TW202114281A - Power storage device - Google Patents
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- H—ELECTRICITY
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/02—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof using combined reduction-oxidation reactions, e.g. redox arrangement or solion
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/66—Current collectors
- H01G11/68—Current collectors characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/66—Current collectors
- H01G11/70—Current collectors characterised by their structure
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
- H01M10/26—Selection of materials as electrolytes
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- H—ELECTRICITY
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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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- H01M4/64—Carriers or collectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/72—Grids
- H01M4/74—Meshes or woven material; Expanded metal
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- 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
- Y02E60/10—Energy storage using batteries
Abstract
Description
本發明係關於蓄電裝置。 The present invention relates to a power storage device.
蓄電裝置可大致區分為：利用了伴隨著較大的物質轉換之化學反應之二次電池，以及不利用化學反應或是利用了僅伴隨著些微材料表面的物質轉換之化學反應之電容器。 Power storage devices can be roughly divided into secondary batteries that use a chemical reaction accompanied by large material conversion, and capacitors that do not use a chemical reaction or use a chemical reaction that only involves material conversion on the surface of a small material.
再者，電容器可區分為電雙層電容器(EDLC：Electric Double-layer Capacitor)以及氧化還原電容器。此等當中，二次電池與EDLC已有市售品，惟氧化還原電容器仍停留在研究階段。EDLC係作為可再生能源(風力發電、太陽能發電)的蓄電裝置而被利用成為油電混合車或電動車的輔助電源。 Furthermore, capacitors can be divided into electric double-layer capacitors (EDLC: Electric Double-layer Capacitor) and redox capacitors. Among these, secondary batteries and EDLC have been commercially available, but redox capacitors are still in the research stage. The EDLC system is used as a power storage device for renewable energy (wind power generation, solar power generation) and used as an auxiliary power source for hybrid vehicles or electric vehicles.
二次電池的放電容量大，但相反地卻在輸出、重複耐久性、充放電時間上存在著課題，此外，EDLC的輸出、重複耐久性、充放電時間優異，惟仍有放電容量小之取捨關係。氧化還原電容器可確保EDLC的輸出、重複耐久性、充放電時間之特徵，並且可改善其缺點之放電容量，因而對其積極地進行研究。 The discharge capacity of the secondary battery is large, but on the contrary, there are problems in the output, repeated durability, and charging and discharging time. In addition, the EDLC has excellent output, repeated durability, and charging and discharging time, but there is still a trade-off for small discharge capacity. relationship. Redox capacitors can ensure the characteristics of EDLC output, repeated durability, charge and discharge time, and can improve the discharge capacity of its shortcomings, so it is actively researched.
以往，氧化還原電容器的電極材料係已利用氧化釕、氧化銦、氧化錳、氧化鎳、氫氧化鎳、氧化鈷、氫氧化鈷、羥基氧化鎳等。氧化釕及氧化銦雖然能力充足，但極為昂貴而仍未達市售階段，氧化錳、氧化鎳、氫氧化鎳、氧化鈷、氫氧化鈷及羥基氧化鎳等之放電容量低。 In the past, ruthenium oxide, indium oxide, manganese oxide, nickel oxide, nickel hydroxide, cobalt oxide, cobalt hydroxide, nickel oxyhydroxide, etc. have been used as electrode materials for redox capacitors. Although ruthenium oxide and indium oxide have sufficient capacity, they are extremely expensive and have not yet reached the commercial stage. Manganese oxide, nickel oxide, nickel hydroxide, cobalt oxide, cobalt hydroxide and nickel oxyhydroxide have low discharge capacities.
於專利文獻1中係提出有使用金屬奈米線作為電容器電極。 Patent Document 1 proposes the use of metal nanowires as capacitor electrodes.
[先前技術文獻] [Prior Technical Literature]
[專利文獻] [Patent Literature]
[專利文獻1]日本特開2011-195865號公報 [Patent Document 1] JP 2011-195865 A
以往，於鹼性電解液中將以銅或鐵為主成分之合金形成為電極時之電容器特性，由於電容的大小及充放電特性的維持中之任一項不足，所以被認為不適合用作為在鹼性電解液中所使用之電極活性物質。 In the past, the capacitor characteristics when an alloy containing copper or iron as the main component is formed as an electrode in an alkaline electrolyte is considered to be unsuitable for use as an electrode due to insufficient capacitance and maintenance of charge and discharge characteristics. Electrode active material used in alkaline electrolyte.
因此，本發明之課題在於提供一種將資源上容易取得之以銅等為代表的遍在性元素(Ubiquitous Element)用作為電極的主成分，並且可達成電容的大小及充放電特性的維持之蓄電裝置。 Therefore, the subject of the present invention is to provide a storage battery that uses ubiquitous elements represented by copper, etc., which are easily available as the main component of the electrode, and can achieve the maintenance of the size of the capacitor and the charging and discharging characteristics. Device.
本發明人對上述課題進行精心探討後，發現到藉由構成為使用特定的電解液及電極之具有特定結構之蓄電裝置，可發揮高放電容量及重複耐久性，因而完成本發明。亦即，本發明係如下列所述。 The inventors of the present invention have carefully studied the above-mentioned issues and found that a power storage device with a specific structure configured to use a specific electrolyte and electrodes can exhibit high discharge capacity and repetitive durability, thus completing the present invention. That is, the present invention is as described below.
本發明(1)為一種蓄電裝置，係具有：絕緣性的外輪廓體，以及被密閉性地保持在前述外輪廓體內之第1電極、第2電極及電解液， The present invention (1) is an electrical storage device having an insulating outer contour body, and a first electrode, a second electrode, and an electrolyte that are hermetically held in the outer contour body, and
前述第1電極與前述第2電極係以隔著前述電解液被隔離之狀態被保持，其中， The first electrode and the second electrode are held in a state of being isolated via the electrolyte solution, wherein,
前述電解液為鹼性電解液， The foregoing electrolyte is an alkaline electrolyte,
前述第1電極及前述第2電極的至少一者或兩者為多孔質導電體， At least one or both of the first electrode and the second electrode are porous electrical conductors,
前述多孔質導電體含有鐵及/或銅作為主成分。 The aforementioned porous conductor contains iron and/or copper as main components.
本發明(2)為前述發明(1)所述之蓄電裝置，其中前述多孔質導電體係以鐵為主成分，前述鹼性電解液的莫耳濃度為0.1至5mol/L。 The invention (2) is the electricity storage device according to the invention (1), wherein the porous conductive system is mainly composed of iron, and the molar concentration of the alkaline electrolyte is 0.1 to 5 mol/L.
本發明(3)為前述發明(1)所述之蓄電裝置，其中前述多孔質導電體係以銅為主成分，前述鹼性電解液的莫耳濃度為0.1至1mol/L。 The invention (3) is the electricity storage device according to the invention (1), wherein the porous conductive system is mainly composed of copper, and the molar concentration of the alkaline electrolyte is 0.1 to 1 mol/L.
