TWI489675B - Air-cathode for metal-air batteries - Google Patents
Air-cathode for metal-air batteries Download PDFInfo
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- TWI489675B TWI489675B TW101147211A TW101147211A TWI489675B TW I489675 B TWI489675 B TW I489675B TW 101147211 A TW101147211 A TW 101147211A TW 101147211 A TW101147211 A TW 101147211A TW I489675 B TWI489675 B TW I489675B
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- 238000009792 diffusion process Methods 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- -1 graphite Alkene Chemical class 0.000 claims description 2
- 238000005253 cladding Methods 0.000 claims 1
- 239000008151 electrolyte solution Substances 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000006870 function Effects 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009993 protective function Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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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- Inert Electrodes (AREA)
- Hybrid Cells (AREA)
Description
本發明是有關於一種空氣陰極，特別是指一種應用於金屬空氣電池的空氣陰極。This invention relates to an air cathode, and more particularly to an air cathode for use in a metal air battery.
金屬空氣電池具有環保、能量密度高、輸出電壓穩定、使用安全可靠等優點，且反應活性物質為空氣中取之不盡的氧氣，可使生產成本大幅降低，相當具有發展潛力，亦是未來提供動力來源的趨勢。The metal air battery has the advantages of environmental protection, high energy density, stable output voltage, safe and reliable use, and the reactive material is inexhaustible oxygen in the air, which can greatly reduce the production cost, has considerable development potential, and is also provided in the future. The trend of power sources.
習知的金屬空氣電池包括一金屬陽極、一可催化空氣中的氧氣進行還原作用的空氣陰極，及一電解液。其中，該空氣陰極包括一集電層、分別形成於該集電層兩相反側的一擴散層，及一觸媒層。該擴散層為一可透氣的薄層，用以將空氣或氧氣擴散導入至該觸媒層；該集電層係為導電性良好的金屬材料，作用是傳導該空氣陰極所產生的電流；該觸媒層則是利用觸媒的催化作用，使氧氣和水轉化為氫氧根離子，以完成該金屬空氣電池的陰極反應。A conventional metal air battery includes a metal anode, an air cathode that catalyzes the reduction of oxygen in the air, and an electrolyte. The air cathode includes a collector layer, a diffusion layer respectively formed on opposite sides of the collector layer, and a catalyst layer. The diffusion layer is a gas permeable thin layer for diffusing air or oxygen into the catalyst layer; the collector layer is a conductive metal material for conducting current generated by the air cathode; The catalyst layer utilizes the catalytic action of the catalyst to convert oxygen and water into hydroxide ions to complete the cathode reaction of the metal air battery.
由此可知，空氣陰極的主要功能包括收集電流、承載觸媒，以及提供反應所需的氣體通道和電子通道，因此，若空氣陰極的功效不彰，該金屬空氣電池的效能及使用壽命也會隨之下降。It can be seen that the main functions of the air cathode include collecting current, carrying the catalyst, and providing the gas passage and electron passage required for the reaction. Therefore, if the efficiency of the air cathode is not good, the performance and service life of the metal air battery will also be It will fall.
為了進一步實現與加強空氣陰極的功能，該集電層必須具備良好的導電性，還要提供足夠的通道讓氣體容易擴 散通過，因此該集電層大多使用導電性良好的金屬材料製作成網狀的結構(例如：銅網、鎳網)。然而，銅網雖具有極佳的導電性，但耐腐蝕程度較差，因此在酸性或鹼性的電解液中容易腐蝕；鎳網雖具有較佳的耐腐蝕性，但材料成本昂貴；而不銹鋼網雖然材料成本適中，但耐腐蝕性及導電性則不理想。In order to further realize and enhance the function of the air cathode, the collector layer must have good electrical conductivity and provide sufficient passage for the gas to be easily expanded. Since the collector layer is dispersed, the collector layer is often formed into a mesh structure (for example, a copper mesh or a nickel mesh) using a metal material having good conductivity. However, although the copper mesh has excellent electrical conductivity, it has poor corrosion resistance and is therefore easily corroded in an acidic or alkaline electrolyte; although the nickel mesh has better corrosion resistance, the material cost is expensive; Although material costs are moderate, corrosion resistance and electrical conductivity are not ideal.
