite oxide, rare-earth element modified lanthana and epoxy novolac type vinylite, the present invention is under the compounding of above-mentioned raw materials, effective conductive path is formed in the insulating layer inside epoxy novolac type vinylite, negative effect of the clad to conductivity is reduced, so that conductivity increases substantially;Simultaneously because the addition of perovskite oxide, rare-earth element modified lanthana, can further increase conductive channel, tunnel current is formed, to improve conductivity;In addition, improving the flexural strength of composite material under the compounding of above-mentioned raw materials.After measured, the conductivity of fuel battery double plates composite material produced by the present invention are as follows: 502~590S/cm;68~75MPa of bending strength.
Description
Technical field
The present invention relates to conducing composite material fields, and in particular to a kind of fuel battery double plates composite material and its preparation
Method and purposes.
Background technique
Bipolar plates are one of Proton Exchange Membrane Fuel Cells (PEMFC) key components, its effect is separate gas and leads to
It crosses flow field and reaction gas is imported into fuel cell, collect conduction electric current and support membrane electrode, while also shouldering entire fuel electricity
The heat dissipation of cell system and drain function.Therefore bipolar plates composite material requires preferable electric conductivity and mechanical property.
Bipolar plates can be divided into following three kinds by material classification at present: graphite bi-polar plate, metal double polar plates and composite material double pole plate,
In, graphite bi-polar plate have good electrical and thermal conductivity and chemical stability, but the machining process time-consuming of graphite bi-polar plate compared with
Long, production efficiency is lower, causes the processing cost of graphite bi-polar plate higher, even more than material cost, in addition, graphite bi-polar plate
Performance is more crisp, and the presence of internal void easily leads to its gas leakage, thus certain thickness must be kept to guarantee its air-tightness, this
Just constrain pile volumetric specific power and the promotion of gravimetric specific power of graphite bi-polar plate;Metal type dies required precision is high, at
This is also high, especially must have good electrical and thermal conductivity to metal base to the dash board of metal base, can be thinned to
0.1mm is also air tight, and gas flow can punch forming, it is easy to accomplish mass production, this is conducive to volumetric specific power
The decline with manufacturing cost is promoted, still, to improve its chemical stability, otherwise metal double polar plates carry out specially treated at face
Easily there is corrosion of metal sheet even rust to wear, causes the reduced service life of battery that catastrophic destruction even occurs;Graphite/resin
Composite material double pole plate has the advantages that good processing performance, easy batch production, good corrosion resistance, at low cost, to become research
Hot spot.
For example, Chinese patent literature CN1054105406092A disclose a kind of fuel battery double plates composite material and its
The raw material composition of preparation method, the composite material is as follows: being used as and is led by two kinds of various sizes of natural flake graphite graded materials
Electric filler, graphene or conductive black as additional conductive filler, epoxy novolac type vinylite as binder, TBPB,
For BPO as resin solidification composite initiator, above-mentioned technology carries out gradation using two kinds of various sizes of natural flake graphites, then adds
Add proper amount of nano filler conductive black or graphene to compound and prepare molding compound with epoxy novolac type vinylite binder, then
By molding compound, molded curing prepares sample under certain temperature, pressure, time.But fuel cell bipolar obtained in above-mentioned technology
The conductivity and bending strength of plate composite material are still to be improved.
Therefore, a kind of novel fuel battery double plates composite material is researched and developed, so that having preferable conductivity and bending resistance
Bent strength character, to meet demand of the fuel cell field to the bipolar plate material of superior performance, this is for those skilled in the art
It is a technical problem urgently to be resolved for member.
Summary of the invention
The present invention provides a kind of fuel battery double plates composite material, which has
Preferable conductivity and flexural strength performance, furthermore the present invention further provides preparation methods and purposes.
The present invention solves the technical solution that above-mentioned technical problem uses are as follows:
First aspect present invention provides a kind of fuel battery double plates composite material, including the following raw material: graphite powder, calcium
Titanium ore oxide, rare-earth element modified lanthana and epoxy novolac type vinylite.