本發明(4)為前述發明(1)至(3)中任一項所述之蓄電裝置，其中前述多孔質導電體含有金屬纖維片。 The invention (4) is the electricity storage device according to any one of the inventions (1) to (3), wherein the porous conductor contains a metal fiber sheet.
本發明(5)為前述發明(1)至(4)中任一項所述之蓄電裝置，其係氧化還原電容器。 The present invention (5) is the power storage device according to any one of the foregoing inventions (1) to (4), which is a redox capacitor.
根據本發明，可提供一種便宜且具有高放電容量與重複耐久性之蓄電裝置。 According to the present invention, it is possible to provide an inexpensive power storage device with high discharge capacity and repeated durability.
10:電源(恆電位器等) 10: Power supply (potentiostat, etc.)
20:主室 20: Main room
21:工作電極 21: working electrode
22:對向電極 22: Counter electrode
30:副室 30: Associate Room
31:參考電極 31: Reference electrode
40:鹽橋 40: Salt Bridge
50,60:電解液 50, 60: electrolyte
70:玻璃濾片 70: glass filter
80:充放電單元 80: charge and discharge unit
100:三電極裝置(蓄電裝置) 100: Three-electrode device (electric storage device)
110:外輪廓體 110: Outer contour
120:電極對 120: Electrode pair
121:第1電極 121: first electrode
122:第2電極 122: second electrode
130:電解液 130: Electrolyte
140:端子 140: Terminal
150:分隔片 150: Separator
200:充放電裝置 200: charging and discharging device
圖1為本發明之蓄電裝置100之概念圖。
FIG. 1 is a conceptual diagram of a
圖2為用以形成導電性奈米結構之三電極方式的裝置之示意圖。 Figure 2 is a schematic diagram of a three-electrode device for forming a conductive nanostructure.
圖3為充放電裝置之示意圖。 Figure 3 is a schematic diagram of a charging and discharging device.
以下係詳細說明本發明之蓄電裝置，惟本發明並不限定於此等。 The following is a detailed description of the power storage device of the present invention, but the present invention is not limited to this.
本發明之蓄電裝置通常是使用作為電容器(較佳為氧化還原電容器)，惟在具有本發明之構成下，亦可使用在其他蓄電裝置(例如二次電池等)。 The power storage device of the present invention is usually used as a capacitor (preferably a redox capacitor), but with the configuration of the present invention, it can also be used in other power storage devices (for example, secondary batteries, etc.).
下列所示之各種物性在無特別言明時，係設為在25℃所測定者。 Unless otherwise stated, the various physical properties shown below are those measured at 25°C.
〈〈〈蓄電裝置〉〉〉 〈〈〈Storage device〉〉〉
〈〈全體構成〉〉 <<Overall composition>>
如圖1所示，本發明之蓄電裝置100係具有：外輪廓體110，以及被密閉性地保持在外輪廓體110內之電極對120(第1電極121、第2電極122)及電解液130。第1電極121及第2電極122係浸漬在電解液130。第1電極121與第2電極122是以隔著電解液130被隔離之狀態被保持著。
As shown in FIG. 1, the
蓄電裝置100通常是具有：用以電性連接外部電路或外部電源(圖中未顯示)與第1電極121(第2電極122)之端子140。
The
端子140只要是形成為可導電者即可，其材質及形狀並無任何限定。端子140可與第1電極121(第2電極122)形成為一體，或是與第
1電極121(第2電極122)形成為不同個體後，使端子140與第1電極121(第2電極122)電性連接。
The
以防止第1電極121與第2電極122之電性接觸者等為目的，蓄電裝置100可於第1電極121與第2電極122之間更包含分隔片150。
For the purpose of preventing electrical contact between the
此分隔片150可使用通常蓄電裝置所使用之分隔片(例如具有絕緣性之不織布或是具有絕緣性及離子穿透性之多孔膜等)。分隔片150的材料、厚度、大小等可因應蓄電裝置100的電構成來適當地調整。
The
在以包含第1電極121、第2電極122及電解液130之電構成作為1單元時，蓄電裝置100可由複數個單元所構成。
When an electrical structure including the
於圖中雖未顯示，惟蓄電裝置100亦可構成為：將第1電極121及第2電極122形成為片狀，隔著具有絕緣性之分隔片150捲取第1電極121及第2電極122，並連同電解液130容納於外輪廓體110內之結構。藉由如此地構成，可提升每單位體積的電容。
Although not shown in the figure, the
其他電構成等並無特別限定，可適用通常的蓄電裝置中所設定之條件等。 Other electrical components are not particularly limited, and conditions and the like set in ordinary power storage devices can be applied.
接著詳細說明屬於本發明的特徵部分之外輪廓體110、電極對120及電解液130。
Next, the
〈〈外輪廓體110〉〉
〈〈
外輪廓體110係構成為：具有絕緣性，除了端子140之外，將外輪廓體110內部與外輪廓體110外部設為無法導通，並且將第1電極121、第2電極122及電解液130保持在密閉狀態。
The
外輪廓體110的形狀及大小只要是可在其內部將第1電極121、第2電極122及電解液130保持在密閉狀態即可，並無特別限定。圖1中係將外輪廓體110形成為箱體型，惟亦可將外輪廓體110形成為圓筒狀或薄板狀，或是將外輪廓體110形成為膜狀並層合全體之構成。
The shape and size of the
在此所示之所謂「密閉狀態」，係表示具有防止電解液130的洩漏之水密性以及不會使外部的氣體(尤其是大氣中的二氧化碳)積極地接觸於電解液之氣密性者。藉由此構成，可防止後述電解液130的變質。此外，所謂外輪廓體110「具有絕緣性」，係表示無法導通(或難以導通)至對使用在各蓄電裝置(電晶體或二次電池等)之外輪廓體所要求的程度。
The so-called "closed state" shown here refers to those having water tightness to prevent leakage of the
外輪廓體110的材料只要是具有絕緣性並且可充分地保持外輪廓體110內部的密閉狀態者即可，並無特別限定，較佳係難以因電解液130而變質之材料。
The material of the
此外，為了同時達成對外輪廓體110全體所要求之性質(例如氣密性或絕緣性)以及對外輪廓體110的內部構成所要求之性質(例如難以因電解液130而變質)，外輪廓體110可具有由複數層所構成之層結構。在此情形下，構成外輪廓體110的一部分之材料可包含具有導電性之材料。
In addition, in order to simultaneously achieve the properties required for the entire outer contour body 110 (for example, airtightness or insulation) and the properties required for the internal structure of the outer contour body 110 (for example, it is difficult to be deteriorated by the electrolyte 130), the
〈〈電極對120〉〉
〈〈Electrode
第1電極121及第2電極122的至少一者或兩者為多孔質導電體。第1電極121及第2電極122較佳係兩者皆為多孔質導電體，惟亦可是僅有任一方為多孔質導電體以外的電極結構體。
At least one or both of the
以下說明多孔質導電體以及多孔質導電體以外的電極結構體。 Hereinafter, the porous conductor and the electrode structure other than the porous conductor will be described.
