CN108550866A - The method that two-dimensional material assisted infusion prepares anode of solid oxide fuel cell - Google Patents
The method that two-dimensional material assisted infusion prepares anode of solid oxide fuel cell Download PDFInfo
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- CN108550866A CN108550866A CN201810408506.4A CN201810408506A CN108550866A CN 108550866 A CN108550866 A CN 108550866A CN 201810408506 A CN201810408506 A CN 201810408506A CN 108550866 A CN108550866 A CN 108550866A
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention discloses a kind of methods that two-dimensional material assisted infusion prepares anode of solid oxide fuel cell, and steps are as follows：（1）Configure graphene oxide solution；（2）The salting liquid of metal is configured, is added in graphene oxide solution and forms maceration extract；（3）Maceration extract is introduced inside porous supporting body, high-temperature calcination under argon gas atmosphere；（4）It is restored under reducing atmosphere.The present invention prepares the anode of solid oxide fuel cell using two-dimensional material assisted infusion, the shortcomings that existing catalyst particle is unevenly distributed when infusion process prepares electrode can be improved, make catalyst particle high degree of dispersion, it is evenly distributed on porous supporting body, reduce the agglomeration between particle, improves the stability of anode.Make that there is the electric conductivity being connected between metallic using the good electron transport ability of two-dimensional graphene simultaneously, improves the conductivity and catalytic performance of anode.
Description
Technical field
The present invention relates to the preparation field of porous electrode, specially a kind of two-dimensional material assisted infusion prepares solid oxidation
The method of object anode of fuel cell.
Background technology
Solid oxide fuel cell（SOFC）, pollution high with energy conversion efficiency be low and fuel source is extensively etc. excellent
Point is a kind of energy resource system of clean and effective, it is considered to be one of the Main way of new energy application from now on.Monocell mainly by
Electrolyte, cathode and anode composition.In anode support type SOFC, in addition to as supporter, anode or fueled electrochemical oxygen
The catalyst for changing reaction, provides reaction interface.In addition, anode also needs to the electronics and gas of transfer reaction generation.
Size by controlling anode pellets can improve the microstructure of anode, and then increase electrochemical reaction area.Leaching
Stain method is a kind of effective method for introducing nano particle, is widely used in the preparation of SOFC electrodes.It is prepared using infusion process
SOFC, stability are always to restrict the biggest obstacle of its application.By taking the Ni/YSZ composite materials being commonly used as an example, work as leaching
When stain amount is relatively low, Ni particles, which are mainly isolated in the form of island, to be existed, and the connection electric conductivity of electrode is poor；With the increasing of impregnation increment
Add, the Ni particles of multiple islands are close to each other, and the surface/interface energy of Ni particles is reduced by sintering, is covered to connect formation
The high conductive network of cover degree.But the sintering of Ni particles, so that the catalytic activity of electrode is reduced, influences the stability of electrode.Research
Show that the anti-caking power of equally distributed Ni catalyst particles is most strong, the distribution of the Ni catalyst by regulating and controlling dipping is conducive to
The activity caused by sintering is inhibited to decline.
Currently, avoiding the sintering of metal catalysis particles, the stability of electrode is improved, while ensureing the metal catalytic grain of dispersion
There is good connection electric conductivity, being still infusion process technology of preparing has critical issue to be solved between son.
Invention content
The problem for the anode of solid oxide fuel cell stability difference that the present invention is prepared for infusion process proposes one kind two
The method that material assisted infusion prepares anode of solid oxide fuel cell is tieed up, is specifically with ultra-thin two-dimension grapheme material
Carrier loads to the metallic catalytic particles of anode on graphene sheet layer, using infusion process by Metal/grapheme composite catalytic layer
It is introduced into multihole anode support.Purpose is that metallic catalytic particles are loaded to two-dimentional material using two-dimensional graphene material as carrier
On material, reduce the agglomeration of metallic.
The present invention adopts the following technical scheme that realization：
A kind of method that two-dimensional material assisted infusion prepares anode of solid oxide fuel cell, includes the following steps：
（1）, will purchase or homemade graphite oxide（GO）It is added in deionized water, magnetic agitation and ultrasonic disperse are each at room temperature
0.5 ~ for 24 hours, it is configured to the graphene oxide solution of a concentration of 0.1 ~ 2mg/ml.
