CN101442128B - Diffusion layer for integral regeneratable fuel cell and preparation thereof - Google Patents
Diffusion layer for integral regeneratable fuel cell and preparation thereof Download PDFInfo
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Abstract
The invention relates to a diffusion layer for an integrated regenerative fuel battery and preparation thereof. The diffusion layer consists of a substrate layer and a microporous layer which is coated on the substrate layer, wherein the microporous layer is formed by mixing an intermetallic compound and noble metal catalyst with a mass ratio of between 0.1:1 and 1:0.1. Compared with the prior art, the diffusion layer has the advantages that: firstly, the diffusion layer has good electrical conductivity; secondly, the diffusion layer has good chemical stability and electrochemical stability and superior corrosion resistance; thirdly, the diffusion layer has low cost; and fourthly, the diffusion layer has simple process and is easy to realize industrialization. Therefore, the novel diffusion layer adopting the intermetallic compound can obviously improve the cycle life of the regenerative fuel battery. The diffusion layer for the regenerative fuel battery with low cost and high durability can be prepared by the method. A regenerative fuel battery chip MEA and a single battery prepared by the prepared diffusion layer have good output performance.
Description
Technical field
The present invention relates to the integral regeneratable fuel cell diffusion layer, particularly be applied to the diffusion layer and the preparation thereof of integral regeneratable fuel cell.
Background technology
Integral regeneratable fuel cell (Unitized Regenerative Fuel Cell is called for short URFC) is a kind of of regeneratable fuel cell (Regenerative Fuel Cell is called for short RFC).Its specific energy is other high energy secondary cell such as lithium ion battery several times up to 400～1000Wh/Kg.For split RFC, the URFC system is simple, and is with low cost, and specific energy and specific power height are easy to miniaturization.Because URFC can satisfy the energy storage demand that discharges and recharges for a long time, application prospect is very wide, especially has incomparable advantage in the space power system field.
URFC can carry out two kinds of mode of operations on same assembly be fuel cell pattern and water electrolysis pattern.During with the fuel cell mode operation, hydrogen electrode is as anode, and reaction generates H
+, output electronics, H
+Move to oxygen electrode by the Nafion film, generate water with oxygen reaction.During with the water electrolysis mode operation, oxygen electrode is as anode, and battery utilizes the electric energy brine electrolysis to generate hydrogen and oxygen stores for future use.
Diffusion layer mainly plays the effect of supporting Catalytic Layer, collected current and electronics, gas and drainage channel being provided for electrochemical reaction in fuel cell.Gas diffusion layers normally is made up of basalis and microporous layers.Base layer material generally adopts graphitization carbon paper or carbon cloth, also uses metal material sometimes.One deck carbon dust that microporous layers is normally made on its surface for the pore structure that improves diffusion layer (claiming leveling to handle) can play and reduce contact resistance, prevents pole catalyze layer " water logging " and prevent that Catalytic Layer is penetrated into the effect of basalis.
The core component of URFC is membrane electrode (MEA), and the proton exchange membrane of employing can be identical with common proton membrane fuel battery with cathode diffusion layer.But as URFC during with the water electrolysis mode operation, the anode oxygen evolution potential is very high, and carbon dust very easily is corroded under high potential.The microporous layers of conventional diffusion layer carbon dust commonly used is made, and this diffusion layer very easily changes because of carbon dust corrosion structure, causes the stability decreases of battery.Use carbon dust to be microporous layers, document (1) (G.Chen, Catalysis Today, 341 (2001)) only provides circulation 3 times battery performance.Other disclosed URFC cycle lives are (2) (L.S.Larry, J.Power Sources 47 (1994)) (3) (T.Ioroi, J.Power Sources124 (2003)) about 10 times only, and single circulation timei is all very short.At present seldom about the research of URFC diffusion layer aspect.Document (3) (4) (U.Wittstakt, J.Power Sources 145 (2005)) is continued to use the diffusion layer technology in the solid polymer water electrolysis, and promptly adopting titanium materials such as sintered titanium plate, titanium foam, titanium net, titanium fiber is substrate.But adopt the titanium basalis merely and do not have the diffusion layer of microporous layers,, thereby reduce the performance of URFC because surface of metal titanium can constantly be oxidized to the very poor oxide-film of electric conductivity analysing under the oxygen condition.It is basalis that document (5) (S.Song, Electrochem.Commun., 8 (2006)) proposes with the carbon paper, IrO
2/ Ti makes microporous layers, has reported this URFC40 hour cycle life.But its used microporous layers material all is a catalyst, IrO
2The load amount up to 2.5mg/cm
2, cost an arm and a leg and prepare a large amount of IrO with suitable aperture
2The diffusion layer of/Ti is very difficult.