〈多孔質導電體〉 〈Porous Conductor〉
多孔質導電體意指具有導電性且其表面或包含表面及內部之多孔質導電體全體為多孔質者，該具體結構並無特別限定。 The porous conductor means one having conductivity and the entire surface or the porous conductor including the surface and the inside is porous, and the specific structure is not particularly limited.
例如，只要是粉體或纖維等之聚集體為多孔質的結構即可。在此情形下，粉體或纖維等之構成物本身可為多孔質或是非多孔質。該例可列舉出以纖維所編織之布料等，即使纖維本身非多孔質，亦可構成為於布料的表面或全體具有孔或間隙之結構。 For example, what is necessary is just to have a porous structure, such as a powder or fiber aggregate. In this case, the structure itself such as powder or fiber may be porous or non-porous. This example includes fabrics woven with fibers. Even if the fibers themselves are not porous, they can be configured to have holes or gaps on the surface or the entire fabric.
於本說明書中，在僅記載為「表面」之情形下，係包含：基材的表面、設置在基材之孔內部的表面、構成基材之構成構件本身的表面、以及形成於基材內部之與外部環境連通之孔內部等的表面。例如在以金屬纖維片作為基材之情形下，意指金屬纖維片的表面、屬於構成物之金屬纖維的表面、以及形成於金屬纖維片內部之與外部環境連通之孔內部的表面。 In this specification, when only described as "surface", it includes: the surface of the substrate, the surface provided in the pores of the substrate, the surface of the constituent member itself constituting the substrate, and the surface formed inside the substrate The surface of the inside of the hole that communicates with the external environment. For example, when a metal fiber sheet is used as a base material, it means the surface of the metal fiber sheet, the surface of the metal fiber belonging to the structure, and the surface of the hole formed in the metal fiber sheet that communicates with the external environment.
在此所謂具有導電性或導電性的材質，意指電阻率為1×1010Ω‧m以下者。導電性的測定方法可藉由一般所知的方法來測定，例如可依據JIS C2139：2008的方法來測定。 The material with conductivity or conductivity here means a material with a resistivity of 1×10 10 Ω·m or less. The method of measuring conductivity can be measured by a generally known method, for example, it can be measured in accordance with the method of JIS C2139:2008.
多孔質導電體的材質係以鐵及/或銅作為主成分。多孔質導電體的材質可為僅以鐵元素為主成分之情形、僅以銅元素為主成分之情形、以及鐵元素及銅元素的合計成為主成分之情形中任一型態。多孔質導電體所含有之鐵或銅可為鐵單體、鐵合金、銅單體、或銅合金、或是此等之混合物中任一型態。於鐵合金或銅合金中，所添加之金屬元素並無特別限定，可配合期望的性質來適當地選擇。多孔質導電體的材質較佳為不鏽鋼及/或銅。 The material of the porous conductor is mainly composed of iron and/or copper. The material of the porous conductor may be any type in which iron is the main component, copper is the main component, or the total of iron and copper is the main component. The iron or copper contained in the porous conductor can be any type of iron, iron alloy, copper, or copper alloy, or a mixture of these. In the iron alloy or the copper alloy, the metal element to be added is not particularly limited, and can be appropriately selected according to the desired properties. The material of the porous conductor is preferably stainless steel and/or copper.
此外，多孔質導電體只要在全體具有導電性下，亦可與非導電性的材質組合。 In addition, as long as the porous conductor is electrically conductive as a whole, it may be combined with a non-conductive material.
所謂多孔質導電體的材質以某物質(鐵及/或銅)作為主成分，意指相對於多孔質導電體的全量，該某元素(鐵元素及銅元素的合計)為50質量%以上、60質量%以上、70質量%以上、80質量%以上、90質量%以上、95質量%以上、99質量%以上或100質量%之情形。 The material of the porous conductor has a certain substance (iron and/or copper) as the main component, which means that the certain element (the total of iron and copper) is 50% by mass or more relative to the total amount of the porous conductor. 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 99% by mass or more, or 100% by mass.
多孔質導電體可為使多數的粉體或纖維等聚集成構成物之多孔質體，較佳係包含：含有由鐵及/或銅所構成之金屬纖維作為主成分之金屬纖維片。所謂由鐵及/或銅所構成之金屬纖維，例如為鐵纖維、鐵合金纖維、銅纖維、銅合金纖維以及此等纖維之混合物。金屬纖維片尤佳為不鏽鋼纖維片及/或銅纖維片。在密閉之狀況下，於使用鹼性電解液之蓄電裝置中將多孔質導電體構成為金屬纖維片之情形下，可確認到電容遠超過伴隨著纖維片之實效表面積的增加之效果而提高至極高的程度。詳細原因雖仍未明瞭，惟已暗示下述的可能性：藉由使用金屬纖維，微觀上於充放電時沿著各金屬纖維的長軸所形成之磁場，係作用於鹼性電解液中之離子(包含氫氧化物離子)的物質移動等而可能有利於電容的提升。 The porous conductor may be a porous body in which a large number of powders or fibers are aggregated into a structure, and preferably includes a metal fiber sheet containing a metal fiber composed of iron and/or copper as a main component. The so-called metal fibers composed of iron and/or copper are, for example, iron fibers, iron alloy fibers, copper fibers, copper alloy fibers, and mixtures of these fibers. The metal fiber sheet is particularly preferably a stainless steel fiber sheet and/or a copper fiber sheet. In an airtight condition, when the porous conductor is constructed as a metal fiber sheet in an electricity storage device using alkaline electrolyte, it can be confirmed that the capacitance far exceeds the effect accompanied by the increase in the effective surface area of the fiber sheet. High degree. Although the detailed reason is still unclear, the following possibility has been suggested: by using metal fibers, microscopically, the magnetic field formed along the long axis of each metal fiber during charging and discharging will act on the alkaline electrolyte. The movement of ions (including hydroxide ions) and the like may contribute to the increase of capacitance.
金屬纖維片在不阻礙本發明之效果下，可含有金屬以外的成分。 The metal fiber sheet may contain components other than metal without hindering the effects of the present invention.
此金屬纖維片的纖維直徑、密度(單位面積重量)、厚度等，可考量剛硬性或導電性、電容等來適當地變更。纖維直徑較佳例如為1μm以上、2μm以上、3μm以上、4μm以上、5μm以上，較佳為100μm以下、50μm以下、30μm以下、25μm以下。單位面積重量較佳例如為10g/m2以 上、50g/m2以上、100g/m2以上、200g/m2以上、較佳為1000g/m2以下、700g/m2以下、500g/m2以下。 The fiber diameter, density (weight per unit area), thickness, etc. of the metal fiber sheet can be appropriately changed in consideration of stiffness, conductivity, capacitance, and the like. The fiber diameter is preferably, for example, 1 μm or more, 2 μm or more, 3 μm or more, 4 μm or more, 5 μm or more, preferably 100 μm or less, 50 μm or less, 30 μm or less, or 25 μm or less. The weight per unit area is preferably, for example, 10 g/m 2 or more, 50 g/m 2 or more, 100 g/m 2 or more, 200 g/m 2 or more, preferably 1000 g/m 2 or less, 700 g/m 2 or less, 500 g/m 2 the following.
