200841508 九、發明說明： 【發明所屬之技術領域】 本發明係有關於一種鋅空氣電池之陽極材料表面 改貝製造方法’尤指一種只需少量三硼酸鋰（Lithium bcm>n Qxide’ LB0、Li2〇3_B2〇3)塗佈於陽極材料之辞 粉顆粒表面，即可抑制氫氣產生進而降低鋅陽極自放 電與提升放電性能之效果。200841508 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to a method for manufacturing a surface modification of an anode material of a zinc-air battery, in particular, a small amount of lithium triborate (Lithium bcm>n Qxide' LB0, Li2 〇3_B2〇3) Coating on the surface of the powder material of the anode material can suppress the generation of hydrogen gas and thereby reduce the effect of self-discharge and lift discharge performance of the zinc anode.
【先前技術J 近年來因石油漲價而引發全球各地對下一 源危機」何時來g#夕1 + I慮，咢找備用能源已成為人類 =之二:任:必::於能源產業之電池相關製造方 @％ _ 字垃顯者提升。目前電池、半導 體及顯不器二J音後〇，|t 丁守 之雪世紀最重要之目標產業，而盆中 之電池此源技術亦為該 、甲 方」，因為掌据了处Λ国無晌如何不外流之「獨家秘 勢。 了 _之市場就_有了料世界之優 仆 現代生活中，可攜式個人電子执備、私叔兑 化’可想而知，在這個潮 子-備漸漸、‘及 之電池，佔有舉足拳:’扮演能源供應者角色 及重量不可過大係必備條件立同：：可攜：設備體積 體積和重量-樣將被嚴格地要求。逼理’：池本身之 較鎳錦電池高之體積容量定^而鋅空氣電池具有 辞空氣電池所造成 二及重量容量密度’而且 ^ 3比含有鎘之鎳鎘電池小 5 200841508 很多。因此，目前錄錦電池已逐漸被其它二次電 取代。 、電池種類繁多，重要之二次電池包含有链離子電 池、錄辞電池、絲空翁# 锌工孔电池、鉛酸電池、鎳鎘電池及 鎳氫化物電池等。其中，以鋅空氣電池係現今所有以 ::質液為基礎之電池系統中比能量最高者，並具有 回質量功率和大雷流放带—# 产 包文兒之優勢。這種優勢使得鋅空 =池能夠Μ電動車輛在—次充電行程、爬坡和加 栖亘:^對月匕里之需求。由此可知，鋅空氣電池係一 肌甲力之電池’其質量能與鎳氫電池相當，體積 月匕夏已超過鎳鎘電池。 、 ^氣電池之發展雖已有8Q年歷史，但 =待解決，例如辞金屬為-高活性之物質 -亥鋅金屬在驗性電解質液中 、 解質液反廡，、生e 具合易和電 =^成自龍氧化成鋅離子，並同時產生 2每成自放電（Se丨fdischarge)效應、充 二後電極形變及不可逆鈍化層 向析屮抖技& α Ώ , 儿兄电呀會在反 出树枝狀！口日日物，以致造 而縮柄帝从 且纷 < 現象，進 法突破Μ ° ^述這些種種原因，使得益 皮目則电動機車電池高成本之困境。 …、 又近年來，許多所發表之鋅空 重在電池結構之組裝$計 ^也專利大多著 電極與電解質⑥φ Y〜加有機與無機物質於 解^中，以提高電池之放電功率與減少自 200841508[Prior Art J In recent years, due to the price increase of oil, it has triggered a crisis in the next source around the world." When to come to g# 夕1 + I, looking for alternative energy has become human = two: Ren: Must:: Battery in the energy industry Related Manufacturers @% _ Words are highlighted. At present, the battery, semiconductor and display device are the second most important target industries, and the source technology of the battery in the basin is also the party, "because it is in the country."晌How to not flow out of the "exclusive secret. The market is _ _ have the world's best servant in modern life, portable personal electronic support, private uncle's can be imagined, in this tide - Gradually, 'and the battery, possessing a full-fledged fist: 'playing the role and weight of the energy supplier can not be too big to meet the necessary conditions:: portable: equipment volume and weight - the sample will be strictly required. The pool itself has a higher volumetric capacity than the nickel-nickel battery, while the zinc-air battery has the second and the weight capacity density caused by the air battery, and ^3 is much smaller than the nickel-cadmium battery containing cadmium, 200841508. Therefore, the current recording battery It has been gradually replaced by other secondary batteries. There are many kinds of batteries, and the important secondary batteries include chain ion batteries, recording batteries, silk emptyings, zinc working holes, lead acid batteries, nickel