The latest result of combining nano ceramic technology of the present invention is introduced the URFC field with the intermetallic compound of electric conductivity excellence.At present, Shang Weiyou uses the relevant report of intermetallic compound as URFC diffusion layer raw material.
Summary of the invention
The object of the present invention is to provide a kind of preparation that is used for diffusion layer and this diffusion layer of integral regeneratable fuel cell, improve the useful life of integral type regenerative fuel cell.
For achieving the above object, the technical solution used in the present invention is:
A kind of diffusion layer that is used for integral regeneratable fuel cell, its microporous layers that goes up coating by basalis and its is formed, and described microporous layers is that the intermetallic compound and the noble metal catalyst of (0.1: 1)～(1: 0.1) mixes by mass ratio.
Described intermetallic compound is TiC, Ti
2N, TiN, Ti (CN), (TiAl) (CN), among (TiAl) N, ZrC, ZrN, Zr (CN), NbC, NbN, Nb (CN), TaC, TaN, Ta (CN) and the CrN one or more, its particle diameter is 1～100nm.
Noble metal catalyst of the present invention is one or more in the oxide of iridium, ruthenium, iridium, the oxide of ruthenium, the blending oxide of iridium ruthenium, loaded iridium, loaded ruthenium, loaded iridium oxide, loaded ru oxide, the loaded iridium ruthenium blending oxide; The particle diameter of catalyst is 2～100nm; The body that supports that solid supported noble metal simple substance or solid supported noble metal oxide are used is Ti, TiO
2, ZrO
2, TiC, TiN, ZrC, ZrN, NbC, NbN, TaC, TaN, among the WC one or more, particle diameter is 1～95nm, the weight content that supports body is 1-90%.
Basalis of the present invention is that conventional porosity is 30～90% carbon paper or titanium base material, and its thickness is 50 microns～500 microns.
The body that supports that solid supported noble metal simple substance of the present invention or solid supported noble metal oxide are used is Ti, TiO
2, ZrO
2, TiC, TiN, ZrC, ZrN, NbC, NbN, TaC, TaN, among the WC one or more, particle diameter is 1～95nm.
Diffusion layer of the present invention preparation is earlier intermetallic compound to be carried out pre-treatment, again with certain mass than mixed noble metal catalyst, mixture be coated on the basalis form.Concrete preparation process is as follows:
1) impurity elimination pre-treatment: with intermetallic compound HCl solution washing, filtration, drying obtain Sample A;
Be specially: intermetallic compound powder is joined in the HCl solution of 1～2mol/L, ultrasonic Treatment 10～60 minutes after filtration, drying, obtains Sample A; The w/v of intermetallic compound and HCl solution is 1g: 1～5ml.
2) Sample A is mixed according to mass ratio (0.1: 1)～(1: 0.1) with noble metal catalyst, this mixture is joined in the solvent again, add PTFE, ultrasonic Treatment is uniformly dispersed mixture, obtains sample B; The mass ratio of PTFE and mixture is (1: 9)～(4: 6);
Described solvent is one or more in C1～C6 alcohol, and the used solvent volume of every 100g mixture is 0.5mL～30mL.
