CN1624961A - Air electrode of multi-layer sintering structure and its manufacturing method - Google Patents
Air electrode of multi-layer sintering structure and its manufacturing method Download PDFInfo
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- CN1624961A CN1624961A CNA2004100910003A CN200410091000A CN1624961A CN 1624961 A CN1624961 A CN 1624961A CN A2004100910003 A CNA2004100910003 A CN A2004100910003A CN 200410091000 A CN200410091000 A CN 200410091000A CN 1624961 A CN1624961 A CN 1624961A
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Abstract
An air electrode, executes the multilayer sintering structure, is composed of at least one layer of base material, two layers of diffused layer and an activating layer coincidence. The base material is the current collector of the air electrode and is made of the metal gauze or metal blister gauze, the upper and the lower sides respectively superpose at least a diffused layer sintered by hydrophobicity carbon material, superpose at least a activating layer outside the diffused layer, every activating layer is sintered by hydrophilicity carbon material adhered with transition metal oxide catalysis; this air electrode can be applied to zinc air battery, negative pole of firing battery or capacitance, especially when applied to the negative pole of zinc air battery, it can avoid the external air influence on the electrolyte in the zinc air battery, in the dry environment, it can maintain the water ratio of zinc positive pole of air battery more than one month, and maintain the stable electric performance.
Description
Technical field
The present invention is relevant a kind of air electrode and method for making thereof that constitutes multi-layer sintering structure, refers to use the negative electrode use of purposes as zinc-air cell especially, and can prevent that the electrolyte of zinc-air cell inside is subjected to the novel air electrode structure of external air ambient influence.
Background technology
Utilize the zinc-air cell (Zn/Aircell) of airborne oxygen molecule as cathode reactant, owing to have specific energy (Specific Energy), and the characteristics of the stable output of discharge voltage of high power capacity, its range of application is quite extensive, comprise Vehicular battery, reach hearing aids battery or the like, all can use zinc-air cell to be power supply source, add and have advantages such as environmental protection and low price, be regarded as the substitute of alkaline battery.
This zinc-air cell uses metallic zinc (Zn) to be anode, and negative electrode then uses airborne oxygen (O
2) or pure oxygen, so the negative electrode of zinc-air cell claims air electrode (air cathode) again, and store electrolyte in zinc-air cell inside, then use potassium hydroxide aqueous solution (KOHsolution).And, this zinc-air cell, after utilizing air electrode that airborne oxygen is carried out the negative electrode chemical reaction and is converted into hydroxide ion (OH-), the zinc anode oxidation that will be made up of zinc metal mixture (zinc slurry, zine plate or zinc paper tinsel) is exported and produce stable discharging voltage again.
Because the air electrode of this zinc-air cell, just as medium, itself can't loss, therefore, when making zinc-air cell, can increase the zinc anode loadings of zinc-air cell, make the capacitance of zinc-air cell and specific energy (Specific Energy) therefore increase, and reach the purpose of miniaturization by this.
But this zinc-air cell must be provided with the gas duct, makes air to enter, so the housing of zinc-air cell can not seal, must make semi-open structure.Yet this semi-open structure will cause zinc-air cell to be very easy to be subjected to the influence of external air ambient, and hinders the serviceability of zinc-air cell and the useful life of shortening zinc-air cell.
Especially, the present employed air electrode structure commonly used of zinc-air cell, the sintering structure of use individual layer, its shortcoming can't long preservation for the moisture content of inner zinc anode.When if external air ambient condition is the environment of high humility, moisture can see through the air electrode of zinc-air cell, and enters into the inside of zinc-air cell, and this phenomenon can cause electrolyte dilution and guiding discharge voltage to descend; Otherwise if external air ambient condition, when the environment of low humidity, the electrolyte of zinc-air cell inside will see through air electrode and the moisture that outwards scatters and disappears, and then causes electrolyte dry and cause battery failure.