多孔質導電體可因應性能或用途來施以安裝用的孔或缺口等加工。 Porous conductors can be processed with holes or notches for installation according to their performance or use.
在多孔質導電體為金屬纖維片之情形下，例如可藉由濕式抄製金屬纖維來製造。濕式抄製金屬纖維而成之纖維片的例子，可列舉出藉由日本特開平07-258706號公報所揭示之方法而製作之金屬纖維燒結片等。 When the porous conductor is a metal fiber sheet, it can be produced by, for example, wet papermaking of metal fiber. Examples of fiber sheets formed by wet paper sheeting of metal fibers include metal fiber sintered sheets produced by the method disclosed in Japanese Patent Application Laid-Open No. 07-258706.
此金屬燒結片可使用合適的不鏽鋼纖維或銅纖維來製作，可調整孔或間隙的大小及分布等，然後可在燒結片形成後進行加工，從可二次加工為各種形狀之點來看，其用途範圍廣泛，故較佳。 This metal sintered sheet can be made of suitable stainless steel fiber or copper fiber, and the size and distribution of holes or gaps can be adjusted. Then it can be processed after the sintered sheet is formed. From the point of view that it can be processed into various shapes by secondary processing, It has a wide range of uses, so it is preferred.
多孔質導電體之孔的形狀、大小、間隔等並無特別限定。孔的大小例如可設為0.01μm至1000μm，較佳為0.1μm至500μm，更佳為1μm至300μm。藉由設為此範圍，可預期放電容量的提升。孔的大小的測定可使用掃描型電子顯微鏡(之後略稱為SEM：例如依據JIS K0132：1997)來測定。此外，此孔的大小可設為孔等所具有之最長直徑(最長邊)，且可使用SEM來拍攝隨機地選出之50個孔，測定所得到之孔之最長直徑(最長邊)的長度，並設為其平均值。 The shape, size, interval, etc. of the pores of the porous conductor are not particularly limited. The size of the hole can be, for example, 0.01 μm to 1000 μm, preferably 0.1 μm to 500 μm, and more preferably 1 μm to 300 μm. By setting it in this range, an increase in discharge capacity can be expected. The size of the hole can be measured using a scanning electron microscope (hereinafter abbreviated as SEM: for example, in accordance with JIS K0132: 1997). In addition, the size of the hole can be set to the longest diameter (longest side) of the hole, etc., and 50 randomly selected holes can be photographed using SEM, and the length of the longest diameter (longest side) of the obtained hole can be measured. And set it as the average value.
接著說明多孔質導電體的特佳型態之具有導電性奈米結構之多孔質導電體。 Next, a porous conductor with a conductive nano structure, which is a particularly preferred type of porous conductor, will be described.
(具有導電性奈米結構之多孔質導電體) (Porous conductor with conductive nano structure)
具有導電性奈米結構之多孔質導電體係以上述多孔質導電體作為基材(例如金屬纖維片)，並於該基材(例如金屬纖維片)的表面上形成導電性奈米結構者。換言之，具有導電性奈米結構之多孔質導電體係包含：多孔質基材(僅改稱為上述多孔質導電體，例如金屬纖維片)，以及形成於多孔質基材的表面之導電性奈米結構。 A porous conductive system with a conductive nanostructure uses the above-mentioned porous conductor as a substrate (for example, a metal fiber sheet), and a conductive nanostructure is formed on the surface of the substrate (for example, a metal fiber sheet). In other words, a porous conductive system with a conductive nanostructure includes: a porous substrate (only renamed the above-mentioned porous conductor, such as a metal fiber sheet), and conductive nanoparticles formed on the surface of the porous substrate structure.
導電性奈米結構的材質只要是可形成於多孔質導電體上之具有導電性之材質即可，並無特別限定。例如可列舉出：金屬、陶瓷、樹脂、玻璃、石墨等，此等當中，若使用至少1種材質即可。 The material of the conductive nanostructure is not particularly limited as long as it is a conductive material that can be formed on the porous conductor. For example, metals, ceramics, resins, glass, graphite, etc. may be mentioned. Among these, at least one material may be used.
此外，可藉由一般所知的方法將非導電體的材質形成為具導電性之材質。例如可列舉出離子植入有如硼般的第13族元素或磷等第15族元素之矽或金剛石等。此外，於藉由離子植入來附加導電性之方法等之可於奈米結構形成後實施之方法之情形下，在將非導電性的奈米結構形成於基材表面後，可藉由進行離子植入等來形成導電性奈米結構。 In addition, the material of the non-conductive body can be formed into a conductive material by a generally known method. For example, silicon or diamond ion-implanted with a group 13 element such as boron or a group 15 element such as phosphorus. In addition, in the case of a method that can be implemented after the formation of the nanostructure, such as the method of adding conductivity by ion implantation, after the non-conductive nanostructure is formed on the surface of the substrate, it can be performed by Ion implantation or the like to form a conductive nanostructure.
從電傳導率等電特性來看，導電性奈米結構的材質較佳為金屬，尤佳為金、鉑、銀、銅、鈷，從顯現可逆性電化學反應之特性來看，更佳為銀、銅、鈷，特佳為銅。 From the point of view of electrical characteristics such as electrical conductivity, the material of the conductive nanostructure is preferably metal, especially gold, platinum, silver, copper, and cobalt. From the point of view of the characteristics of exhibiting reversible electrochemical reactions, it is more preferred. Silver, copper, cobalt, copper is particularly preferred.
導電性奈米結構的形狀並無特別限定，可列舉出：多角形狀、圓形狀、橢圓形狀等之粒狀；多角形狀、圓形狀、橢圓形狀等之板狀；針狀；多角形狀、圓形狀、橢圓形狀等之柱狀；纖維狀；樹枝狀；結晶成長中的架構晶體形狀等，亦可為將此等形狀組合複數種之形狀(複合性結構)。 The shape of the conductive nanostructure is not particularly limited, and examples include: granular shapes such as polygonal, round, and elliptical shapes; plate shapes such as polygonal, round, and elliptical shapes; needle-like shapes; polygonal shapes and round shapes Columnar shapes such as oval and elliptical shapes; fibrous shapes; dendritic shapes; structural crystal shapes during crystal growth, etc., can also be a combination of these shapes (composite structure).
複合性結構的例子可列舉出樹枝狀，例如可形成為從纖維狀的結構中分枝，使纖維狀的結構成長，然後纖維狀的結構從纖維狀的結構 中重複地成長之結構。此複雜的重複結構可顯著地增大形成於多孔質導電體之導電性奈米結構的表面積，而能夠提升放電容量或重複耐久性。 Examples of composite structures include dendritic shapes. For example, it can be formed to branch from a fibrous structure to grow the fibrous structure, and then the fibrous structure changes from the fibrous structure A structure that grows repeatedly in the middle. This complex repeating structure can significantly increase the surface area of the conductive nanostructure formed on the porous conductor, and can increase the discharge capacity or repeat durability.