cadmium batteries and nickel hydride batteries. Etc. The zinc-air battery system is now the most energy-efficient in the battery system based on the :: liquefaction-based battery system, and has the advantage of returning mass power and large mine-flowing belt-# production package Wener. This advantage makes zinc air = The pool can smash the electric vehicle in the - charging journey, climbing and adding sputum: ^ the demand for the moon sill. It can be seen that the zinc air battery is a muscle-powered battery whose quality can be comparable to that of a nickel-hydrogen battery. The volume of the moon has exceeded the nickel-cadmium battery. The development of the gas battery has been 8Q years old, but it is still to be solved. For example, the metal is a high-activity substance-hai zinc metal in the electrolyte solution, the solution Liquid 庑,, raw e with yiyi and electricity = ^ into the self-dragon oxidized into zinc ions, and simultaneously produced 2 per self-discharge (Se丨fdischarge) effect, after the second electrode deformation and irreversible passivation layer & α Ώ , Brothers and elders will be in the opposite of the dendrites! The mouth and the sun, so that the creation and shrinking of the Emperor from the "and the phenomenon", the breakthrough of the law ^ ° These reasons, so that Yipi The high cost of electric motor vehicle batteries. ..., and in recent years, Xu Many published zinc voids are assembled in the battery structure. Most of the patents are also used in the electrode and electrolyte 6φ Y~ plus organic and inorganic substances to improve the discharge power of the battery and reduce it from 200841508.
放電效應。以早期铉办_ + L 卞功鋅工虱電池為得到較好之 例，其係在鋅電極方面 > 肊為 改善至最低： ' 使用下列方法將鋅腐餘速率 金； (A)添加含汞、鎘、錫 鋁 、鎘及鉛之金屬合 (B)將乳化鋅浸透在電解質液中 電解質液之添加物。 卫便用$極或 八士述方法雖然在抑制鋅之氫氣釋放 之金屬，但限於環境污染考 ’、啟有效 ^ 里卜現已被迫放棄不用。 電产：=二鋅空氣電池雖然具有高質量功率和大 有早期.提出以汞作為添加物以抑制辞之=即 而基於環境為前提下，仍無法為產業適用然 一般習用者係無法符合使用者於實際使用時故’ 【發明内容】 厅而。 本發明之主要目的係 提升放電功率。的係在於，降低鋅陽極自放電與 極材：：λ上之目的’本發明係-種鋅空氣電池之陽 =枓表面改質製造方法’係將 r之鋅粉顆粒’置入-利用溶液法合成之= 液中均勻混合’以進行表面塗佈與：質:待 4後再控㈣燒之溫度及時間，以獲得經表面塗= 200841508 改質過之鋅陽極材料。藉此 佈於鋅粉顆粒表面， 里之二媢酸鋰塗 觸，進而大幅降低鋅陽朽ί 與電解質液之接 ΐ瓜鮮&極產生自全雷 产 其抑制效率約為78%。 士 ”風軋之機會， 此提升放電功率與深 里外，更 率，不僅具有梦迭方、;：以有效地增進鋅陽極使用 ^ 有 方法間車及環境汙染少，f日跖+ L -廉故本發明辞空氣電池β# 科係比以傳統改質方也之以極材 中。 去更為適合應用於鋅空氣電池 【實施方式】 請參閱『第1圖』所示，係本發 意圖。如圖所示：本發明係一種辞^氣電不 料表面改質製造方法，其至少包括下列步驟：5材 (A )形成一三硼酸鋰（Lith LB〇、Li2〇3.B⑹先 二讀， 量將顯（η卿）料合/h化學計 組A — r 礼化鋰（Li〇H.H2〇)溶 …热水乙醇或其他有機溶劑中，混合攪拌 色渾濁三硼酸鋰先驅物溶液； y 性物2進行表面塗佈12:將—鋅空氣電池陽極活 粉顆粒加入該三卿先驅物溶液中，由一 σ曰波辰盪器震盪混合以進行表面塗佈； 使 (c )進行改質1 3 :加熱授拌以進行改質 200841508 溶劑揮發而形成一灰色乾燥固體；以及 ⑼煆燒獲得-表面塗佈改f過之鋅陽極㈣ 1 4 .將该乾煉固體置入—高溫爐内煆燒，經由控制 煆燒反應溫度及假燒反應時間，以獲得經三删酸鐘表 面塗佈改質過之鋅陽極材料。 