Above-mentioned fuel battery double plates composite material, it is preferable that the preparation method of the rare-earth element modified lanthana
It is as follows:
Lanthana is distributed in the aqueous solution containing rare earth element to carry out ion-exchange reactions, to collect after the reaction was completed
Solid phase, the solid phase is through drying, roasting, as through rare-earth element modified lanthana;The rare earth element is yttrium or cerium.
Preferably, the concentration of the aqueous solution containing rare earth element is 0.1~0.5mol/L;The lanthana with it is described dilute
The mass ratio of earth elements is 1:(5~10);Reaction temperature is 20~80 DEG C, the time is 4~6h;The temperature of the drying be 90~
150 DEG C, the time be 1~3h;The temperature of the roasting is 400~600 DEG C, the time is 1~6h.
Preferably, the perovskite oxide is La0.7Sr0.3Fe0.3Mn0.7O3、LaCuO3、La0.6Sr0.4FeO3Or
LaFe0.3Mn0.7O3。
In above-mentioned fuel battery double plates composite material, it is preferable that the graphite powder and the perovskite oxide, described
The mass ratio of rare-earth element modified lanthana, the epoxy novolac type vinylite is (65~85): (1~2): (0.5~
1): (10~20).
Second aspect of the present invention provides a kind of preparation method of above-mentioned fuel battery double plates composite material, including as follows
Step:
(1) graphite powder, perovskite oxide, rare-earth element modified lanthana and epoxy novolac type vinylite are adopted
It is mixed with ultrasound, the ultrasonic mixing time is 10~20min, preferably 15min, forms blend;
(2) by the step (1) blend carry out vacuum drying, drying temperature be 50~70 DEG C, preferably 60 DEG C,
Time is 6~10h, preferably 8h;
(3) will it is dry in the step (2) after blend be pressed and molded in molding die, pressure temperature is 90~
110 DEG C, preferably 100 DEG C, pressure pressure are 12~20Mpa, and the pressure time is 20~30min;Then formed in 140~170 DEG C
20~40min is kept the temperature, demoulds and fuel battery double plates composite material is made.
Third aspect present invention provides a kind of fuel battery double plates composite material that above-mentioned preparation method is prepared.
Fourth aspect present invention, provides a kind of above-mentioned fuel battery double plates composite material or above-mentioned preparation method is prepared into
To fuel battery double plates composite material preparing the purposes in fuel battery double plates.
Above-mentioned technical proposal of the invention has the advantages that
(1) fuel battery double plates composite material of the present invention, including graphite powder, perovskite oxide, rare earth element
Modified lanthana and epoxy novolac type vinylite, the present invention is under the compounding of above-mentioned raw materials, in epoxy novolac type ethylene
Effective conductive path is formed in insulating layer inside base resin, negative effect of the clad to conductivity is reduced, so that electric
Conductance increases substantially;Simultaneously because the addition of perovskite oxide, rare-earth element modified lanthana, can further increase
Conductive channel forms tunnel current, to improve conductivity;In addition, improving composite material under the compounding of above-mentioned raw materials
Flexural strength.After measured, the conductivity of fuel battery double plates composite material produced by the present invention are as follows: 502~590S/cm;
68~75MPa of bending strength.
Specific embodiment
Technical solution of the present invention will be clearly and completely described below, it is clear that described embodiment is this hair
Bright a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not having
Every other embodiment obtained under the premise of creative work is made, shall fall within the protection scope of the present invention.In addition, below
Technical characteristic involved in described different embodiments of the present invention as long as they do not conflict with each other can be mutual
In conjunction with.
Embodiment 1
Present embodiments provide a kind of fuel battery double plates composite material;
Above-mentioned fuel battery double plates composite material includes the following raw material: graphite powder, LaCuO3, cerium modified lanthana and
Epoxy novolac type vinylite;
In above-mentioned raw materials, graphite powder and LaCuO3, cerium modified lanthana, epoxy novolac type vinylite mass ratio
For 65:2:0.5:10.