而於此技術領域者均知：如該集電層的金屬導電結構發生腐蝕，不但會對該空氣陰極的機械強度造成影響，且腐蝕的生成物也會增加該集電層表面的電阻，導致電池的輸出功率降低。因此，提供一種高導電性及耐腐蝕性的空氣陰極，以實現高效能的金屬空氣電池，則是本發明研究改良的重要方向。However, it is known in the technical field that if the metal conductive structure of the collector layer is corroded, not only the mechanical strength of the air cathode is affected, but also the corrosion product increases the resistance of the surface of the collector layer, resulting in The output power of the battery is reduced. Therefore, providing an air cathode having high conductivity and corrosion resistance to realize a high-performance metal air battery is an important direction for research and improvement of the present invention.
因此，本發明之目的，即在提供一種可以提高該空氣陰極的導電性，並提升該金屬空氣電池整體效能的空氣陰極。Accordingly, it is an object of the present invention to provide an air cathode which can improve the electrical conductivity of the air cathode and enhance the overall performance of the metal air battery.
於是，本發明金屬空氣電池的空氣陰極，包含一呈網狀結構的集電層、一第一導電層、一第一擴散層、一第二擴散層、一觸媒層，及一透氣層。Therefore, the air cathode of the metal-air battery of the present invention comprises a collector layer having a mesh structure, a first conductive layer, a first diffusion layer, a second diffusion layer, a catalyst layer, and a gas permeable layer.
該集電層包括彼此反向的一第一表面，及一第二表面；該第一導電層選自石墨烯材料並形成於該集電層的第一表面；該第一擴散層形成於該第一導電層的表面；該第二擴散層與該集電層的第二表面連接；該觸媒層形成於該 第一擴散層的表面；該透氣層形成於該第二擴散層的表面。The collector layer includes a first surface opposite to each other, and a second surface; the first conductive layer is selected from a graphene material and formed on the first surface of the collector layer; the first diffusion layer is formed on the first diffusion layer a surface of the first conductive layer; the second diffusion layer is connected to the second surface of the collector layer; the catalyst layer is formed on the a surface of the first diffusion layer; the gas permeable layer is formed on a surface of the second diffusion layer.
有關本發明之前述及其他技術內容、特點與功效，在以下配合參考圖式的一個較佳實施例的詳細說明中，將可清楚的呈現。The foregoing and other objects, features, and advantages of the invention will be apparent from the
參閱圖1，本發明金屬空氣電池的空氣陰極的較佳實施例包含一集電層1、一第一導電層2、一第二導電層3、一第一擴散層4、一第二擴散層5、一觸媒層6、一透氣層7，及一包覆網8。Referring to FIG. 1, a preferred embodiment of an air cathode of a metal-air battery of the present invention comprises a collector layer 1, a first conductive layer 2, a second conductive layer 3, a first diffusion layer 4, and a second diffusion layer. 5. A catalyst layer 6, a gas permeable layer 7, and a coated web 8.
該集電層1是由導電性良好的金屬材料製成並呈網狀的結構，用以傳導電流並提供足夠的通道讓氧氣擴散通過，該集電層1包括彼此反向的一第一表面11，及一第二表面12。The collector layer 1 is made of a metal material having good conductivity and has a mesh structure for conducting electric current and providing sufficient passage for oxygen to diffuse through, and the collector layer 1 includes a first surface opposite to each other. 11, and a second surface 12.
該第一、二導電層2、3選自石墨烯材料並分別形成於該集電層1的第一、二表面11、12，較佳地，該第一、二導電層2、3的厚度為微米。此外，要說明的是，該第一、二導電層2、3還可進一步形成於該集電層1的網狀結構中，也可僅包含形成於該第一表面11的第一導電層2。The first and second conductive layers 2, 3 are selected from graphene materials and are respectively formed on the first and second surfaces 11, 12 of the collector layer 1, preferably, the thickness of the first and second conductive layers 2, 3. For micrometers. In addition, it should be noted that the first and second conductive layers 2, 3 may be further formed in the network structure of the collector layer 1, or may only include the first conductive layer 2 formed on the first surface 11. .
該第一、二擴散層4、5分別形成於該第一、二導電層2、3的表面，令空氣或氧氣能夠擴散進入至該觸媒層6，並且防止該金屬空氣電池內部的電解液產生外漏。The first and second diffusion layers 4, 5 are respectively formed on the surfaces of the first and second conductive layers 2, 3, so that air or oxygen can diffuse into the catalyst layer 6, and the electrolyte inside the metal air battery is prevented. Produce an external leak.