3) sample B evenly is coated on the side of the hydrophobization carbon paper that contains 1～30wt%PTFE or titanium base material,, 320～380 ℃ of sintering 30～90 minutes, can obtains diffusion layer of the present invention behind the natural cooling more earlier 220～280 ℃ of sintering 30～90 minutes; The consumption of mixture is every square centimeter of basalis 1mg～6mg.
The diffusion layer that the present invention is prepared, its thickness are 55 microns～600 microns, and porosity is 5～80%.
The diffusion layer of preparation is assembled into monocell, carries out the cycle life evaluation, test process is as follows:
1. the preparation of integral regeneratable fuel cell core component MEA (membrane electrodeassemblies):
With catalyst, Nafion solution and aqueous isopropanol, obtain ink shape catalyst pulp after in ultrasonic wave, fully disperseing, mixing.Use spray gun under the carrying of nitrogen current feed liquid evenly being sprayed on the proton exchange membrane of handling well, thereby obtain catalytic membrane CCM (Catalyst Coated Membrane).Wherein negative electrode adopts the Pt/C catalyst, and Pt load amount is 0.25mg/cm
2, Nafion content is 25%.Anode adopts Pt and IrO
2Composite catalyst, wherein, Pt load amount is 2.1mg/cm
2, IrO
2The load amount is 0.9mg/cm
2, used proton exchange membrane is the Nafion115 film.
Anode diffusion layer adopts the prepared diffusion layer of the present invention, and cathode diffusion layer uses the cathode diffusion layer of general fuel cell.Promptly containing on the hydrophobization carbon paper of 1wt%～30wt%PTFE, applying the microporous layers that contains PTFE and carbon dust in a side.This cathode diffusion layer is earlier 220～280 ℃ of sintering 30～90 minutes, and the back was 320～380 ℃ of sintering 30～90 minutes.
To be 5cm
2Anode diffusion layer and the cathode diffusion layer both sides that place CCM, place hydraulic press, impose the pressure of 0.2MPa under 140～160 ℃, kept 2 minutes, and made whole assembly preheating, impose the pressure of 1.0MPa then, kept 1～2 minute, cooling rapidly promptly makes MEA afterwards.
2. monocell assembling and test:
Currect collecting net is a stainless (steel) wire, and end plate is the stainless steel end plate.With MEA, currect collecting net, encapsulant and cell end plate are assembled into monocell.The monocell operating condition is:
(1) fuel cell (FC) pattern: H
2/ O
2, the humidification degree is 0～100%, and the monocell working temperature is 60～80 ℃, and the humidification temperature is 75～90 ℃.
(2) water electrolysis (WE) pattern: the constant current electrolysis, constant current density is at 100～500mA/cm
2, 60～80 ℃ of battery temperatures, 65～85 ℃ of inflow temperatures.
(3) circulation experiment: each cycle period FC mode operation 2h, WE mode operation 2h.Move the voltage attenuation ratio under certain current density of test after 15 circulations.
The latest result of combining nano ceramic technology of the present invention, the intermetallic compound with the electric conductivity excellence of novelty is introduced the URFC field.Intermetallic compound be a class by transition metal and C, N, H, the metallic compound that the less nonmetalloid of atomic radiuses such as B forms.Wherein, larger-size transition metal atom occupies the site position of lattice, and the less non-metallic atom of size then embeds among the gap of lattice regularly.Intermetallic compound has tangible metallicity such as good electrical conductivity and metallic luster, has the features such as high stability, high rigidity and high-melting-point of ceramic material again.Because intermetallic compound has superior electric conductivity, replaces carbon dust with it, can guarantee that diffusion layer has suitable conductivity.And intermetallic compound has incomparable chemical stability of carbon dust and electrochemical stability, can make diffusion layer keep the stable of structure in the URFC cyclic process, and therefore can improve the cycle life of URFC widely.A spot of noble metal catalyst mixes in intermetallic compound, these catalyst itself have good conductivity, thereby can't weaken the conductivity of diffusion layer, active oxygen owing to compound surface between these catalyst energy catalytic metals is combined into oxygen molecule rapidly simultaneously, thereby further weakened the corrosion of active oxygen, stablized diffuse layer structure microporous layers.