所謂奈米大小的結構，係設為構成導電性奈米結構之至少一邊的長度(剖面的直徑或短軸)未達1μm之結構。此外，同樣地，所謂微米大小的結構，係設為構成結構之一邊的長度(剖面的直徑或短軸)為0.001至1mm之結構。 The so-called nano-sized structure is a structure in which the length of at least one side (diameter or minor axis of the cross section) of the conductive nano structure is less than 1 μm. In addition, similarly, the so-called micron-sized structure is a structure in which the length of one side of the constituent structure (the diameter or the minor axis of the cross section) is 0.001 to 1 mm.
導電性奈米結構並無特別限定。例如於樹枝狀的導電性奈米結構之情形下，樹枝狀結構全體可為微米大小，且至少相當於樹枝的枝部分可為奈米大小。亦即，導電性奈米結構本身的大小並無限定，只要是至少一部分具有奈米大小的結構部分之結構即可。 The conductive nanostructure is not particularly limited. For example, in the case of a dendritic conductive nanostructure, the entire dendritic structure may be micrometer in size, and at least the branch part corresponding to a branch may be nanometer in size. That is, the size of the conductive nanostructure itself is not limited, as long as it is a structure that has at least a part of a nano-sized structure.
此外，作為其他例子，於導電性奈米結構為纖維狀之情形下，只要是至少其剖面的短徑(或短軸)為奈米大小即可，在此情形下，纖維的長度只要在不妨礙本發明的效果下，並無特別限定。例如導電性奈米結構全體的大小，亦即導電性奈米結構距離多孔質導電體表面之最長的長度可設為0.001至1000μm，較佳為0.01至500μm。 In addition, as another example, when the conductive nanostructure is fibrous, at least the minor axis (or minor axis) of the cross-section should be nanometer-sized. In this case, the length of the fiber It is not particularly limited as long as it hinders the effect of the present invention. For example, the size of the entire conductive nanostructure, that is, the longest length of the conductive nanostructure from the surface of the porous conductor can be set to 0.001 to 1000 μm, preferably 0.01 to 500 μm.
此外，於導電性奈米結構為複合性結構之情形下，構成導電性奈米結構之奈米大小的結構部分的大小，其構成奈米大小的結構之至少一邊的長度(剖面上的直徑或短軸)可設為未達1μm，較佳為1至500nm，尤佳為5至300nm。 In addition, when the conductive nanostructure is a composite structure, the size of the nano-sized structural part constituting the conductive nanostructure is the length of at least one side of the nano-sized structure (the diameter or the cross-section The short axis) can be set to less than 1 μm, preferably 1 to 500 nm, and particularly preferably 5 to 300 nm.
導電性奈米結構之大小的測定會因導電性奈米結構的大小而有所不同，可使用SEM(例如依據JIS K0132：1997)或穿透型電子顯微 鏡(TEM：依據JIS H7804：2004)等來測定。此外，亦可組合複數種測定方法。 The measurement of the size of the conductive nanostructure varies with the size of the conductive nanostructure. SEM (for example, according to JIS K0132:1997) or transmission electron microscopy can be used Mirror (TEM: in accordance with JIS H7804: 2004) and the like are measured. In addition, multiple measurement methods can also be combined.
(具有導電性奈米結構之多孔質導電體的製造方法) (Manufacturing method of porous conductor with conductive nano structure)
具有導電性奈米結構之多孔質導電體的製造方法可使用一般所知的方法。例如可列舉出：氣相反應蒸鍍法、自組裝法(self-assembly method)、使用微影技術之方法、電子束加工、FIB(Focus ion beam；聚焦離子束)加工、電化學方法等。當中尤佳為製造費用本身便宜，設備簡便且便宜之電化學方法，更佳為藉由日本專利第5574158號所進行之銅奈米結構體的製造方法等。同樣的，亦可較佳地使用日本國際公開第2019/059238號所揭示之方法。 The method for producing a porous conductor having a conductive nanostructure can use a generally known method. For example, gas phase reaction evaporation method, self-assembly method, method using lithography technology, electron beam processing, FIB (Focus ion beam; focused ion beam) processing, electrochemical method, etc. can be cited. Among them, the electrochemical method with cheap manufacturing cost, simple and inexpensive equipment is particularly preferred, and the method for manufacturing copper nanostructures by Japanese Patent No. 5574158 is more preferred. Similarly, the method disclosed in Japanese International Publication No. 2019/059238 can also be preferably used.
下列係說明屬於合適例子之依據三電極法所進行之銅之奈米結構物的形成方法。 The following is a suitable example for the formation of copper nanostructures based on the three-electrode method.
如圖2所示，係採用由電源、具備工作電極與對向電極之主室、副室、鹽橋及參考電極所構成之三電極式單元裝置。 As shown in Figure 2, a three-electrode unit device consisting of a power supply, a main chamber with a working electrode and a counter electrode, a sub-chamber, a salt bridge, and a reference electrode is used.
電源並無特別限定，較佳為恆電位器。恆電位器為使工作電極的電位相對於參考電極成為一定之裝置，其係正確地測量工作電極與對向電極間之電位，並且使電流幾乎不往參考電極流動之架構。在未使用恆電位器之情形下，必須另外進行相同的調整。 The power source is not particularly limited, but a potentiostat is preferred. The potentiostat is a device that makes the potential of the working electrode relative to the reference electrode constant. It is a structure that accurately measures the potential between the working electrode and the counter electrode, and makes almost no current flow to the reference electrode. If the potentiostat is not used, the same adjustment must be made separately.
將多孔質導電體作為工作電極。對向電極並無特別限定，可使用一般所知的材質。例如可列舉出鉑。參考電極只要是一般所知的參考電極即可，並無特別限定，例如可列舉出飽和甘汞電極。 Use a porous conductor as a working electrode. The counter electrode is not particularly limited, and generally known materials can be used. For example, platinum can be cited. The reference electrode is not particularly limited as long as it is a generally known reference electrode. For example, a saturated calomel electrode can be cited.
於主室中，係於蒸餾水中注入由屬於銅錯合物之硫酸四氨銅(II)或硫酸銅(II)、硫酸鋰、及氨水所調製之電解液，於副室中，係於蒸餾水中注入由硫酸鋰及氨水所調製之電解液。 In the main chamber, an electrolyte prepared by copper (II) tetraammonium sulfate or copper (II) sulfate, lithium sulfate, and ammonia, which is a copper complex, is injected into distilled water. In the auxiliary chamber, it is connected to distilled water. Inject the electrolyte prepared by lithium sulfate and ammonia water.