（2）, weigh a certain amount of nickel nitrate and be added in deionized water, certain density ammonia spirit is added until completely molten
Solution.Above-mentioned mixed solution is added to step（1）Graphene oxide solution in, magnetic agitation or ultrasound a period of time, make
Ni2+It is fully connected on GO lamellas, obtains being supported on the nickel hydroxide colloid on graphene oxide.
（3）, will load have nickel hydroxide graphene oxide solution introduce multihole anode support in, it is freeze-dried
Afterwards, it is warming up to 300 ~ 500 DEG C of 0.5 ~ 4h of calcining under argon gas atmosphere protection, obtains being supported on redox graphene（RGO）On
Nickel oxide.It repeats the above process 5 ~ 80 times.
（4）, by the above-mentioned anode for being impregnated with graphene-supported nickel oxide, calcine 1 under 600 ~ 800 DEG C of hydrogen atmosphere ~
4h makes nickel oxide be reduced to nickel, obtains the anode of solid oxidized fuel cell.
As being further described below for the present invention：
Step（1）In, graphene oxide solution can also be the aqueous solution of addition organic amine and alcohol medium.
Step（2）In, a concentration of 5 ~ 50mmol/L of nickel nitrate solution.Ammonia concn is 25% ~ 28%.Nickel nitrate solution and
The volume ratio of graphene oxide solution is 1:（1~50）.Nickel nitrate solution can also be the nitrate, acetate, oxalic acid of metal
One or more of salt, acylate, the metal include Ni, Au, Ag, Pt, Cu, Pd, Ru, Rh, Ce or Co.
The method that two-dimensional material assisted infusion of the present invention prepares anode of solid oxide fuel cell, utilizes two
Graphene auxiliary is tieed up in multihole anode support impregnated of high degree of dispersion and equally distributed metallic catalytic particles, reduces catalysis
The agglomeration phenomenon of agent, while making that using the good electron transport ability of two-dimensional graphene, there is between metallic connection
Electric conductivity improves the conductivity and catalytic performance of anode.
Description of the drawings
Fig. 1 shows photos of the porous YSZ made from embodiment 1 after freeze-dried.
Fig. 2 a indicate the SEM figures of horizontal cross-sections of the porous YSZ after high temperature sintering made from embodiment 1.
Fig. 2 b indicate the SEM figures of vertical sections of the porous YSZ after high temperature sintering made from embodiment 1.
Fig. 3 indicates nickel nitrate and the freeze-dried SEM figures with after high temperature reduction of graphene oxide mixed solution, specially
The nickel nano particle of oxidation graphene film load.
Fig. 4 a indicate the SEM figures of NiO/RGO made from embodiment 1.
Fig. 4 b indicate the SEM figures of Ni/RGO composite catalytic layers made from embodiment 1.
Specific implementation mode
Specific embodiments of the present invention are described in detail below in conjunction with the accompanying drawings.
Embodiment 1
A kind of method that two-dimensional material assisted infusion prepares anode of solid oxide fuel cell, steps are as follows：
（1）, with Hummers methods prepare graphene oxide, 100mg graphite oxides are weighed after being separated by filtration and are added to 200mL
In ionized water, it is configured to the graphene oxide solution of a concentration of 0.5mg/ml, 100mg cetyl trimethyls are added into solution
Ammonium bromide, at room temperature ultrasound 30min after magnetic agitation 4h.
（2）, nickel nitrate solution that configuration concentration is 20mmol/L, be slowly added to a concentration of 28% ammonia spirit until complete
Fully dissolved.It weighs the above-mentioned solution of 20mL and is added to step（1）Graphene oxide solution in, magnetic agitation 2h, makes Ni at room temperature2+
It is fully connected on GO lamellas, obtains being supported on the nickel hydroxide colloid on graphene oxide.Mixed solution is heated to 90 DEG C
Extra ammonium hydroxide is set to volatilize until solution is neutrality.
（3）, the preparation method of multihole anode support it is as follows：
3.1, configuration quality score is the sodium alginate colloidal sol of 1.5wt%, and sodium alginate is made fully to dissolve.In sodium alginate soln
It is middle that the 8YSZ that solid concentration is 5wt% is added（The zirconium oxide of 8% stabilized with yttrium oxide）Electrolyte powder, mixing and ball milling 8h.
3.2, it to being injected into the glass beaker of 100mL after mixed slurry froth in vacuum, is uniformly sprayed on slurry upper layer
The CaCl of a concentration of 1.5mol/L2Solution stands 48h.