Summary of the invention
In view of this, main purpose of the present invention, promptly be to provide a kind of air electrode that constitutes multi-layer sintering structure, use comprises and can be used as zinc-air cell, fuel battery negative pole or electric capacity use, and utilize it to have the multiple stratification isolation structures of two layers of diffusion layer and one deck active layer at least, reach and effectively slow down the purpose that moisture passes through, therefore when using as the negative electrode of zinc-air cell, can prevent that the electrolyte of zinc-air cell inside can be subjected to the influence of external air ambient, make the problem that the zinc anode moisture content of present zinc-air cell can't long preservation, can obtain effective solution, especially under dry environment, can impel the zinc anode moisture content of zinc-air cell to keep reaching more than one month, make zinc-air cell can long term maintenance stable electrically.
Another main purpose of the present invention, be that a kind of manufacture method of air electrode is being provided, by technology such as the coating of dry type carbon dust, high pressure pressing and sintering, make a kind of high-density air electrode of multi-layer sintering structure, when this air electrode is used as the negative electrode of zinc-air cell, the electrolyte that can prevent inside battery is subjected to external air ambient influence, and the zinc anode moisture content of zinc-air cell can be kept for a long time, especially under dry environment, can impel the zinc-air cell can the stable electrical utilance of long term maintenance.
The air electrode of the multi-layer sintering structure among the present invention comprises following formation:
The multilayer layered structure is coincided up and down by one deck base material at least, two layers of diffusion layer and one deck active layer and constitutes, wherein, above-mentioned base material is as the current collector of air electrode, make by woven wire or metal foaming net, and the both sides up and down of above-mentioned base material, repeatedly be equipped with the diffusion layer that one deck is made by hydrophobicity carbon material sintering respectively, and repeatedly put the outside at the diffusion layer of above-mentioned base material one side, then repeatedly put one deck active layer at least, and every layer of active layer made by the hydrophily carbon material sintering that is attached with the transition metal oxide catalyst.
The air electrode method for making of the multi-layer sintering structure among the present invention may further comprise the steps:
A. be base material with metal foaming net or woven wire, make the current collector of air electrode;
B. use hydrophobicity carbon dust or carbon materials such as acetylene reduction carbon black or coking carbon black, with aqueous polytetrafluoroethyldispersion aaerosol solution binder and deionized water, by 2: 1: 50 or 3: 1: 50 mixed;
The hydrophobicity carbon dust that mixes the polytetrafluoroethylene adhesive agent is dried operation;
After finishing oven dry, the hydrophobicity carbon dust that mixes the polytetrafluoroethylene adhesive agent is evenly coated the both sides up and down of the base material of step a, constitute one deck diffusion layer;
Make the driving fit of hydrophobicity carbon dust with the high pressure pressurization again;
To being attached with this base material of hydrophobicity carbon dust, impose 200-400 ℃ of heat sintering 20-40 minute, make the hydrophobicity carbon dust that mixes the polytetrafluoroethylene adhesive agent, be sintered into cancellated fixed toner, constitute the diffusion layer of air electrode, adjust the thickness of diffusion layer again with rivet bucker;
C. use hydrophily carbon dust or carbon materials such as acetylene reduction carbon black, coking carbon black, CNT (carbon nano-tube) or nano-sized carbon bugle, with polytetrafluoroethylene adhesive agent and transition metal oxide catalytic powder, by 4: 1: 1 or 3: 1: 2 mixed, add entry, methyl alcohol or isopropyl alcohol again as solvent, be uniformly mixed into mixed slurry;
Mixed slurry is coated on the diffusion layer surface of base material upside with spray gun spraying or other coating method again, constituted one deck active layer;
To being attached with this base material of diffusion layer and active layer, impose 200-400 ℃ of heat sintering 10-60 minute, make the hydrophily carbon dust that mixes polytetrafluoroethylene adhesive agent and transition metal oxide catalytic powder, be sintered into the fixed toner that contains the transition metal oxide catalytic powder, and the active layer of formation air electrode, adjust the thickness of active layer again with rivet bucker, make the air electrode of stromatolithic multi-layer sintering structure.
Description of drawings
Fig. 1 is first kind of laminated shape multi-layer sintering structure schematic diagram of air electrode shown in the present.