對參考電極施加-1.0V至-2.0V並通電0.10至20C/cm2的電量，藉此使硫酸四氨銅(II)或硫酸銅(II)進行二電子還原，使銅析出於作為工作電極的前述多孔質導電體而形成奈米結構。此時進行0.1至120分鐘的通電，可得到在表面及內部具有導電性奈米結構之多孔質導電體。 Applying -1.0V to -2.0V to the reference electrode and energizing the electricity of 0.10 to 20C/cm 2 , thereby causing copper tetraammonium sulfate (II) or copper sulfate (II) to undergo two-electron reduction, so that copper is precipitated as a working electrode The aforementioned porous conductor forms a nanostructure. At this time, conduct electricity for 0.1 to 120 minutes to obtain a porous electrical conductor with a conductive nanostructure on the surface and inside.
〈多孔質導電體以外的電極結構體〉 <Electrode structure other than porous conductor>
多孔質導電體以外的電極結構體可使用以往蓄電裝置所使用之導電板等。 For electrode structures other than the porous conductors, conductive plates and the like used in conventional electricity storage devices can be used.
此等電極材料可與多孔質導電體同樣地採用以鐵或銅作為主成分之金屬材料，除此之外，亦可使用：鋁、鎳、鈦、金、銀、鉑、鈷、鉛及鋅或含有此等之合金等之金屬材料，或是活性碳等碳材料等。 These electrode materials can be made of metal materials with iron or copper as the main component in the same way as porous conductors. In addition, they can also be used: aluminum, nickel, titanium, gold, silver, platinum, cobalt, lead, and zinc Or metal materials containing these alloys, or carbon materials such as activated carbon.
第1電極121及第2電極122的形狀及大小(面積及厚度)、第1電極121及第2電極122的隔間距離等，可因應蓄電裝置100的電構成來適當地調整。
The shape and size (area and thickness) of the
〈〈電解液130〉〉
〈
電解液130典型而言為含有氫氧化鉀水溶液、氫氧化鈉水溶液、氫氧化鋰水溶液等鹼金屬的氫氧化物作為溶質之鹼性電解液，惟亦可為氫氧化銨、氫氧化四烷基銨的水溶液、鹼土金屬的氫氧化物的水溶液等。
The
在電解液為氫氧化鉀水溶液、氫氧化鈉水溶液、氫氧化鋰水溶液之情形下，電解液130中之鹼金屬離子的莫耳濃度會因電極材質而使
較佳範圍有所不同，惟較佳為0.1至5mol/L，尤佳為0.1至1mol/L，更佳為0.2至1mol/L。
When the electrolyte is potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, or lithium hydroxide aqueous solution, the molar concentration of alkali metal ions in the
詳細而言，於多孔質導電體以鐵為主成分之情形下，電解液130之鹼金屬離子的莫耳濃度較佳為0.1至5mol/L。此外，於多孔質導電體以銅為主成分之情形下，電解液130之鹼金屬離子的莫耳濃度較佳為0.1至1mol/L。
In detail, in the case where the porous conductor contains iron as the main component, the molar concentration of alkali metal ions in the
電解液130的pH較佳為12以上，尤佳為13以上。
The pH of the
〈〈〈發明之效果〉〉〉 〈〈〈Effect of Invention〉〉〉
鐵或銅等係便宜且容易取得，另一方面卻容易反應而難以控制反應，所以為不適合作為蓄電裝置的電極材料之材料。雖可考量藉由將蓄電裝置的電解液作為鹼電解質以控制反應，惟在此情形下會產生蓄電裝置的急遽劣化，而導致重複耐久性惡化之結果。尤其在將電極材料作為多孔質材料之情形下，雖有利於初期放電容量的提升，另一方面卻無法避免急遽的劣化。 Iron, copper, etc. are cheap and easy to obtain. On the other hand, they are easy to react and difficult to control the reaction. Therefore, they are not suitable materials for electrode materials of power storage devices. Although it can be considered that the electrolyte of the power storage device is used as an alkaline electrolyte to control the reaction, in this case, rapid deterioration of the power storage device will occur, resulting in repeated durability deterioration. In particular, when the electrode material is used as a porous material, although it is beneficial to increase the initial discharge capacity, on the other hand, rapid deterioration cannot be avoided.
本發明人們係詳細地探討實驗結果，發現到於構成蓄電裝置時，若電解液的密封不足，電解液130會吸附氣體中的二氧化碳，結果使電解液130變質(電解液130的pH降低)，對鐵及銅之作用產生變化，而暗示產生急遽的電極劣化之可能性。
The inventors studied the experimental results in detail and found that if the electrolyte is not sealed enough to form an electrical storage device, the
根據此發現，在形成本發明之構成時，首先係使用鐵或銅(或是鐵合金、銅合金)，同時也將氧化還原反應所需之銅、鐵等留置在電極，而變得能夠重複進行氧化還原反應(充放電反應)，因而達成銅、鐵等對蓄電
裝置之應用。其結果可提供一種便宜並且具有穩定且優異的電特性(高放電容量與重複耐久性)之蓄電裝置100。
Based on this finding, when forming the structure of the present invention, iron or copper (or iron alloy, copper alloy) is first used, and copper, iron, etc. required for the oxidation-reduction reaction are also left in the electrode, so that it can be repeated. Oxidation-reduction reaction (charge-discharge reaction), thus achieving the effect of copper, iron, etc. on the storage of electricity
Application of the device. As a result, it is possible to provide an
(實施例) (Example)
接著藉由實施例及比較例來詳細說明本發明之效果。惟本發明並不限定於此等實施例。 Next, the effects of the present invention will be described in detail with examples and comparative examples. However, the present invention is not limited to these embodiments.
〈〈〈實施例及比較例〉〉〉 〈〈〈Examples and Comparative Examples〉〉〉
所有的電極係將平面尺寸成形為1cm×2cm，並將1cm×1cm浸漬在電解液而使用。所使用之電極的材質如下列所示。 All the electrodes are formed into a plane size of 1cm×2cm and used by immersing 1cm×1cm in the electrolyte. The materials of the electrodes used are as follows.
〈〈不鏽鋼纖維片〉〉 〈〈Stainless Steel Fiber Sheet〉〉
實施例1至4及比較例1係使用經抄製及燒結之不鏽鋼纖維片作為多孔質導電體。 Examples 1 to 4 and Comparative Example 1 used paper-made and sintered stainless steel fiber sheets as porous electrical conductors.
此不鏽鋼纖維片係纖維直徑：8μm、厚度：100μm、單位面積重量：300g/m2、佔積率：33%。單位面積重量為金屬纖維片之每1平方公尺之纖維片的重量。佔積率為金屬纖維片之每單位體積之所佔的金屬纖維的比率，數值愈少，表示金屬纖維片中的空隙愈多。 This stainless steel fiber sheet has fiber diameter: 8 μm, thickness: 100 μm, unit area weight: 300 g/m 2 , and occupation rate: 33%. The weight per unit area is the weight of the fiber sheet per square meter of the metal fiber sheet. The occupation area is the ratio of the metal fiber per unit volume of the metal fiber sheet. The smaller the value, the more voids in the metal fiber sheet.