乂 當本發㈣運料H制溶液法將—定 2量之餐與水合氫氧驗溶解在—無水乙醇或以 有機溶劑中，於混合攪拌3〇分鐘後，形成一白色渾蜀Discharge effect. In the early days, the _ + L 卞 锌 锌 锌 为 为 为 , , , , , , _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Mercury, cadmium, tin aluminum, cadmium and lead metal (B) impregnate emulsified zinc in the electrolyte solution in the electrolyte solution. Although Wei Wei used the method of $ pole or eight scholars to suppress the release of hydrogen from zinc, it was limited to environmental pollution test and was effective. Electricity production: = two zinc air battery, although it has high quality power and large early stage. It is proposed that the use of mercury as an additive to suppress the resignation = that is, based on the environment, it is still not applicable to the industry. When the actual use, [the content of the invention]. The main object of the present invention is to increase the discharge power. The system is to reduce the zinc anode self-discharge and the pole material:: λ on the purpose of the present invention - the zinc-air battery of the anode = 枓 surface modification manufacturing method ' is to put the zinc powder particles of r' into the utilization solution Method of synthesis = uniform mixing in the liquid for surface coating and: quality: after 4 and then control (four) burning temperature and time to obtain surface modified = 200841508 modified zinc anode material. Thereby, it is coated on the surface of the zinc powder particles, and the lithium disilicate is coated, thereby greatly reducing the connection between the zinc and the electrolyte solution. The melon fresh & extremely self-produced has a suppression efficiency of about 78%. "Winners" opportunity, this increase in discharge power and deep inside and outside, more rate, not only has a dream of Fang,;: to effectively promote the use of zinc anode ^ There are ways to car and environmental pollution, f 跖 + L - The invention is based on the fact that the air battery β# is more suitable for the zinc air battery than the conventional one. [Embodiment] Please refer to the figure shown in Figure 1. Intention: As shown in the figure: The present invention is a method for manufacturing a surface modification which includes at least the following steps: 5 (A) forms a lithium triborate (Lith LB〇, Li2〇3.B(6) first two Read, the quantity will be displayed (η qing) feed / h chemist group A — r Lithium (Li〇H.H2〇) dissolved... hot water ethanol or other organic solvent, mixing and stirring turbid lithium borohydride precursor Solution; y substance 2 for surface coating 12: adding zinc-air battery anode powder particles to the Sanqing precursor solution, and oscillating and mixing by a σ-wave-waver to perform surface coating; Reforming 1 3 : Heating and mixing to reform 200841508 Solvent volatilization to form a gray dry solid And (9) simmering obtained - surface coating modified zinc anode (four) 1 4 . The dry solid is placed in a high temperature furnace simmering, by controlling the simmering reaction temperature and the smoldering reaction time to obtain The surface of the three acid-cut clocks is coated with the modified zinc anode material. 乂When the hair of the present invention (4), the solution of the H solution is prepared by dissolving the amount of the meal with the hydrated hydrogen and oxygen in the anhydrous ethanol or in an organic solvent. After mixing for 3 minutes, a white crucible is formed.