3.3, each 5mm of layer on wet base is cut off, it is with deionized water that sample clean is clean, green body is soaked in 1mol/L
Glucolactone solution in replace for 24 hours.
3.4, sample is soaked in t-butanol solution and carries out exchange of solvent for 24 hours, it is freeze-dried（-50℃）After be put into
Dumping 2h in 600 DEG C of high temperature furnace.Sample after dumping obtains the YSZ with straight-through pore structure through 1400 DEG C of high temperature sintering 4h
Supporter.It is as shown in Figure 1 the sample photo after freeze-drying, Fig. 2 a and Fig. 2 b are respectively the level section of sample after high temperature sintering
The aperture of face and vertical section figure, clear opening is 80 ~ 120 μm.
The preparation method of the anode support, process is simple, easily operated, and Metal/grapheme can greatly be promoted multiple
Close application of the catalyst in fuel cell electrode.
（4）, by step（2）Mixed solution be impregnated into step（3）It is freeze-dried in the multihole anode support of preparation
Afterwards, it is warming up to 500 DEG C of calcining 2h under argon gas atmosphere protection, obtains being supported on redox graphene（RGO）On nickel oxide,
As shown in fig. 4 a.
Repeat step（4）Operation 20 times.
（5）, by the above-mentioned anode for being impregnated with graphene-supported nickel oxide, calcine 2h under 700 DEG C of hydrogen atmosphere, make oxygen
Change nickel and be reduced to nickel, obtains the solid oxidized fuel cell anode with Ni/RGO composite catalytic layers, as shown in Figure 4 b.
In embodiment 1, nickel nitrate solution can also be nitrate, acetate, oxalates, the acylate of metal, metal
Including Ni, Au, Ag, Pt, Cu, Pd, Ru, Rh, Ce or Co.
The dipping method of catalyst is to be dripped to maceration extract leaching in multihole anode support using dropper or needle tubing, every time
The amount of maceration extract is instilled until can not permeating or in the way of solution impregnates vacuum filtration.
When impregnating a variety of salting liquids, the salting liquid of metal can be respectively configured, it is molten that graphene oxide then is added simultaneously
In liquid, mixed solution is impregnated into multihole anode support.It is molten can also graphene oxide to be added in metal salt solution respectively
In liquid, several metal salts/graphene mixed solution is impregnated into multihole anode support successively.
Multihole anode support be stabilized with yttrium oxide zirconium oxide, aluminium oxide, cerium oxide and its doping oxide etc. with make
The porous refractory ceramics supporter that hole agent is prepared after being sufficiently mixed.The side of addition pore creating material may be used in multihole anode support
Prepared by formula, pore creating material includes substance readily volatilized under the high temperature such as graphite, flour, starch, fiber.It can also will be with anode-supported
The mode for carrying out pore-creating is removed with nitric acid after the metal oxide reduction of co-sintering on body.The technologies systems such as 3D printing can also be used
The standby anode support with honeycomb hole.
Multihole anode support can also be a certain or several progress in the oxide of nickel, cobalt and iron magnesium-yttrium-transition metal
Mixing, then mixed with doped zirconia or doped cerium oxide and pore creating material, elemental metals and oxygen are formed after sintering and reduction
The composite material of compound ceramics composition；Anode material can also be the oxide material for having selective catalysis effect to fuel, packet
Include the composite oxide material of 2 kinds in La, Sr, Ba, Ca, Cr, Ti, Mg, Mo, Fe, Mn these metallic elements or Multiple components
The composite material mixed with pore creating material.
Embodiment 2
A kind of method that two-dimensional material assisted infusion prepares anode of solid oxide fuel cell, steps are as follows：
（1）, weigh 100mg graphene oxides and be added in the ethanol amine of 25mL, magnetic agitation and ultrasonic disperse are each at room temperature
30min；Then it is added in 100mL deionized waters, continues magnetic agitation 10h.
（2）, the copper acetate and nickel acetate solution of a concentration of 10mmol/L is respectively configured, ammonia spirit is slowly added dropwise until complete
Fully dissolved, each above-mentioned solution of 50mL that measures are added in graphene oxide solution, at room temperature magnetic agitation 2h.
（3）, YSZ multihole anode supports prepared by embodiment 1 are dipped into step（2）Mixed solution in, using true
The mode that sky filters is freeze-dried after impregnating.It is to slowly warm up to 500 DEG C of calcining 2h under argon gas atmosphere protection, obtains reduction-oxidation
Graphene-supported copper oxide and nickel oxide composite catalytic layer.