〈〈銅纖維片〉〉 〈〈Copper Fiber Sheet〉〉
實施例5至9及比較例2、3係使用經抄製及燒結之銅纖維片作為多孔質導電體。此銅纖維片係使用：纖維直徑：18.5μm、厚度：100μm、單位面積重量：300g/m2、佔積率：33%者。 Examples 5 to 9 and Comparative Examples 2 and 3 used paper-made and sintered copper fiber sheets as porous conductors. This copper fiber sheet uses: fiber diameter: 18.5μm, thickness: 100μm, unit area weight: 300g/m 2 , occupying area: 33%.
〈〈具有銅系的導電性奈米結構之多孔質導電體〉〉 〈〈Porous conductor with copper-based conductive nanostructure〉〉
根據下列步驟來製造具有銅系的導電性奈米結構之多孔質導電體。 According to the following steps, a porous conductor with a copper-based conductive nanostructure is manufactured.
〈導電性奈米結構製作用電解液的調製〉 <Preparation of Electrolyte for Fabrication of Conductive Nanostructures>
(硫酸四氨銅(II)電解液) (Tetraammonium copper(II) sulfate electrolyte)
將硫酸四氨銅(II)(Aldrich公司製、純度98%)0.31g與作為輔助電解質的硫酸鋰(和光純藥公司製、純度99.0%)0.64g溶解於蒸餾水40.2mL。將NH3水(關東化學公司製、氨含量29%水溶液)9.8mL添加於此溶液，並藉由磁攪拌機攪拌30分鐘，而形成硫酸四氨銅(II)的濃度為25mM之導電性奈米結構製作用電解液。 0.31 g of copper tetraammine sulfate (manufactured by Aldrich, 98% purity) and 0.64 g of lithium sulfate (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.0%) as an auxiliary electrolyte were dissolved in 40.2 mL of distilled water. 9.8 mL of NH 3 water (manufactured by Kanto Chemical Company, 29% ammonia content aqueous solution) was added to this solution and stirred with a magnetic stirrer for 30 minutes to form a conductive nanometer with a concentration of 25 mM copper tetraammonium sulfate (II) Electrolyte for structural production.
〈具有導電性奈米結構之多孔質導電體的製造裝置〉 <Manufacturing device for porous conductor with conductive nano structure>
使用圖2的三電極法來製作具有導電性奈米結構之評估試樣。電源係使用恆電位器(北斗電工公司製、型號HAB-151)，且如圖2所示般連接3極式單元。將前述所調製之電解液注入於電解單元的主室。此外，並製作出從前述所調製之電解液中僅排除硫酸四氨銅(II)之電解液，並將此注入於副室。 The three-electrode method shown in Figure 2 was used to prepare an evaluation sample with a conductive nanostructure. The power supply uses a potentiostat (manufactured by Beidou Electric Co., Ltd., model HAB-151), and is connected to a 3-pole unit as shown in Figure 2. The electrolytic solution prepared above is injected into the main chamber of the electrolysis cell. In addition, an electrolyte solution in which only copper tetraammonium sulfate (II) sulfate is excluded from the electrolyte solution prepared above is produced, and this is injected into the sub-chamber.
然後於恆電位器之工作電極的端子使用經抄製及燒結之銅纖維片基材作為多孔質基材，並將鉑板連接於對向電極端子，以及將飽和甘汞電極(TOA Eleectrics公司製、型號HC-205C、以下略稱為SCE)連接於參考電極的端子。 Then use the copper fiber sheet substrate made and sintered as the porous substrate for the terminal of the working electrode of the potentiostat, connect the platinum plate to the opposite electrode terminal, and connect the saturated calomel electrode (manufactured by TOA Eleectrics, Model HC-205C (hereinafter abbreviated as SCE) is connected to the terminal of the reference electrode.
〈具有導電性奈米結構之多孔質導電體的製造〉 <Manufacturing of Porous Conductor with Conductive Nanostructure>
將-1.45V的電位施加於工作電極並通電3.0C/cm2的電量。於實施主室中，此時硫酸四氨銅(II)進行二電子還原而使銅析出。同時由於氨發揮作為型態控制劑的作為，所以銅並非以單純的膜型態，而是以樹枝結晶(Dendrite)狀、纖維狀、棒狀、針狀等之各種形狀的奈米線而析出。電解結 束後，從電解液中取出形成有銅奈米線之基材，並藉由蒸餾水重複洗淨而得到實施例10的電極。 A potential of -1.45V was applied to the working electrode and a power of 3.0C/cm 2 was energized. In the main chamber of the implementation, at this time, copper tetraammonium sulfate (II) undergoes two-electron reduction to precipitate copper. At the same time, because ammonia acts as a morphology control agent, copper is not precipitated as a simple film, but as nanowires of various shapes such as dendrites, fibers, rods, and needles. . After the electrolysis, the substrate on which the copper nanowire was formed was taken out from the electrolyte and washed repeatedly with distilled water to obtain the electrode of Example 10.
〈〈具有鈷系的導電性奈米結構之多孔質導電體〉〉 〈〈Porous conductor with cobalt-based conductive nanostructure〉〉
根據下列步驟來製造具有鈷系的導電性奈米結構之多孔質導電體。 According to the following steps, a porous conductor with a cobalt-based conductive nanostructure is produced.
〈導電性奈米結構製作用電解液的調製〉 <Preparation of Electrolyte for Fabrication of Conductive Nanostructures>
(氯化六氨鈷(III)電解液) (Cobalt(III) Hexammonia Chloride Electrolyte)
將氯化六氨鈷(III)(Aldrich公司製、純度99%以上)0.508g與作為輔助電解質的硫酸鋰(和光純藥公司製、純度99.0%)1.28g溶解於蒸餾水100mL，藉由磁攪拌機攪拌30分鐘，而形成六氨鈷濃度為19mM之電解液(硫酸鋰的濃度為0.1M)。 Dissolve 0.508 g of cobalt(III) chloride (manufactured by Aldrich, purity 99% or more) and 1.28 g of lithium sulfate (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.0%) as an auxiliary electrolyte in 100 mL of distilled water and use a magnetic stirrer Stir for 30 minutes to form an electrolyte with a concentration of hexahydrocobalt of 19mM (the concentration of lithium sulfate is 0.1M).
(具有導電性奈米結構之多孔質導電體的製造裝置) (Manufacturing device for porous conductor with conductive nano structure)
使用圖2的三電極法來製作具有導電性奈米結構之評估試樣。電源係使用恆電位器(北斗電工公司製、型號HAB-151)，且如圖2所示般連接3極式單元。將前述所調製之電解液注入於電解單元的主室。將溶解有0.1M的硫酸鋰之電解質水溶液注入於副室。此外，於副室中浸漬參考電極。主室與副室係藉由鹽橋而電生連接。 The three-electrode method shown in Figure 2 was used to prepare an evaluation sample with a conductive nanostructure. The power supply uses a potentiostat (manufactured by Beidou Electric Co., Ltd., model HAB-151), and is connected to a 3-pole unit as shown in Figure 2. The electrolytic solution prepared above is injected into the main chamber of the electrolysis cell. An electrolyte aqueous solution in which 0.1M lithium sulfate is dissolved is injected into the sub-chamber. In addition, the reference electrode is immersed in the auxiliary chamber. The main room and the auxiliary room are electrically connected by a salt bridge.