Ll 〇3也〇3先驅物溶液。將鋅空氣電池陽極活性物之 :粉顆粒加入該三硼酸鋰先驅物溶液中，以 ;器震4混合溶液約15分鐘至丨小時，以進行 其中，该二硼酸鋰先驅物溶液之 锌 粉顆粒之0.〇5〜2.〇%重量百分比之間。」布而佔鋅 再於_下加熱攪拌以進行改f，使該 ::成-灰色乾燥固體。並將該乾燥固體置軍’： :=trHr通反應溫度及煅燒 酸鍾表面塗佈：質:之 1鋅至：小時後，即可獲得經三， 种又貝過之辞陽極材料。 明之：粒^ #2圖及第3圖』所示，係分別為本笋 ;:鋅％極自放電產生氫氣比較示意圖及本發明‘ 電池性能測續+立因 ^ %之 〇.5伏特⑺了 ώ圖所示：於放電戴止電壓為 ^ ^^ ^ r,T^°'64 ^A} ^ "，J ^^ /液法5成之三硼酸鋰（LB0)分別以〇 m 9 200841508Ll 〇3 also 〇3 precursor solution. The zinc-air battery anode active material: the powder particles are added to the lithium triborate precursor solution, and the mixture solution is shaken for about 15 minutes to 丨 hours to carry out the zinc powder particles of the lithium diborate precursor solution. 0. 〇 5~2. 〇% by weight between. The cloth is zinc and then heated and stirred under _ to change f to make the ::-grey dry solid. And the dry solids are placed in the '::=trHr reaction temperature and calcined acid clock surface coating: quality: 1 zinc to: after hours, the three kinds of anode materials can be obtained. Mingzhi: grain ^ #2 diagram and diagram 3, respectively, is the bamboo shoots;: Zinc% extreme self-discharge hydrogen generation comparison diagram and the present invention 'Battery performance test + Dependency ^% of the 〇. 5 volts (7) The diagram shows: the discharge voltage is ^ ^^ ^ r, T ^ ° '64 ^ A} ^ ", J ^ ^ / liquid method 50% lithium triborate (LB0) respectively 〇 m 9 200841508
Wt.%、0.1 wt·%、〗·〇 wt.%& 2 0糾％塗佈於鋅粉顆粒 表面上以進行表面改質，並以—未塗佈之鋅陽極作為 對照組。藉由各別之未改質鋅陽極曲線2工 LBO表面處理鋅陽極曲線2 2、〇.丨糾.％ lb〇表面處 理鋅陽極曲線2 3、KOwWLBO表面處理辞陽極曲 線24及2.〇 Wt.% LB〇表面處理鋅陽極曲線25可 知，當塗佈（M wt.%三硼酸鐘進行表面改質時， 鋅粉顆粒表面形成—層厚度約為25q奈米（_)之= :b層’而該鈍化層可減少鋅陽極與電解質液接觸之機 抑制效率約可達78 %，進而可抑制氣氣 以提高電池安全之可靠性。 產生 之敦冤电合里為L57安時（Α 而經過o.l wt.%三爾 ，度為8】％， 詈描弁兔〗7Π ^ 士 貝辞^極後’其放電電容 里k升為1.7G约，放電深度也相 足顯示經由三硼酸鋰表面改質過德夕力3為彳，足 僅可增加放電電容量，亦择、 、辛陽極材料，不 且所需之原料成本亦為低廉==極之使用率’並 少，由此可知，本發明係比 用於鋅空氣電池中。 、去更為適合 綜上所述，本發明係—種辞十 表面改質製造方法’可有效改善;^以之陽極材 用材料表面塗佈法，以減少白之種種缺點， %極與電解質液之 200841508 生自放電輿氧氣之機會， 、有政地増進鋅陽極使用 ，果也相當顯著，不僅所 裒兄之/于染也較少，進而 更實用、更符合使用者之 請之要件，爰依法提出專 觸二達到大幅降低鋅陽極產 亚能增加放電功率與深度， 率，·其製造方法簡單，改質 需原料成本低廉，同時對於 使本發明之產生能更進步、 所須，確已符合發明專利申 利申請。 a惟以上所述者，僅為本發明之較佳實施例而已， 备不能以此限定本發明實施之範圍；&，凡依本發明 申凊專利織及發明說明書内容所作之簡單的等效變 化與修飾，皆應仍屬本發明專利涵蓋之範圍内。文 200841508 【圖式簡單說明】Wt.%, 0.1 wt.%, 〖·〇 wt.%& 2 0%% was applied to the surface of the zinc powder particles for surface modification, and an uncoated zinc anode was used as a control group. By the respective unmodified zinc anode curve 2 LBO surface treatment zinc anode curve 2 2, 〇. 丨 ..% lb 〇 surface treatment zinc anode curve 2 3, KOwWLBO surface treatment anodic curve 24 and 2. 〇 Wt .% LB〇 surface treatment zinc anode curve 25 shows that when coated (M wt.