該觸媒層6形成於該第一擴散層4的表面，而該透氣 層7則形成於該第二擴散層5的表面，其中，該觸媒層6可催化氧氣進行陰極化學反應並轉化成為氫氧根離子。The catalyst layer 6 is formed on the surface of the first diffusion layer 4, and the gas is permeable A layer 7 is formed on the surface of the second diffusion layer 5, wherein the catalyst layer 6 catalyzes a cathode chemical reaction of oxygen and is converted into a hydroxide ion.
該包覆網8具有多數網格並包覆在該觸媒層6的外圍，可用以限制該觸媒層6，令該觸媒層6不易剝落而可延長使用壽命。較佳地，該包覆網8遮蔽該觸媒層6的面積不大於該觸媒層6與電解液反應的面積的25%，以免該觸媒層6被過度遮蔽而影響其與電解液間的反應。此外，該包覆網8也可進一步包覆至該透氣層7，使整體結構更加穩固。較佳地，該包覆網8遮蔽該透氣層7的面積不大於該透氣層7與空氣或氧氣接觸的面積的25%，以免該透氣層7被過度遮蔽而影響空氣或氧氣擴散進入。再者，該包覆網8的網格除了可以是四邊形外，也可以是呈蜂巢狀或是呈柵欄狀。The covered mesh 8 has a plurality of meshes and is coated on the periphery of the catalyst layer 6, and can be used to restrict the catalyst layer 6, so that the catalyst layer 6 is not easily peeled off and the service life can be prolonged. Preferably, the cover mesh 8 shields the area of the catalyst layer 6 by no more than 25% of the area of the catalyst layer 6 reacted with the electrolyte to prevent the catalyst layer 6 from being over-shielded and affecting the electrolyte. Reaction. In addition, the covered mesh 8 can be further coated to the gas permeable layer 7 to make the overall structure more stable. Preferably, the covering mesh 8 shields the gas permeable layer 7 by an area not more than 25% of the area of the gas permeable layer 7 in contact with air or oxygen, so that the gas permeable layer 7 is prevented from being excessively shielded from affecting the diffusion of air or oxygen. Furthermore, the mesh of the covered net 8 may be in the form of a honeycomb or a fence, in addition to a quadrilateral.
當利用本發明空氣陰極為一般金屬空氣電池的陰極時，該觸媒層6會與電解液接觸，而該透氣層7則與外界的空氣接觸，此時外界的空氣即會經過該透氣層7、該第二擴散層5、該第二導電層3、該集電層1、該第一導電層2、該第一擴散層4至該觸媒層6，而外界空氣中的氧氣即滲入該觸媒層6，並配合電解液及陽極產生電化學反應，而藉由形成在該集電層1表面且由石墨烯構成的第一、二導電層2、3，則可更進一步提升該空氣陰極所產生之氧化電流的傳遞。When the air cathode of the present invention is used as the cathode of a general metal air battery, the catalyst layer 6 is in contact with the electrolyte, and the gas permeable layer 7 is in contact with the outside air, and the outside air passes through the gas permeable layer 7 at this time. The second diffusion layer 5, the second conductive layer 3, the collector layer 1, the first conductive layer 2, the first diffusion layer 4 to the catalyst layer 6, and oxygen in the outside air penetrates into the The catalyst layer 6 is combined with the electrolyte and the anode to generate an electrochemical reaction, and the first and second conductive layers 2 and 3 formed on the surface of the collector layer 1 and composed of graphene can further enhance the air. The transfer of the oxidizing current generated by the cathode.
本發明該第一、二導電層2、3所選用的石墨烯材料在 常溫下的電子遷移率高、電阻率低，為一優良的導體，是目前在室溫下電阻率最小也最薄的材料。因此，可藉由該第一、二導電層2、3有效地增加該集電層1的導電性，並加強傳導該空氣陰極所產生的電流，且該第一、二導電層2、3對於該集電層1也具有保護的作用，可減少電解液對於該集電層1的腐蝕程度，進而提升該空氣陰極的使用效率並延長使用壽命。The graphene material selected for the first and second conductive layers 2, 3 of the present invention is It has a high electron mobility and a low resistivity at normal temperature, and is an excellent conductor. It is the material with the lowest and the lowest resistivity at room temperature. Therefore, the conductivity of the collector layer 1 can be effectively increased by the first and second conductive layers 2, 3, and the current generated by the air cathode can be enhanced, and the first and second conductive layers 2, 3 are The collector layer 1 also has a protective function, which can reduce the degree of corrosion of the electrolyte layer to the collector layer 1, thereby improving the use efficiency of the air cathode and prolonging the service life.