然後將經抄製及燒結之銅纖維片基材作為多孔質基材而連接於恆電位器之工作電極的端子，將鉑板連接於對向電極端子，以及將飽和甘汞電極(SCE)連接於參考電極的端子。 Then the copper fiber sheet substrate that has been copied and sintered is used as a porous substrate and connected to the terminal of the working electrode of the potentiostat, the platinum plate is connected to the counter electrode terminal, and the saturated calomel electrode (SCE) is connected to The terminal of the reference electrode.
〈具有導電性奈米結構之多孔質導電體的製造〉 <Manufacturing of Porous Conductor with Conductive Nanostructure>
將-1.07V的電位施加於工作電極並通電3.0C/cm2的電量。此時六氨鈷(III)離子進行三電子還原而使鈷析出。同時由於氨發揮作為型態控制劑 的作為，所以鈷並非以單純的膜型態，而是以枝狀結晶狀、纖維狀、棒狀、針狀等之各種形狀的奈米線而析出。電解結束後，從電解液中取出形成有鈷奈米線之基材，並藉由蒸餾水重複洗淨而得到實施例11至12的電容器電極。 A potential of -1.07V was applied to the working electrode and a power of 3.0C/cm 2 was energized. At this time, the cobalt(III) hexaamine ion undergoes three-electron reduction to precipitate cobalt. At the same time, because ammonia acts as a form control agent, cobalt is not precipitated in a simple film form, but in dendritic crystals, fibers, rods, needles, and other shapes of nanowires. After the electrolysis, the base material on which the cobalt nanowire was formed was taken out from the electrolyte and washed repeatedly with distilled water to obtain the capacitor electrodes of Examples 11 to 12.
〈〈〈評估試驗〉〉〉 〈〈〈Evaluation Test〉〉〉
根據下列步驟來實施包含上述多孔質導電體之蓄電裝置的評估試驗。 The evaluation test of an electrical storage device including the above-mentioned porous conductor was carried out according to the following procedure.
〈〈充放電耐性評估試驗〉〉 〈〈Charge and discharge resistance evaluation test〉〉
使用圖3所示之裝置來進行充放電耐性評估試驗。電源係使用充放電單元(北斗電工公司製、型號HJ1010mSM8A)，將實施例1至10及比較例1至3的電極連接於工作電極，將鉑板連接於對向電極端子，以及將SCE連接於參考電極的端子。此外，電流密度於實施例1至4、11及比較例1中設為3mA/cm2，於實施例5至10、12及比較例2、3中設為10mA/cm2來進行測定。結果如表1所示。外輪廓容器係使用聚苯乙烯製，密閉狀態是在以矽栓來蓋住外輪廓容器之狀態下進行充放電試驗，開放狀態是在未使用矽栓之狀態進行充放電試驗。電解液係採用如表所示之電解液。 The device shown in Figure 3 was used to conduct a charge-discharge resistance evaluation test. The power supply system uses a charging and discharging unit (manufactured by Beidou Electric Co., model HJ1010mSM8A). The electrodes of Examples 1 to 10 and Comparative Examples 1 to 3 are connected to the working electrode, the platinum plate is connected to the counter electrode terminal, and the SCE is connected to The terminal of the reference electrode. In addition, the current density was set to 3 mA/cm 2 in Examples 1 to 4, 11 and Comparative Example 1, and 10 mA/cm 2 in Examples 5 to 10, 12 and Comparative Examples 2 and 3 to be measured. The results are shown in Table 1. The outer contour container is made of polystyrene. The closed state is the charging and discharging test with the outer contour container covered with a silicon plug, and the open state is the charging and discharging test without the silicon plug. The electrolyte is as shown in the table.
〈電容的大小〉 <The size of the capacitor>
電容的大小係從充放電的第1次至第100次為止之各充放電曲線中算出，並將至第100次為止前所得到之最大容量設為容量的大小。 The size of the capacitor is calculated from each charge and discharge curve from the first charge and discharge to the 100th charge and discharge, and the maximum capacity obtained up to the 100th charge is used as the size of the capacity.
〈電容的變化〉 <Change in capacitance>
電容的變化係從充放電的第1次至第100次為止前所得到之最大容量中，以至第1000次為止之電容的變化來進行測定。 The change in capacitance was measured from the maximum capacitance obtained before the first charge and discharge to the 100th time, and the change in capacitance up to the 1000th time.
以充放電1000次後的電容低於充放電100次為止前所得到之最大容量的80%之情形為「×」，以80%以上之情形為「○」。 The case where the capacitance after 1,000 times of charging and discharging is less than 80% of the maximum capacity obtained before 100 times of charging and discharging is "×", and the case of more than 80% is "○".
[表1]
[表2]
在此係準備使用1cm×1cm的銅板作為工作電極者，來作為其外的比較例(比較例4)。電解液為0.1mol/L的KOH水溶液。進行與上述相同的充放電試驗，可得知電容為0.039mAh。 Here, a 1cm×1cm copper plate is prepared as a working electrode as a comparative example (Comparative Example 4). The electrolyte is a 0.1 mol/L KOH aqueous solution. Performing the same charge and discharge test as above, it can be seen that the capacitance is 0.039 mAh.
考量到電極的表背兩面，上述比較例4中之每單位實效表面積的電容係將上述電容除以2cm2而成為0.02mAh/cm2。另一方面，由於從單位面積重量所算出之實效表面積為7.59cm2，所以實施例7中之每單位實效表面積的電容係將電容1.9mAh除以此實效表面積而成為0.25mAh/cm2。 Taking into consideration the front and rear surfaces of an electrode table, the comparative example 4 per unit of effective surface area of the capacitance of the capacitor divided by the Department of 2cm 2 becomes 0.02mAh / cm 2. On the other hand, since the effective surface area calculated from the unit area weight is 7.59 cm 2 , the capacitance per unit effective surface area in Example 7 is 0.25 mAh/cm 2 by dividing the capacitance of 1.9 mAh by this effective surface area.
如此，於本發明之構成中使用金屬纖維片作為電極之情形下，與使用金屬板作為電極之情形(比較例4)相比，可確認到考量到實效面積在內之每單位面積的電容極高。 In this way, when the metal fiber sheet is used as the electrode in the structure of the present invention, compared with the case where the metal plate is used as the electrode (Comparative Example 4), it can be confirmed that the capacitance per unit area including the effective area is considered. high.
100:三電極裝置(蓄電裝置) 100: Three-electrode device (electric storage device)
110:外輪廓體 110: Outer contour
120:電極對 120: Electrode pair
121:第1電極 121: first electrode
122:第2電極 122: second electrode
130:電解液 130: Electrolyte
140:端子 140: Terminal
150:分隔片 150: Separator
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