In a word, compare with existing background technology, diffusion layer of the present invention has following characteristics:
1. adopt the intermetallic compound that has good stability to prepare microporous layers, can weaken the corrosion of active oxygen greatly, improve the useful life of integral type regenerative fuel cell basalis.
2. adopt the superior intermetallic compound of electric conductivity to replace carbon dust, can make diffusion layer have suitable conductivity, thereby make the fuel battery performance of URFC similar with common proton membrane fuel battery.
3. mix a spot of noble metal catalyst in the microporous layers, can promote the association reaction of active oxygen, improve the stability of diffusion layer when URFC water electrolysis mode operation, and then improve the cycle life of URFC.
The present invention has the following advantages with traditional diffusion layer phase ratio: 1) have good electrical conductivity; 2) chemistry and electrochemical stability are good, have excellent corrosion resistance; 3) with low cost; 4) technology is simple, is easy to industrialization.Therefore, the present invention adopts the new diffusion layer of intermetallic compound can improve the cycle life of regenerative fuel cell significantly.By the present invention, can obtain low cost, the diffusion layer that the regenerative fuel cell of high-durability is used.The diffusion layer of preparation had output performance preferably after making regenerative fuel cell chip MEA and monocell.
Description of drawings
Fig. 1 is the cycle performance figure of embodiment 1;
Fig. 2 is the cycle performance figure of reference example.
Embodiment
Below by embodiment in detail the present invention is described in detail.
Embodiment 1
The TiC powder 100mg that gets particle diameter and be 8 nanometers is added in the hydrochloric acid solution of 10 milliliters of 2mol/L, and ultrasonic Treatment 15 minutes after filtration, drying, obtains comparatively pure TiC powder 90mg.
Get the TiC powder 80mg of gained and Ir that particle diameter the is 10nm mixed according to mass ratio 4:1, this mixture of 90g in the 10ml isopropyl alcohol, is added 10mgPTFE again, ultrasonic Treatment makes and mixes, and obtains viscous liquid.Thick solution evenly is coated in contain that 7wt%PTFE, porosity are 60%, thickness is that 190 microns, area are 20cm
2Carbon paper on, 260 ℃ of sintering 30 minutes,, obtain thickness of the present invention behind the natural cooling and be 220 microns, porosity and be 50% anode diffusion layer 360 ℃ of sintering 30 minutes.
The preparation of integral regeneratable fuel cell acp chip MEA:, obtain ink shape catalyst pulp after in ultrasonic wave, fully disperseing, mixing with catalyst, Nafion solution and 5ml aqueous isopropanol.Use spray gun under the carrying of nitrogen current, feed liquid evenly to be sprayed on the both sides of the proton exchange membrane of handling well, make CCM.The negative electrode that MEA is used and the Catalytic Layer of anode, diffusion layer area are 5cm
2, used proton exchange membrane is the Nafion115 film.
Wherein negative electrode adopts the Pt/C catalyst, and Pt load amount is 0.25mg/cm
2, Nafion content is 25wt%.
Anode adopts Pt and IrO
2Composite catalyst, wherein, Pt load amount is 2.1mg/cm
2, IrO
2The load amount is 0.9mg/cm
2
Cathode diffusion layer preparation is on the carbon paper that contains behind the hydrophobization of 20wt%PTFE, is compounded with the microporous layers of PTFE and carbon dust in a side, and the carbon dust consumption is 1.5mg/cm in the microporous layers
2, PTFE content is 30wt%.This diffusion layer is earlier 250 ℃ of sintering 30 minutes, and the back was 350 ℃ of sintering 30 minutes.