In the present embodiment, above-mentioned cerium modified lanthana the preparation method is as follows:
By 1g lanthana be distributed to concentration be 0.5mol/L cerous nitrate aqueous solution in (mass ratio=1 of lanthana and cerium:
5) ion exchange, and at 20 DEG C is carried out, is filtered after reacting 6h, solid phase is collected, the solid phase is placed in 150 DEG C of dry 1h, and
Afterwards in 400 DEG C of roasting 6h, cerium modified lanthana is made;
Invention further provides the preparation methods of above-mentioned fuel battery double plates composite material, include the following steps:
(1) by the graphite powder of above-mentioned selected mass ratio, LaCuO3, cerium modified lanthana and epoxy novolac type vinyl tree
Rouge is mixed using ultrasound, and the ultrasonic mixing time is 10min, forms blend;
(2) blend in the step (1) is subjected to vacuum drying, drying temperature is 70 DEG C, time 6h;
(3) blend is pressed and molded in molding die after will be dry in the step (2), and pressure temperature is 90
DEG C, pressure pressure is 20Mpa, and the pressure time is 20min;Then in 140 DEG C of molded heat insulation 40min, demoulds and fuel cell is made
Bipolar plates composite material.
Embodiment 2
Present embodiments provide a kind of fuel battery double plates composite material;
Above-mentioned fuel battery double plates composite material includes the following raw material: graphite powder, La0.7Sr0.3Fe0.3Mn0.7O3, yttrium changes
The lanthana and epoxy novolac type vinylite of property;
In above-mentioned raw materials, graphite powder and La0.7Sr0.3Fe0.3Mn0.7O3, the modified lanthana of yttrium, epoxy novolac type vinyl
The mass ratio of resin is 85:1:1:20.
In the present embodiment, the modified lanthana of above-mentioned yttrium the preparation method is as follows:
By 1g lanthana be distributed to concentration be 0.1mol/L yttrium nitrate aqueous solution in (mass ratio=1 of lanthana and yttrium:
10) ion exchange, and at 80 DEG C is carried out, is filtered after reacting 4h, solid phase is collected, the solid phase is placed in 90 DEG C of dry 3h, and
Afterwards in 600 DEG C of roasting 1h, the modified lanthana of yttrium is made;
Invention further provides the preparation methods of above-mentioned fuel battery double plates composite material, include the following steps:
(1) by graphite powder, the La of above-mentioned selected mass ratio0.7Sr0.3Fe0.3Mn0.7O3, the modified lanthana and phenolic aldehyde ring of yttrium
Oxygen type vinylite is mixed using ultrasound, and the ultrasonic mixing time is 20min, forms blend;
(2) blend in the step (1) is subjected to vacuum drying, drying temperature is 50 DEG C, time 10h;
(3) blend is pressed and molded in molding die after will be dry in the step (2), and pressure temperature is 110
DEG C, pressure pressure is 12Mpa, and the pressure time is 30min;Then in 170 DEG C of molded heat insulation 20min, demoulds and fuel cell is made
Bipolar plates composite material.
Embodiment 3
Present embodiments provide a kind of fuel battery double plates composite material;
Above-mentioned fuel battery double plates composite material includes the following raw material: graphite powder, La0.6Sr0.4FeO3, the modified oxygen of yttrium
Change lanthanum and epoxy novolac type vinylite;
In above-mentioned raw materials, graphite powder and La0.6Sr0.4FeO3, yttrium modified lanthana, epoxy novolac type vinylite
Mass ratio is 80:1.5:0.8:15.
In the present embodiment, the modified lanthana of above-mentioned yttrium the preparation method is as follows:
By 1g lanthana be distributed to concentration be 0.2mol/L yttrium nitrate aqueous solution in (mass ratio=1 of lanthana and yttrium:
8) ion exchange, and at 60 DEG C is carried out, is filtered after reacting 5h, solid phase is collected, the solid phase is placed in 120 DEG C of dry 2h, and
Afterwards in 500 DEG C of roasting 5h, the modified lanthana of yttrium is made;
Invention further provides the preparation methods of above-mentioned fuel battery double plates composite material, include the following steps:
(1) by graphite powder, the La of above-mentioned selected mass ratio0.6Sr0.4FeO3, the modified lanthana and epoxy novolac type second of yttrium
Ene based resins are mixed using ultrasound, and the ultrasonic mixing time is 15min, form blend;
(2) blend in the step (1) is subjected to vacuum drying, drying temperature is 60 DEG C, time 8h;
(3) blend is pressed and molded in molding die after will be dry in the step (2), and pressure temperature is 100
DEG C, pressure pressure is 15Mpa, and the pressure time is 25min;Then in 150 DEG C of molded heat insulation 30min, demoulds and fuel cell is made
Bipolar plates composite material.