Fig. 2 is second kind of laminated shape multi-layer sintering structure schematic diagram of air electrode shown in the present.
Fig. 3 is the third laminated shape multi-layer sintering structure schematic diagram of air electrode shown in the present.
Fig. 4 is the manufacturing flow chart of air electrode shown in the present.
Fig. 5 is the electrical analysis chart of IV of air electrode shown in the present.
Fig. 6 is that zinc-air cell uses air electrode shown in the present to be negative electrode, be negative electrode with the single face air electrode commonly used that uses comparative example, through placing 25 ℃ of temperature, in the dry air of humidity 20RH% after 7 days, measured zinc-air cell zinc anode moisture content variation diagram.
Fig. 7 is that zinc-air cell uses air electrode shown in the present to be negative electrode, be negative electrode with the single face air electrode of generally commonly using that uses comparative example, through placing 25 ℃ of temperature, in the dry air of humidity 20RH% after 7 days, measured zinc-air cell zinc anode utilance variation diagram.
The element numbers simple declaration:
Air electrode ... ... 10
Base material ... ... ... 11
Diffusion layer ... ... 12
Active layer ... ... 13
Embodiment
Please refer to Fig. 1 to Fig. 3, air electrode shown in the present 10 constitutes stromatolithic multi-layer sintering structure, have and slow down the effect that moisture passes through, by one deck base material 11, at least two layers of diffusion layer 12 and at least one deck active layer 13 coincide up and down and constitute.The thickness range of this air electrode 10 is that 0.8-2.0mm, density range are 0.1-30.0g/cm
3, use comprises that can be used as zinc-air cell, fuel battery negative pole or electric capacity uses.
The both sides up and down of this base material 11 are then repeatedly put the diffusion layer 12 that a layer thickness is 0.2-0.8mm respectively, and perhaps, the downside of this base material 11 are the structures that constitute the above diffusion layer 12 of one deck, and every layer of diffusion layer 12 is made of hydrophobicity carbon material.
This diffusion layer 12 uses the purpose of hydrophobicity carbon material, be when air electrode shown in the present 10 uses as the negative electrode of zinc-air cell, the diffusion layer 12 of this air electrode 10, can bring into play and make air diffuse into, but the bath composition that can prevent zinc-air cell inside changes, make the electrolyte of zinc-air cell inside can not be subjected to the influence of external air ambient, and can promote the zinc anode moisture content of zinc-air cell to keep by longer-term.
And repeatedly put in the outside of the diffusion layer 12 of these base material 11 upsides, repeatedly put one deck active layer 13 at least, and every layer of active layer 13 is made of the hydrophily carbon material that is attached with catalyst.
The purpose that this active layer 13 uses by the hydrophily carbon material that is attached with catalyst, be when air electrode shown in the present 10 uses as the negative electrode of zinc-air cell, utilize the active layer 13 of this air electrode 10, come catalytic oxygen to carry out the negative electrode chemical reaction and be converted into hydroxide ion, and via electrolyte and anode zinc metal reaction generation electric current.Wherein, be attached to the catalyst on this active layer 13, can select transition metal oxide or salt for use, for example, transition metal oxide or salts such as iron, cobalt, nickel, manganese.