Anode diffusion layer and cathode diffusion layer are placed the both sides of CCM, place hydraulic press, impose the pressure of 0.2MPa under 140 ℃, kept 2 minutes, make whole assembly preheating, impose the pressure of 1.0 Pa then, kept 1 minute, cooling rapidly promptly makes MEA afterwards.
Monocell assembling and test: currect collecting net is a stainless (steel) wire; End plate is the stainless steel end plate.With MEA, currect collecting net, encapsulant and cell end plate are assembled into monocell.The monocell operating condition is: (1) FC pattern: H
2/ O
2, the humidification degree is 100%, and the monocell working temperature is 80 ℃, and the humidification temperature is 85 ℃ of (2) WE patterns: constant current density is at 200mA/cm
2, 80 ℃ of battery temperatures, 80 ℃ of inflow temperatures.(3) circulation experiment: each cycle period FC mode operation 2h, WE mode operation 2h.Test result shows: 200mA/cm
2Under move 15 circulations (60h) backs FC output voltage and only descend 10%, the WE decomposition voltage only rises 1.6%.See accompanying drawing 1.
The reference example
Get 100mg Vulcan XC-72 carbon dust, be added in the hydrochloric acid solution of 10 milliliters of 2mol/L, ultrasonic Treatment 30 minutes after filtration, drying, obtains comparatively pure carbon dust 90mg.
The carbon dust of gained is replaced the compound of TiC and Ir, be prepared into anode diffusion layer according to consumption and the preparation method identical with embodiment 1.
The test condition of this diffusion layer is identical with embodiment 1 with test process.Test result shows: 200mA/cm
2Under circulate 3 (6h) back FC output voltage that circulates descend and 100% promptly lose performance.See accompanying drawing 2.
Compared as can be seen by Fig. 1 and 2, the diffusion layer that adopts the present invention to prepare can improve the stability of URFC greatly, and improve useful life greatly.
Embodiment 2
The ZrN powder 100mg that gets particle diameter and be 50 nanometers is added in the hydrochloric acid solution of 40 milliliters of 1mol/L, and ultrasonic Treatment 60 minutes after filtration, drying, obtains comparatively pure ZrN powder 95mg.
ZrN powder 90mg, the particle diameter of getting gained are the IrO of 40nm
2/ TiN5mg, particle diameter are the IrO of 20nm
25mg mixes, and this mixture of 40g in 10ml ethylene glycol, is added 60mgPTFE again, and ultrasonic Treatment makes and mixes, and obtains viscous liquid.With the even blade coating of thick solution contain that 35wt%PTFE, porosity are 40%, thickness is that 400 microns, area are 20cm
2Carbon paper on, 270 ℃ of sintering 80 minutes,, obtain thickness of the present invention behind the natural cooling and be 425 microns, porosity and be 30% anode diffusion layer 370 ℃ of sintering 80 minutes.
Monocell assembling and test monocell operating condition are identical with embodiment 1.Test result shows: 200mA/cm
2Under move 15 circulations (60h) backs FC output voltage and only descend 12%, the WE decomposition voltage only rises 1.2%.Compare with the reference example, the diffusion layer that adopts the present invention to prepare can improve the stability of URFC greatly.
Embodiment 3
(TiAl) that gets particle diameter and be 80 nanometers (CN) powder 100mg is added in the hydrochloric acid solution of 20 milliliters of 1mol/L, and ultrasonic Treatment 30 minutes after filtration, drying, obtains comparatively pure (TiAl) (CN) powder 90mg.