Embodiment 4
Present embodiments provide a kind of fuel battery double plates composite material;
Above-mentioned fuel battery double plates composite material includes the following raw material: graphite powder, LaFe0.3Mn0.7O3, cerium modified oxygen
Change lanthanum and epoxy novolac type vinylite;
In above-mentioned raw materials, graphite powder and LaFe0.3Mn0.7O3, cerium modified lanthana, epoxy novolac type vinylite
Mass ratio is 70:1.2:0.6:12.
In the present embodiment, above-mentioned cerium modified lanthana the preparation method is as follows:
By 1g lanthana be distributed to concentration be 0.4mol/L cerous nitrate aqueous solution in (mass ratio=1 of lanthana and cerium:
6) ion exchange, and at 30 DEG C is carried out, is filtered after reacting 4h, solid phase is collected, the solid phase is placed in 130 DEG C of dry 3h, and
Afterwards in 550 DEG C of roasting 2h, cerium modified lanthana is made;
Invention further provides the preparation methods of above-mentioned fuel battery double plates composite material, include the following steps:
(1) by graphite powder, the LaFe of above-mentioned selected mass ratio0.3Mn0.7O3, cerium modified lanthana and epoxy novolac type second
Ene based resins are mixed using ultrasound, and the ultrasonic mixing time is 18min, form blend;
(2) blend in the step (1) is subjected to vacuum drying, drying temperature is 65 DEG C, time 7h;
(3) blend is pressed and molded in molding die after will be dry in the step (2), and pressure temperature is 105
DEG C, pressure pressure is 18Mpa, and the pressure time is 28min;Then in 160 DEG C of molded heat insulation 35min, demoulds and fuel cell is made
Bipolar plates composite material.
Embodiment 5
Present embodiments provide a kind of fuel battery double plates composite material;
Above-mentioned fuel battery double plates composite material includes the following raw material: graphite powder, LaFe0.3Mn0.7O3, cerium modified oxygen
Change lanthanum and epoxy novolac type vinylite;
In above-mentioned raw materials, graphite powder and LaFe0.3Mn0.7O3, cerium modified lanthana, epoxy novolac type vinylite
Mass ratio is 75:1.8:0.8:18.
In the present embodiment, above-mentioned cerium modified lanthana the preparation method is as follows:
By 1g lanthana be distributed to concentration be 0.1mol/L cerous nitrate aqueous solution in (mass ratio=1 of lanthana and cerium:
9) ion exchange, and at 70 DEG C is carried out, is filtered after reacting 6h, solid phase is collected, the solid phase is placed in 150 DEG C of dry 3h, and
Afterwards in 400 DEG C of roasting 1h, cerium modified lanthana is made;
Invention further provides the preparation methods of above-mentioned fuel battery double plates composite material, include the following steps:
(1) by graphite powder, the LaFe of above-mentioned selected mass ratio0.3Mn0.7O3, cerium modified lanthana and epoxy novolac type second
Ene based resins are mixed using ultrasound, and the ultrasonic mixing time is 11min, form blend;
(2) blend in the step (1) is subjected to vacuum drying, drying temperature is 55 DEG C, time 9h;
(3) blend is pressed and molded in molding die after will be dry in the step (2), and pressure temperature is 110
DEG C, pressure pressure is 18Mpa, and the pressure time is 30min;Then in 170 DEG C of molded heat insulation 40min, demoulds and fuel cell is made
Bipolar plates composite material.
Experimental example 1
Measure the conductivity and bending strength of fuel battery double plates composite material made from Examples 1 to 5.Its result is such as
Shown in table 1.
The conductivity and bending strength of fuel battery double plates composite material made from 1 Examples 1 to 5 of table
Conductivity (s/cm) | Bending strength (MPa) | |
Embodiment 1 | 502 | 70 |
Embodiment 2 | 511 | 68 |
Embodiment 3 | 590 | 74 |
Embodiment 4 | 583 | 75 |
Embodiment 5 | 567 | 72 |
As shown in Table 1, the bending strength of fuel battery double plates composite material made from the embodiment of the present invention is above US
DOE technical indicator (25MPa).