Repeat step（3）Operation 5 ~ 50 times.
（4）, by the above-mentioned anode for being impregnated with graphene-supported nickel oxide, calcine 2h under 700 DEG C of hydrogen atmosphere, make oxygen
Change copper and nickel oxide reduction, obtains the solid oxidized fuel cell anode with Cu-Ni/RGO composite catalytic layers.
Embodiment 3
A kind of method that two-dimensional material assisted infusion prepares anode of solid oxide fuel cell, steps are as follows：
（1）, weigh 100mg graphene oxides and be added in 100mL deionized waters, ultrasonic disperse after magnetic agitation 2h at room temperature
30min。
（2）, cerous nitrate solution that configuration concentration is 10mmol/L, ammonia spirit is added until be completely dissolved, measures 20mL
Above-mentioned solution is added in graphene oxide solution, at room temperature magnetic agitation 2h.By mixed solution be heated to 90 DEG C make it is extra
Ammonium hydroxide volatilization is until solution is neutrality.
（3）, by NiO and solid YSZ electrolyte according to mass ratio be 0.25 ~ 9:1 ratio mixing, grinds after pore creating material is added
Grind 2h.It weighs the anode powder after grinding and is put into the compression moulding under the pressure of 10MPa ~ 2000MPa in grinding tool.By anode green body
0.1 ~ 10h is calcined at a high temperature of 900 ~ 1500 DEG C, obtains porous Ni/YSZ anodes.
（4）, by step（3）The porous Ni/YSZ anodes prepared are dipped into step（2）Mixed solution in, taken out using vacuum
The mode of filter is freeze-dried after impregnating.500 DEG C of calcining 2h are warming up under argon gas atmosphere protection.
Repeat step（4）Operation 20 times, obtains with CeO2/ RGO composite catalytic layers modify Ni/YSZ anodes.
The present embodiment has the beneficial effect that：Cerium oxide has good oxygen transmittability, can improve anode to fuel gas
The catalytic of body oxidation reaction improves the phase reaction area of anode, while two-dimensional graphene can improve the electric conductivity of anode.
It should be pointed out that for the those skilled in the art of the art, without departing from the principle of the present invention,
Several improvement and application can also be made, these are improved and application is also considered as protection scope of the present invention.
Claims (10)
1. a kind of method that two-dimensional material assisted infusion prepares anode of solid oxide fuel cell, it is characterised in that：Including
Following steps：
（1）, graphite oxide is added in deionized water, magnetic agitation and ultrasonic disperse each 0.5 ~ for 24 hours, are configured to concentration at room temperature
For the graphene oxide solution of 0.1 ~ 2mg/mL；
（2）, weigh nickel nitrate be added deionized water in prepare nickel nitrate solution a concentration of 5 ~ 50mmol/L, be added it is a concentration of
Above-mentioned mixed solution is added to step by 25% ~ 28% ammonia spirit up to being completely dissolved（1）Graphene oxide solution in,
Magnetic agitation or supersound process；
（3）, there is the graphene oxide solution of nickel hydroxide to be introduced in multihole anode support by dipping the load, it is chilled dry
After dry, it is warming up to 300 ~ 500 DEG C of 0.5 ~ 4h of calcining under argon gas atmosphere protection, obtains being supported on the oxygen on redox graphene
Change nickel；
Repeat the process 5 ~ 80 times of above-mentioned dipping and reduction；
（4）, by the above-mentioned anode for being impregnated with graphene-supported nickel oxide, 1 ~ 4h is calcined under 600 ~ 800 DEG C of hydrogen atmosphere, is made
Nickel oxide is reduced to nickel, obtains the anode of solid oxidized fuel cell.
2. the method that two-dimensional material assisted infusion according to claim 1 prepares anode of solid oxide fuel cell,
It is characterized in that：The volume ratio of nickel nitrate solution and graphene oxide solution is 1:（1~50）.
3. two-dimensional material assisted infusion according to claim 1 or 2 prepares the side of anode of solid oxide fuel cell
Method, it is characterised in that：Organic amine or alcohol medium are added in graphene oxide solution.
4. the method that two-dimensional material assisted infusion according to claim 1 prepares anode of solid oxide fuel cell,
It is characterized in that：The nickel nitrate solution is by a kind of or several in the nitrate of metal, acetate, oxalates, acylate
Kind solution is replaced, and the metal includes Ni, Au, Ag, Pt, Cu, Pd, Ru, Rh or Co.