Disclosed air electrode 10, its manufacturing process comprise following each step as shown in Figure 4:
A. be base material 11 with metal foaming net or woven wire, make the current collector of air electrode 10;
B. make the diffusion layer 12 of air electrode 10;
B-1) use hydrophobicity carbon dust or carbon materials such as acetylene reduction carbon black or coking carbon black, with polytetrafluoroethylene (PTFE) aqueous suspension solution adhesive (binder) and deionized water, pressed 2: 1: 50, perhaps 3: 1: 50 mixed;
B-2) then, the hydrophobicity carbon dust that mixes the polytetrafluoroethylene (PTFE) adhesive agent is dried operation, preferred embodiment, be dry to moisture below 4%;
B-3) finish oven dry after, the hydrophobicity carbon dust that mixes the polytetrafluoroethylene (PTFE) adhesive agent is evenly coated the both sides up and down of base material 11, pressurize in the high pressure mode again and make the driving fit of hydrophobicity carbon dust;
B-4) step b-3 is attached with the base material 11 of hydrophobicity carbon dust, impose 200-400 ℃ of heat sintering 20-40 branch, but preferred embodiment was with 300-350 ℃ of heat sintering 20-40 minute, the feasible hydrophobicity carbon dust that mixes the polytetrafluoroethylene (PTFE) adhesive agent, be sintered into cancellated fixed toner, and the diffusion layer 12 of formation air electrode 10, adjust the thickness of diffusion layer 12 to 0.2-0.8mm with rivet bucker again;
B-5) make diffuse layer structure more than two layers as need, can repeat b-3, the operation of b-4 step, up to making required sandwich construction;
C. make the active layer 13 of air electrode 10;
C-1) use hydrophily carbon dust or carbon materials such as acetylene reduction carbon black, coking carbon black, CNT (carbon nano-tube) or nano-sized carbon bugle, with polytetrafluoroethylene (PTFE) adhesive agent and transition metal oxide catalytic powder, by 4: 1: 1 or 3: 1: 2 mixed, add entry, methyl alcohol or isopropyl alcohol again as solvent, be uniformly mixed into mixed slurry; Wherein, the transition metal oxide catalytic powder can be selected transition metal oxide or salts such as iron, cobalt, nickel, manganese for use;
C-2) with spray gun spraying or other coating method the mixed slurry of step c-1 is coated on diffusion layer 12 surfaces of base material 11 upsides again, promptly constituted one deck active layer 13;
C-3) step c-2 is attached with the base material 11 of diffusion layer 12 and active layer 13, impose 200-400 ℃ of heat sintering 10-60 minute, but preferred embodiment was with 350-400 ℃ of heat sintering 20-40 minute, the feasible hydrophily carbon dust that mixes polytetrafluoroethylene (PTFE) adhesive agent and transition metal oxide catalytic powder, be sintered into the fixed toner that contains the transition metal oxide catalytic powder, and the active layer 13 of formation air electrode 10, the thickness of adjusting active layer 13 with rivet bucker is promptly made a kind of air electrode 10 of stromatolithic multi-layer sintering structure to 0.2-0.8mm again;
C-4) make active layer structure more than two layers as need, can repeat c-2, the operation of c-3 step, up to finishing required sandwich construction.
Embodiment
The air electrode 10 of present embodiment, its structure is base material 11 and the current collector that constitutes air electrode 10 with the nickel screen as shown in Figure 1, and one deck diffusion layer 12 is respectively repeatedly put in the both sides up and down of this nickel screen, and the outside of the diffusion layer 12 of these base material 11 upsides, repeatedly put one deck active layer 13 again.The thickness of air electrode 10 is 0.8mm, and density range is 0.1-30.0g/cm
3,
Wherein, the method for making of this diffusion layer 12 is, uses hydrophobicity coking carbon black and polytetrafluoroethylene (PTFE) adhesive agent and deionized water to dry after the mixed with 3: 1: 50, coats the both sides up and down of nickel screen again, through 200 ℃ of sintering after 20 minutes and make; And the method for making of this active layer 13 is, the transition metal oxide that uses hydrophily coking carbon black, polytetrafluoroethylene (PTFE) adhesive agent, uses as the catalyst purposes was with 4: 1: 1 mixed, and the methyl alcohol, isopropyl alcohol, the deionized water mixed diluting that add about 500 times of weight become mixed slurry, after being sprayed at diffusion layer 12 surfaces of nickel screen upside with spray gun again, make after 10 minutes with 400 ℃ of sintering.
Then, the air electrode 10 of present embodiment is carried out electrochemical analysis, comprise air electrode IV testing electrical property, water cut test, and anode discharge utilance test.According to following test result, show the made air electrode 10 of present embodiment, when using as the negative electrode of zinc-air cell, can prevent that the electrolyte of zinc-air cell inside is subjected to the influence of external air ambient, make that the zinc anode moisture content of zinc-air cell can long preservation, especially under dry environment, can impel the zinc-air cell can the stable electrical utilance of long term maintenance.