綜上所述，本發明空氣陰極藉由該第一、二導電層2、3的高電子遷移率及低電阻率，增加該集電層1的導電性並提供一良好的電子通道，亦可降低該集電層1被電解液腐蝕的速度，進一步加強該空氣陰極的功能，並有效提升該金屬空氣電池的使用效能，延長使用壽命，故確實能達成本發明之目的。In summary, the air cathode of the present invention increases the conductivity of the collector layer 1 and provides a good electron passage by the high electron mobility and low resistivity of the first and second conductive layers 2, 3. The purpose of the present invention can be achieved by reducing the speed at which the collector layer 1 is corroded by the electrolyte, further enhancing the function of the air cathode, and effectively improving the use efficiency of the metal-air battery and prolonging the service life.
惟以上所述者，僅為本發明的較佳實施例而已，當不能以此限定本發明實施的範圍，即大凡依本發明申請專利範圍及發明說明內容所作之簡單的等效變化與修飾，皆仍屬本發明專利涵蓋的範圍內。The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All remain within the scope of the invention patent.
1‧‧‧集電層1‧‧‧ collector layer
11‧‧‧第一表面11‧‧‧ first surface
12‧‧‧第二表面12‧‧‧ second surface
2‧‧‧第一導電層2‧‧‧First conductive layer
3‧‧‧第二導電層3‧‧‧Second conductive layer
4‧‧‧第一擴散層4‧‧‧First diffusion layer
5‧‧‧第二擴散層5‧‧‧Second diffusion layer
6‧‧‧觸媒層6‧‧‧ catalyst layer
7‧‧‧透氣層7‧‧‧ breathable layer
8‧‧‧包覆網8‧‧‧Covered net
圖1是本發明金屬空氣電池的空氣陰極之較佳實施例的示意圖。BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic illustration of a preferred embodiment of an air cathode for a metal air battery of the present invention.
1‧‧‧集電層1‧‧‧ collector layer
11‧‧‧第一表面11‧‧‧ first surface
12‧‧‧第二表面12‧‧‧ second surface
2‧‧‧第一導電層2‧‧‧First conductive layer
3‧‧‧第二導電層3‧‧‧Second conductive layer
4‧‧‧第一擴散層4‧‧‧First diffusion layer
5‧‧‧第二擴散層5‧‧‧Second diffusion layer
6‧‧‧觸媒層6‧‧‧ catalyst layer
7‧‧‧透氣層7‧‧‧ breathable layer
8‧‧‧包覆網8‧‧‧Covered net
Claims (5)
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| TW101147211A TWI489675B (en) | 2012-12-13 | 2012-12-13 | Air-cathode for metal-air batteries |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW101147211A TWI489675B (en) | 2012-12-13 | 2012-12-13 | Air-cathode for metal-air batteries |
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| TW201424087A TW201424087A (en) | 2014-06-16 |
| TWI489675B true TWI489675B (en) | 2015-06-21 |
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| CN109671954B (en) * | 2018-12-14 | 2021-10-29 | 宁波石墨烯创新中心有限公司 | Multilayer metal-air battery cathode and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI223464B (en) * | 2002-02-20 | 2004-11-01 | Evionyx Inc | Metal air cell system |
| EP2270905A1 (en) * | 2009-06-15 | 2011-01-05 | BAE Systems PLC | Metal-air electrochemical cells and methods of manufacturing same |
| CN102414874A (en) * | 2009-04-13 | 2012-04-11 | 应用材料公司 | Composite materials containing metallized carbon nanotubes and nanofibers |
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- 2012-12-13 TW TW101147211A patent/TWI489675B/en active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI223464B (en) * | 2002-02-20 | 2004-11-01 | Evionyx Inc | Metal air cell system |
| CN102414874A (en) * | 2009-04-13 | 2012-04-11 | 应用材料公司 | Composite materials containing metallized carbon nanotubes and nanofibers |
| EP2270905A1 (en) * | 2009-06-15 | 2011-01-05 | BAE Systems PLC | Metal-air electrochemical cells and methods of manufacturing same |
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| TW201424087A (en) | 2014-06-16 |
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