(TiAl) that gets gained (CN) powder 50mg and particle diameter is that the IrRu/Ti of 90nm is according to 1: 1 mixed of mass ratio, with this mixture of 30g in 1ml propyl alcohol and 3mL ethanol, add 20mgPTFE again, ultrasonic Treatment makes and mixes, and obtains viscous liquid.With the even blade coating of thick solution contain that 20wt%PTFE, porosity are 65%, thickness is that 280 microns, area are 20cm
2The titanium fiber on, 260 ℃ of sintering 60 minutes,, obtain thickness of the present invention behind the natural cooling and be 310 microns, porosity and be 50% anode diffusion layer 360 ℃ of sintering 60 minutes.
The preparation of integral regeneratable fuel cell acp chip MEA, monocell assembling and operating condition are identical with embodiment 1.Test result shows: 200mA/cm
2Under move 15 circulations (60h) backs FC output voltage and only descend 8%, the WE decomposition voltage only rises 1.4%.Compare with the reference example, the diffusion layer that adopts the present invention to prepare can improve the stability of URFC greatly.
Embodiment 4
The CrN powder 100mg that gets particle diameter and be 100 nanometers adds in the hydrochloric acid solution of 20 milliliters of 1mol/L, and ultrasonic Treatment 50 minutes after filtration, drying, obtains comparatively pure CrN powder 92mg.
CrN powder 66mg and the particle diameter of getting gained are the IrRuO of 60nm
2/ WC in the 2ml butanols, adds 20mgPTFE with this mixture of 120g according to 6: 1 mixed of mass ratio again, and ultrasonic Treatment makes and mixes, and obtains viscous liquid.With the even blade coating of thick solution contain that 25wt%PTFE, porosity are 70%, thickness is that 450 microns, area are 20cm
2Titanium foam on, 230 ℃ of sintering 50 minutes,, obtain thickness of the present invention behind the natural cooling and be 468 microns, porosity and be 55% anode diffusion layer 350 ℃ of sintering 50 minutes.
The preparation of integral regeneratable fuel cell acp chip MEA, monocell assembling and operating condition are identical with embodiment 1.Test result shows: 200mA/cm
2Under move 15 circulations (60h) backs FC output voltage and only descend 10%, the WE decomposition voltage only rises 1.7%.Compare with the reference example, the diffusion layer that adopts the present invention to prepare can improve the stability of URFC greatly.
Embodiment 5
Get particle diameter and be the 20mg NbC powder of 20 nanometers and Ta (CN) 80mg that particle diameter is 60 nanometers and add in the hydrochloric acid solution of 20 milliliters of 1mol/L, ultrasonic Treatment 45 minutes after filtration, drying, obtains the mixed-powder 85mg of comparatively pure NbC and Ta (CN).
Getting the NbC of gained and mixed powder 60mg and the particle diameter of Ta (CN) is the RuO of 30nm
2/ ZrO
2According to 3: 1 mixed of mass ratio, again with this mixture of 50g in the 15ml isopropyl alcohol, add the PTFE of 20mg again, ultrasonic Treatment makes and mixes, and obtains viscous liquid.With the even blade coating of thick solution contain that 10wt%PTFE, porosity are 45%, thickness is that 300 microns, area are 20cm
2Sintered titanium on, 240 ℃ of sintering 50 minutes,, obtain thickness of the present invention behind the natural cooling and be 312 microns, porosity and be 35% anode diffusion layer 330 ℃ of sintering 60 minutes.
The preparation of integral regeneratable fuel cell acp chip MEA, monocell assembling and operating condition are identical with embodiment 1.Test result shows: 200mA/cm
2Under move 15 circulations (60h) backs FC output voltage and only descend 5%, the WE decomposition voltage only rises 2.0%.Compare with the reference example, the diffusion layer that adopts the present invention to prepare can improve the stability of URFC greatly.