Fuel battery double plates composite material produced by the present invention conductivity with higher and bending strength.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (9)
1. a kind of fuel battery double plates composite material, which is characterized in that including the following raw material: graphite powder, perovskite oxide,
Rare-earth element modified lanthana and epoxy novolac type vinylite.
2. fuel battery double plates composite material according to claim 1, which is characterized in that described rare-earth element modified
Lanthana the preparation method is as follows:
Lanthana is distributed in the aqueous solution containing rare earth element to carry out ion-exchange reactions, it is solid to collect after the reaction was completed
Phase, the solid phase is through drying, roasting, as through rare-earth element modified lanthana.
3. fuel battery double plates composite material according to claim 2, which is characterized in that
The concentration of the aqueous solution containing rare earth element is 0.1~0.5mol/L;The matter of the lanthana and the rare earth element
Amount is than being 1:(5~10);The rare earth element is yttrium or cerium.
4. fuel battery double plates composite material according to claim 3, which is characterized in that
The reaction temperature is 20~80 DEG C, the time is 4~6h;
The temperature of the drying is 90~150 DEG C, the time is 1~3h;
The temperature of the roasting is 400~600 DEG C, the time is 1~6h.
5. fuel battery double plates composite material according to claim 1, which is characterized in that the perovskite oxide is
La0.7Sr0.3Fe0.3Mn0.7O3、LaCuO3、La0.6Sr0.4FeO3Or LaFe0.3Mn0.7O3。
6. fuel battery double plates composite material according to claim 1, which is characterized in that the graphite powder and the calcium
Titanium ore oxide, the rare-earth element modified lanthana, the epoxy novolac type vinylite mass ratio be (65~
85): (1~2): (0.5~1): (10~20).
7. a kind of preparation method of fuel battery double plates composite material described in any one of claims 1-6, which is characterized in that
Include the following steps:
(1) by graphite powder, perovskite oxide, rare-earth element modified lanthana and epoxy novolac type vinylite using super
Sound is mixed, and the ultrasonic mixing time is 10~20min, forms blend;
(2) blend in the step (1) is subjected to vacuum drying, drying temperature is 50~70 DEG C, the time is 6~10h;
(3) blend is pressed and molded in molding die after will be dry in the step (2), and pressure temperature is 90~110
DEG C, pressure pressure is 12~20Mpa, and the pressure time is 20~30min;Then in 140~170 DEG C of 20~40min of molded heat insulation,
It demoulds and fuel battery double plates composite material is made.
8. a kind of fuel battery double plates composite material being prepared by preparation method as claimed in claim 7.
9. one kind is by fuel battery double plates composite material described in any one of claims 1-6 or system as claimed in claim 7
The fuel battery double plates composite material that Preparation Method is prepared is preparing the purposes in fuel battery double plates.
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CN201811116196.5A CN109244501B (en) | 2018-09-25 | 2018-09-25 | Fuel cell bipolar plate composite material and preparation method and application thereof |
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CN1238919C (en) * | 2003-12-26 | 2006-01-25 | 清华大学 | Process for preparing fuel cell bipolar plate and composite material used thereof |
SE535245C2 (en) * | 2010-08-02 | 2012-06-05 | Gett Fuel Cells Internat Ab | Fuel cells without octrolytes |
CN102044678B (en) * | 2010-11-26 | 2012-10-03 | 中国科学院上海硅酸盐研究所 | Cathode side current collection material of solid oxide fuel cell and preparation method thereof |
CN102569828A (en) * | 2010-12-22 | 2012-07-11 | 清华大学 | Microcrystal graphite compound for double-pole plate of fuel cell and preparation method of microcrystal graphite compound |
CN102760896B (en) * | 2011-04-29 | 2015-01-21 | 中国科学院大连化学物理研究所 | Current collection component of anode supporting tube type solid oxide fuel cell and application thereof |
CN105406092B (en) * | 2015-11-04 | 2018-08-07 | 四川大学 | A kind of fuel battery double plates composite material and preparation method |
CN107790120B (en) * | 2017-09-15 | 2020-06-16 | 天津大学 | Cerium modified lanthanum oxide catalyst and preparation method and application thereof |
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