Air electrode IV testing electrical property (the discharge sweep test of current density versus potential):
Air electrode that present embodiment is made 10 is fixed with anchor clamps, adds 7 moles of KOH aqueous solution, uses the Hg/HgO electrode to be reference electrode, and the Pt electrode is a counter electrode, with the electrochemical analyser scanning analysis, and the result of the electrical figure of gained IV, as shown in Figure 5.
By IV testing electrical property result shown in Figure 5, show the made air electrode 10 of present embodiment, be lower than in the operating voltage with the test of Hg/HgO reference electrode-during 0.5V, current density has arrived 0.25A/cm
2More than, so by the made air electrode 10 of present embodiment, catalytic oxygen carries out the negative electrode chemical reaction and is converted into hydroxide ion rapidly, and produce electric current via KOH electrolyte and anode metal reaction.
Compare with the air or the gas electrode of general higher density or high pressure processing, general air or gas electrode can be compressed because of the gas duct, and causing the extraneous gas can't be smoothly by causing electrical decline, current density only can arrive 0.025-0.080A/cm
2, and the made air electrode 10 of present embodiment, current density can reach 0.25A/cm
2More than
Water cut test:
Use the air electrode 10 of present embodiment to insert the metallic cathode shell, housing diameter 8cm, average mark are furnished with the ventilative circular hole of 32 diameter 0.85mm, and form zinc-air cell jointly with barrier film or polyelectrolyte, colloidal state zinc anode, metal anode shell.Wherein, this colloidal state zinc anode mixes stirring by alloy zinc powder, corrosion inhibitor, interfacial agent, tackifier, the KOH aqueous solution with proper proportion and makes.
After zinc-air cell assembling finished, place the dry air of 25 ℃ of temperature and humidity 20RH%, experience after 7 days, zinc-air cell is decomposed, and use the water cut test machine to test the moisture content (105 ℃, 35 minutes) of colloidal state zinc anode, test result is as shown in Figure 6.
And comparative example to select thickness for use be the air electrode that 0.3mm and 0.4mm have the individual layer sintering structure, promptly, general single face air electrode commonly used, and make zinc-air cell under the same conditions, and under the same conditions, the moisture content (105 ℃, 35 minutes) of test colloidal state zinc anode, test result as shown in Figure 6.
Moisture content result by colloidal state zinc anode shown in Figure 6, show the made air electrode 10 of present embodiment, owing to constitute stromatolithic multi-layer sintering structure, when using, has the maintenance effect really for the zinc anode moisture content of zinc-air cell as the negative electrode of zinc-air cell.
The test of anode discharge utilance:
Use and the identical zinc-air cell of test colloidal state zinc anode moisture content, place the dry air of 25 ℃ of temperature and humidity 20RH%, experience after 7 days, with discharging and recharging instrument under the discharging current of C15 (200mA), the zinc anode discharge utilance of test zinc-air cell, test result as shown in Figure 7.
Wherein, zinc anode discharge utilance is calculated according to following formula:
And comparative example to select thickness for use be the air electrode of 0.3mm and 0.4mm tool individual layer sintering structure, that is, and general single face air electrode commonly used, and make zinc-air cell under the same conditions, and under the same conditions, the zinc anode discharge utilance of test zinc-air cell, test result is as shown in Figure 7.
Result by colloidal state zinc anode discharge utilance shown in Figure 7 shows the made air electrode 10 of present embodiment, owing to constitute stromatolithic multi-layer sintering structure, the utilance that is positioned in the dry air environment for the prolongation zinc-air cell truly has help.
Claims (12)
1. the air electrode of a multi-layer sintering structure is characterized by:
Above-mentioned multilayer layered structure is coincided up and down by one deck base material at least, two layers of diffusion layer and one deck active layer and constitutes, wherein, above-mentioned base material is as the current collector of air electrode, make by woven wire or metal foaming net, and the both sides up and down of above-mentioned base material, repeatedly be equipped with the diffusion layer that one deck is made by hydrophobicity carbon material sintering respectively, and repeatedly put the outside at the diffusion layer of above-mentioned base material one side, then repeatedly put one deck active layer at least, and every layer of active layer made by the hydrophily carbon material sintering that is attached with the transition metal oxide catalyst.