% triborate clock for surface modification, the surface of zinc powder particles is formed - layer thickness is about 25q nanometer (_) = : b layer 'The passivation layer can reduce the inhibition efficiency of the zinc anode to the electrolyte solution by about 78%, thereby suppressing the gas to improve the safety of the battery. The resulting electricity is L57 ampere. After ol wt.% Saner, the degree is 8]%, 詈 弁 〗 〗 7 Π ^ 士 辞 ^ 极 极 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其After upgrading the Dexia 3, it can only increase the discharge capacity, and also choose the anodic anode material. The required raw material cost is also low == the usage rate is low, so it is known that The invention is more suitable for use in a zinc-air battery, and is more suitable for the above, the invention is a series of ten The surface modification manufacturing method can be effectively improved; the surface coating method for the anode material is used to reduce the various shortcomings of the white, and the electrolyte of the electrolyte and the liquid is 200841508. The use of the anode is also quite remarkable. It is not only the one that is used by the brothers, but also more practical and more in line with the requirements of the user. With the depth, rate, and its manufacturing method is simple, the quality of the raw materials required for upgrading is low, and at the same time, for the purpose of making the invention more advanced, it is necessary to meet the application for the invention patent application. The preferred embodiments of the present invention are not intended to limit the scope of the present invention; & the simple equivalent changes and modifications made in accordance with the present invention and the contents of the invention are still Within the scope of the invention patent. Wen 200841508 [Simple description of the diagram]
Ά 1 I® 5 4^1 DOΆ 1 I® 5 4^1 DO
意圖。 作流程示意圖。 時陽極自放電產生氫氣比較示 池性能測試示意圖。 第3圖，係本發明之電 【主要元件符號說明】 步驟1 1、1 2、i 3、i 4 未改質鋅陽極曲線2 1 0.05wt·% LB0表面處理鋅陽極曲線2 2 0.1 wt.°/〇 LBO表面處理鋅陽極曲線2 3 1.0 wt·% LBO表面處理鋅陽極曲線2 4 2.0 wt·% LB0表面處理鋅陽極曲線2 5intention. A schematic diagram of the process. At the time of anode self-discharge, a schematic diagram of the performance comparison test of hydrogen is performed. Fig. 3 is a diagram of the main components of the invention. Step 1 1 , 1 2, i 3, i 4 Unmodified zinc anode curve 2 1 0.05wt·% LB0 surface treatment zinc anode curve 2 2 0.1 wt. °/〇LBO surface treatment zinc anode curve 2 3 1.0 wt·% LBO surface treatment zinc anode curve 2 4 2.0 wt·% LB0 surface treatment zinc anode curve 2 5