5. the method that two-dimensional material assisted infusion according to claim 1 prepares anode of solid oxide fuel cell,
It is characterized in that：When impregnating various metals salting liquid, the salting liquid of metal is respectively configured, it is molten that graphene oxide then is added simultaneously
In liquid, mixed solution is impregnated into multihole anode support；Alternatively, graphene oxide solution is added in metal salt solution respectively
In, several metal salts/graphene mixed solution is impregnated into multihole anode support respectively successively.
6. the method that two-dimensional material assisted infusion according to claim 5 prepares anode of solid oxide fuel cell,
It is characterized in that：Dipping method is the method dripped to maceration extract leaching using dropper or needle tubing in multihole anode support, often
The secondary amount for instilling maceration extract is not until can not permeating；Or porous anode is dipped into maceration extract using the side of vacuum filtration
Formula impregnates.
7. the method that two-dimensional material assisted infusion according to claim 1 prepares anode of solid oxide fuel cell,
It is characterized in that：The material of the multihole anode support is zirconium oxide, aluminium oxide, cerium oxide and its doping of stabilized with yttrium oxide
The porous refractory ceramics supporter that oxide etc. is prepared after being sufficiently mixed with pore creating material；
Either nickel, cobalt and iron magnesium-yttrium-transition metal oxide in it is a certain or several mixed, then with doped zirconia
Or doped cerium oxide and pore creating material mix, and the composite wood of elemental metals and oxide ceramics composition is formed after sintering and reduction
Material；
Either to fuel have selective catalysis effect oxide material, including La, Sr, Ba, Ca, Cr, Ti, Mg, Mo, Fe,
The composite material that the composite oxide material of two or more ingredients in these metallic elements of Mn is mixed with pore creating material.
8. the method that two-dimensional material assisted infusion according to claim 1 prepares anode of solid oxide fuel cell,
It is characterized in that：The multihole anode support is prepared using Ionic gelation method, specific as follows：
I, the sodium alginate soln that mass fraction is 0.5 ~ 2wt% and the electrolyte powder that solid concentration is 5wt% ~ 20wt% is mixed
It closes, 4 ~ 12h of ball milling；Electrolyte powder is the zirconium oxide of stabilized with yttrium oxide or the cerium oxide of samarium oxide/oxidation Gd2 O3；
II, it after to mixed slurry froth in vacuum, is injected into cylindrical die, by the CaCl of a concentration of 0.5 ~ 2mol/L2Solution
Even spraying demoulds the wet base of solidification for obtaining having straight-through pore structure to pulp surface after standing 36 ~ 72h；
Green body is soaked in glucolactone effects of ion displacement 12 ~ for 24 hours by the surface layer and bottom for III, cutting off wet base；
Ⅸ, processing is dried to wet base, the green body after drying is put into draft glue discharging furnace, dump temperature is 550 ~ 650 DEG C, dumping
Sample afterwards obtains the anode support with straight-through pore structure through 1300 ~ 1500 DEG C of 2 ~ 4h of high temperature sintering.
9. the method according to claim 8 for preparing multihole anode support, it is characterised in that：Multihole anode support
Aperture size is 5 ~ 200 μm, and porosity is 20% ~ 80%.