2. the air electrode of multi-layer sintering structure according to claim 1 is characterized by, and the thickness of above-mentioned air electrode is that 0.8-2.0mm, density are 0.1-30.0g/cm
3, use as zinc-air cell, fuel battery negative pole or electric capacity.
3. the air electrode of multi-layer sintering structure as claimed in claim 1 or 2 is characterized by, and above-mentioned base material is made with wire nettings such as woven wire, metal knitted net or metal foaming nets.
4. the air electrode of multi-layer sintering structure as claimed in claim 1 or 2 is characterized by, and the catalyst that every layer of active layer adheres to is transition metal oxide or salts such as iron, cobalt, nickel, manganese.
5. the air electrode of multi-layer sintering structure as claimed in claim 1 or 2 is characterized by, and every layer of diffusion layer made by acetylene reduction carbon black or coking carbon black sintering.
6. the air electrode of multi-layer sintering structure as claimed in claim 1 or 2 is characterized by, and every layer of active layer reduces carbon black, coking carbon black, CNT (carbon nano-tube) or nano-sized carbon bugle sintering by acetylene and make.
7. the air electrode of multi-layer sintering structure as claimed in claim 1 or 2, it is characterized by, above-mentioned base material is made with nickel screen, every layer of diffusion layer selects for use acetylene reduction carbon black or coking carbon black sintering to make, and every layer of active layer selects for use acetylene reduction carbon black, coking carbon black, CNT (carbon nano-tube) or nano-sized carbon bugle sintering to make.
8. the air electrode method for making of a multi-layer sintering structure, its feature may further comprise the steps:
A. be base material with metal foaming net or woven wire, make the current collector of air electrode;
B. use hydrophobicity carbon dust or carbon materials such as acetylene reduction carbon black or coking carbon black, with aqueous polytetrafluoroethyldispersion aaerosol solution binder and deionized water, by 2: 1: 50 or 3: 1: 50 mixed;
The hydrophobicity carbon dust that mixes the polytetrafluoroethylene adhesive agent is dried operation;
After finishing oven dry, the hydrophobicity carbon dust that mixes the polytetrafluoroethylene adhesive agent is evenly coated the both sides up and down of the base material of step a, constitute one deck diffusion layer;
Make the driving fit of hydrophobicity carbon dust with the high pressure pressurization again;
To being attached with this base material of hydrophobicity carbon dust, impose 200-400 ℃ of heat sintering 20-40 minute, make the hydrophobicity carbon dust that mixes the polytetrafluoroethylene adhesive agent, be sintered into cancellated fixed toner, constitute the diffusion layer of air electrode, adjust the thickness of diffusion layer again with rivet bucker;
C. use hydrophily carbon dust or carbon materials such as acetylene reduction carbon black, coking carbon black, CNT (carbon nano-tube) or nano-sized carbon bugle, with polytetrafluoroethylene adhesive agent and transition metal oxide catalytic powder, by 4: 1: 1 or 3: 1: 2 mixed, add entry, methyl alcohol or isopropyl alcohol again as solvent, be uniformly mixed into mixed slurry;
Mixed slurry is coated on the diffusion layer surface of base material upside with spray gun spraying or other coating method again, constituted one deck active layer;
To being attached with this base material of diffusion layer and active layer, impose 200-400 ℃ of heat sintering 10-60 minute, make the hydrophily carbon dust that mixes polytetrafluoroethylene adhesive agent and transition metal oxide catalytic powder, be sintered into the fixed toner that contains the transition metal oxide catalytic powder, and the active layer of formation air electrode, adjust the thickness of active layer again with rivet bucker, make the air electrode of stromatolithic multi-layer sintering structure.
9. as the air electrode method for making of multi-layer sintering structure as described in the claim 8, it is characterized by, when step b is dried operation to the hydrophobicity carbon dust that mixes the polytetrafluoroethylene adhesive agent, dry to moisture below 4%.