Claims (6)
1. diffusion layer that is used for integral regeneratable fuel cell, it is characterized in that: its microporous layers that goes up coating by basalis and its is formed, and described microporous layers is that the intermetallic compound and the noble metal catalyst of (0.1: 1)～(1: 0.1) mixes by mass ratio;
Described intermetallic compound is TiC, Ti
2N, TiN, Ti (CN), (TiAl) (CN), among (TiAl) N, ZrC, ZrN, Zr (CN), NbC, NbN, Nb (CN), TaC, TaN, Ta (CN) and the CrN one or more, its particle diameter is 1～100nm;
Described noble metal catalyst is one or more in the oxide of iridium, ruthenium, iridium, the oxide of ruthenium, the blending oxide of iridium ruthenium, loaded iridium, loaded ruthenium, loaded iridium oxide, loaded ru oxide, the loaded iridium ruthenium blending oxide, and the particle diameter of catalyst is 2～100nm.
2. diffusion layer according to claim 1 is characterized in that: the body that supports that solid supported noble metal simple substance or solid supported noble metal oxide are used is Ti, TiO
2, ZrO
2, TiC, TiN, ZrC, ZrN, NbC, NbN, TaC, TaN, among the WC one or more, particle diameter is 1～95nm, the weight content that supports body is 1-90%.
3. diffusion layer according to claim 1 is characterized in that: basalis is that porosity is 30～90% carbon paper or titanium base material, and its thickness is 50 microns～500 microns.
4. the preparation method of the described diffusion layer of claim 1 is characterized in that: the concrete operations step is,
1) impurity elimination pre-treatment: with intermetallic compound HCl solution washing, filtration, drying obtain Sample A;
2) Sample A is mixed according to mass ratio (0.1: 1)～(1: 0.1) with noble metal catalyst, this mixture is joined in the solvent again, add PTFE, ultrasonic Treatment is uniformly dispersed mixture, obtains sample B; The mass ratio of PTFE and mixture is (1: 9)～(4: 6);
3) sample B evenly is coated on the side of the hydrophobization carbon paper that contains 1～30wt%PTFE or titanium base material,, 320～380 ℃ of sintering 30～90 minutes, can obtains described diffusion layer behind the natural cooling more earlier 220～280 ℃ of sintering 30～90 minutes; The consumption of mixture is every square centimeter of basalis 1mg～6mg.
5. according to the described preparation method of claim 4, it is characterized in that: the impurity elimination pre-treatment process of step 1) is, intermetallic compound powder joined in the HCl solution of 1～2mol/L, and ultrasonic Treatment 10～60 minutes after filtration, drying, obtains Sample A; The w/v of intermetallic compound and HCl solution is 1g: 1～5ml.
6. according to the described preparation method of claim 4, it is characterized in that: step 2) described in solvent be in C1～C6 alcohol one or more, the used solvent volume of every 100g mixture is 0.5mL～30mL.
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| CN105810952B (en) * | 2014-12-30 | 2018-10-26 | 北京有色金属研究总院 | A kind of lithium-air battery air cathode composite carrier and preparation method thereof |
| CN105810951B (en) * | 2014-12-30 | 2018-10-26 | 北京有色金属研究总院 | A kind of lithium-air battery air cathode and preparation method thereof |
| CN105119007B (en) * | 2015-08-05 | 2017-12-08 | 黄河科技学院 | A kind of preparation method of corrosion-resistant fuel battery gas diffusion layer |
| CN107579264B (en) * | 2017-08-18 | 2019-12-10 | 上海交通大学 | Reversible fuel cell cathode flow field structure and reversible fuel cell |
| CN110611107A (en) * | 2018-06-16 | 2019-12-24 | 浙江晨阳新材料有限公司 | Fuel cell comprising gas diffusion layer |
| CN113937306A (en) * | 2021-10-08 | 2022-01-14 | 南昌智能新能源汽车研究院 | Gas diffusion layer for improving heat transfer of proton exchange membrane fuel cell |
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| CN1967916A (en) * | 2005-11-16 | 2007-05-23 | 中国科学院大连化学物理研究所 | Double-purpose oxygen pole used for integral reproducible fuel battery and its manufacturing method |
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