10. a kind of method that two-dimensional material assisted infusion prepares anode of solid oxide fuel cell, it is characterised in that：Including
Following steps：
（1）, graphite oxide is added in deionized water, magnetic agitation and ultrasonic disperse each 0.5 ~ for 24 hours, are configured to concentration at room temperature
For the graphene oxide solution of 0.1 ~ 2mg/mL；
（2）, weigh cerous nitrate be added deionized water in prepare cerous nitrate solution a concentration of 5 ~ 50mmol/L, be added it is a concentration of
Above-mentioned mixed solution is added to step by 25% ~ 28% ammonia spirit up to being completely dissolved（1）Graphene oxide solution in,
Magnetic agitation or supersound process；
（3）, by NiO and solid YSZ electrolyte according to mass ratio be 0.25 ~ 9:1 ratio mixing, grinds after pore creating material is added
2h weighs the anode powder after grinding and is put into the compression moulding under the pressure of 10MPa ~ 2000MPa in grinding tool, anode green body is existed
0.1 ~ 10h is calcined at a high temperature of 900 ~ 1500 DEG C, obtains porous Ni/YSZ anodes；
（4）, by step（3）The porous Ni/YSZ anodes prepared are dipped into step（2）Mixed solution in, using vacuum filtration
Mode is freeze-dried after impregnating；500 DEG C of calcining 2h are warming up under argon gas atmosphere protection；
（5）, repeat step（4）Repeatedly, it obtains with CeO2/ RGO composite catalytic layers modify Ni/YSZ anodes.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110117807A (en) * | 2019-03-09 | 2019-08-13 | 深圳市中科墨磷科技有限公司 | A kind of two-dimensional material-transition metal hetero-junctions preparation of sections method |
| CN111081909A (en) * | 2019-12-26 | 2020-04-28 | 郑州大学 | Compressible quasi-solid nickel-iron battery prepared based on 3D printing technology and preparation method |
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| CN114433077A (en) * | 2020-11-02 | 2022-05-06 | 中国科学院大连化学物理研究所 | Graphene-based bifunctional catalyst, preparation method and application |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102332588A (en) * | 2011-10-17 | 2012-01-25 | 哈尔滨工业大学 | Method for preparing anode of solid oxide fuel cell by using immersion method |
| CN103236550A (en) * | 2013-04-22 | 2013-08-07 | 陕西煤业化工技术研究院有限责任公司 | Graphene-modified nickel-base composite anode material of solid oxide fuel cell and preparation method thereof |
| CN103274704A (en) * | 2013-05-07 | 2013-09-04 | 清华大学 | Micron-order honeycomb ceramic and method for adjusting and controlling pore diameter and size of pore wall of micron-order honeycomb ceramic |
| WO2016177951A1 (en) * | 2015-05-06 | 2016-11-10 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Catalyst supported by carbon nanotubes and by graphene, and method for preparing same |
| JP2017142949A (en) * | 2016-02-09 | 2017-08-17 | 株式会社デンソー | Fuel battery single cell |
-
2018
- 2018-05-02 CN CN201810408506.4A patent/CN108550866B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102332588A (en) * | 2011-10-17 | 2012-01-25 | 哈尔滨工业大学 | Method for preparing anode of solid oxide fuel cell by using immersion method |
| CN103236550A (en) * | 2013-04-22 | 2013-08-07 | 陕西煤业化工技术研究院有限责任公司 | Graphene-modified nickel-base composite anode material of solid oxide fuel cell and preparation method thereof |
| CN103274704A (en) * | 2013-05-07 | 2013-09-04 | 清华大学 | Micron-order honeycomb ceramic and method for adjusting and controlling pore diameter and size of pore wall of micron-order honeycomb ceramic |
| WO2016177951A1 (en) * | 2015-05-06 | 2016-11-10 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Catalyst supported by carbon nanotubes and by graphene, and method for preparing same |
| JP2017142949A (en) * | 2016-02-09 | 2017-08-17 | 株式会社デンソー | Fuel battery single cell |
Cited By (9)
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| CN110117807A (en) * | 2019-03-09 | 2019-08-13 | 深圳市中科墨磷科技有限公司 | A kind of two-dimensional material-transition metal hetero-junctions preparation of sections method |
| CN111081909A (en) * | 2019-12-26 | 2020-04-28 | 郑州大学 | Compressible quasi-solid nickel-iron battery prepared based on 3D printing technology and preparation method |
| CN111081909B (en) * | 2019-12-26 | 2022-04-08 | 郑州大学 | 3D printing compressible quasi-solid nickel-iron battery and preparation method |
| CN112151818A (en) * | 2020-10-26 | 2020-12-29 | 中北大学 | Alkaline system direct methanol fuel cell anode catalyst and preparation method thereof |
| CN114433077A (en) * | 2020-11-02 | 2022-05-06 | 中国科学院大连化学物理研究所 | Graphene-based bifunctional catalyst, preparation method and application |
| CN114433077B (en) * | 2020-11-02 | 2023-06-06 | 中国科学院大连化学物理研究所 | Graphene-based bifunctional catalyst, preparation method and application |
| CN114944491A (en) * | 2022-07-14 | 2022-08-26 | 天津工业大学 | Three-dimensional gradient carbon skeleton composite material for inhibiting growth of lithium dendrites and preparation method thereof |
| CN116072892A (en) * | 2023-01-16 | 2023-05-05 | 福州大学 | Method for improving Ba-containing composite oxygen electrode by surface reconstruction |
| CN116072892B (en) * | 2023-01-16 | 2024-04-30 | 福州大学 | Method for improving Ba-containing composite oxygen electrode by surface reconstruction |
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