10. as the air electrode method for making of multi-layer sintering structure as described in the claim 9, it is characterized by, at step b to being attached with the above-mentioned base material of hydrophobicity carbon dust, impose 300-350 ℃ of heat sintering 20-40 minute, and at step c to being attached with the above-mentioned base material of diffusion layer and active layer, impose 350-400 ℃ of heat sintering 20-40 minute.
11. the air electrode method for making as multi-layer sintering structure as described in the claim 10 is characterized by, the employed transition metal oxide catalytic powder of step c is selected transition metal oxide or salts such as iron, cobalt, nickel, manganese for use.
12. air electrode method for making as multi-layer sintering structure as described in claim 8 to 11 arbitrary, it is characterized by, when making more than two layers diffuse layer structure, coating carbon dust and the sintering step of repetitive operation step b, up to making required sandwich construction, adjust the thickness of diffusion layer again with rivet bucker; When making more than two layers active layer structure, coating sizing-agent and the sintering step of repetitive operation step c are up to making required sandwich construction, to make the air electrode of stromatolithic multi-layer sintering structure.
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| CN100408727C (en) * | 2005-06-14 | 2008-08-06 | 河北工业大学 | Air electrode and its manufacturing method |
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| CN101295791B (en) * | 2007-04-24 | 2011-01-26 | 中国科学院大连化学物理研究所 | Ternary complex cathode material of intermediate/low temperature solid-oxide fuel battery |
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| CN102210042A (en) * | 2008-09-08 | 2011-10-05 | 新加坡南洋理工大学 | Electrode materials for metal-air batteries, fuel cells and supercapacitors |
| CN102598400A (en) * | 2009-10-29 | 2012-07-18 | 索尼公司 | Lithium-air battery |
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| CN101207221B (en) * | 2006-12-22 | 2011-02-16 | 傅理平 | Cylinder metal foaming battery |
| CN101295791B (en) * | 2007-04-24 | 2011-01-26 | 中国科学院大连化学物理研究所 | Ternary complex cathode material of intermediate/low temperature solid-oxide fuel battery |
| US9660310B2 (en) | 2008-09-08 | 2017-05-23 | Nanyang Technological University | Electrode materials for metal-air batteries, fuel cells and supercapacitors |
| CN102210042A (en) * | 2008-09-08 | 2011-10-05 | 新加坡南洋理工大学 | Electrode materials for metal-air batteries, fuel cells and supercapacitors |
| CN101882682A (en) * | 2009-05-04 | 2010-11-10 | 协盈电子工业股份有限公司 | Method for manufacturing flexible cathode electrode sheet |
| CN102598400A (en) * | 2009-10-29 | 2012-07-18 | 索尼公司 | Lithium-air battery |
| CN103187598A (en) * | 2011-12-30 | 2013-07-03 | 财团法人金属工业研究发展中心 | Electrical energy generation device and cathode thereof |
| CN103187598B (en) * | 2011-12-30 | 2015-05-06 | 财团法人金属工业研究发展中心 | Electrical energy generation device and cathode thereof |
| CN105098199A (en) * | 2015-06-12 | 2015-11-25 | 中国科学院宁波材料技术与工程研究所 | Gas diffusion layer, preparation method and metal-air battery |
| CN105098199B (en) * | 2015-06-12 | 2019-04-12 | 中国科学院宁波材料技术与工程研究所 | A kind of gas diffusion layers, preparation method and a kind of metal-air battery |
| CN108028392A (en) * | 2016-01-20 | 2018-05-11 | 株式会社Lg化学 | Cathode, the lithium-air battery and its manufacture method with the cathode of the lithium-air battery of the side reaction trapping layer of metallic catalyst are introduced with part |
| CN108028392B (en) * | 2016-01-20 | 2021-08-17 | 株式会社Lg化学 | Positive electrode for lithium-air battery having side reaction preventing layer partially incorporating metal catalyst, lithium-air battery having the same, and method for manufacturing the same |
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