1341,869 九'發明說明： 【發明所屬之技術領域】 本案所屬之技術領域主要為新能源科技之氫能固库儲存 術。另就發日麟屬之製程技術觀點，亦與儲氫合金之;;煉技術 有關。 【先前技術】 隨著全球石化能源使用量大幅成長，並將逐漸枯竭，以及在大 規模使用石化π源下所產生之S〇2、C0、N〇x等有害人體與環境 物質，與排放大里二氧化碳造成之溫室效應，引發全球性氣候 • 變遷等一系列問題下，世界各國莫不致力於新能源科技之開 發。其中之氫能，因其副產品只有水沒有二氧化碳，完全無污 染又不會造成溫室效應，已被國際能源總署規劃為未來主要能 源之-。但在實際應用上，因為氫氣之分子量太小，以至於儲 存體積太過龐大，雖然可採用超高壓方式儲存，卻又引發安全 上之疑慮。 "" 直到1980年代以後，可將氫以固態方式儲氫之儲氫合金產品 問世後，終於解決氫的儲存密度與安全性上之問題。惟現行商 業上之儲氫合金，無論是過渡金屬系AB2儲氫合金、或是稀土 金屬系儲氫合金其儲氫重量密度仍嫌太低，不到2. 〇重量 百分比’因此=容量儲氫合金之研發乃目前國際發展之趨勢。 其中之鎂线氫合金’由於具有儲氫量高、質餘、原料成本 低廉之優點’因此被視為才目當有發展潛力之儲氫合金，但純鎖 因活性大，表面易形成阻礙氫分子吸附之氧化層而影響氫原子 於合金表面減速率’導賴鎂不|被活化、吸放氫動力差， 吸放氫溫度過高，因此無法成為實用之儲氫合金。 針對純鎂吸放氫動力學性質較差的問題，經過許多學者之研 - 九’發現藉由具有催化效果之鎳的添加，可改善Mg-Ni儲氫合 金中的吸放氫反應速率’同時對初始活化性能亦有催化之效 果。而7相之MgzNi則為Mg-Ni儲氫合金系統中活化反應速率 5 '9V- 最快、吸放氫性質最佳之儲氫合金。 ^於鎂_。〇與錄（1455。〇兩種金屬的賴差異很大，易 炼，不均勻致儲氫合金成分不均勻之問題’且鎮的蒸 乳壓很高’ |r於賴過程產生揮發，使初舰比成分產生嚴g ，差’造成過多的共晶結構與不會吸氫之《相_h生成。為 解決上述_過程巾成分產生嚴重偏差問題，新—代之真空 ，爐雖絲設树上檢測魏，細對於Mg_Ni儲氫合金而 言丄卻因相圖上之天然特性，使得Mg-Ni熔融液，即使透過最 精岔之線上檢測功能，將成分準確控制在鎂與鎳原子比為2 : 1之情況下，凝固後仍然無法得到100%純的7相Mg2Ni。 因為根據鎂與叙二元平衡相圖，在此—成份下，早在高於 761 c r相Mg2Ni之熔點溫度以上’熔點1147°c不會吸氫之 相MgNh已先行凝固析出。又因—相之MgNh其組成遠比γ 相之MpNi含有較高之Ni，因此造成其餘尚未凝固之Mg_Ni熔 ，液偏，原本鎂與鎳原子比為2 :丨之7相Mg2Ni組成，成為 虽鎂狀態。此一富鎂狀態Mg-Ni炫融液，在降溫至低於mi。匚 後，根據鎂與鎳之二元平衡相圖，在此一成份下，不僅會生成 T相之MgWi，在507C之共晶溫度還會得到包括純鎂相在内 之共晶組織。也就是說，即使在巨觀組成完全符合τ相之比例 下，其微觀之組織結構卻是在7相之啦撕中摻雜有冷相之 MgNh與純鎂固溶相。所以傳統熔煉法無法製備活化反應速率 快、吸放氫性質佳之高純度Mg2Ni儲氫合金。 ^ 【發明内容】 有鑑於上述問題，本案發明人特別利用物理冶金之偏析原理， 在一寬廣之成份範圍中，且在低溫（遠低於純鎳之炫點） 以簡單的裝置來連續製造高純度MpNi儲氫合金。其具體内容 為先將純鎂金屬塊原料置入一個熔點超過鎂熔點今屬 内，然後捕性氣驗訂，_電_之加熱㈣賴原^ 之^鋼接1來再將_粉徐徐加入盛有炼融顯體 上升至械力獅與加熱升溫，舰融液體溫度 液^ 習知技術須精密準確地控制炫融 财料無縣設餘之線上檢 佔全======，1341, 869 IX 'Invention Description: 【Technical Fields Where the Invention Included】 The technical field to which this case belongs is mainly the hydrogen energy solid storage of new energy technology. In addition, the viewpoint of the process technology of the Japanese genus is also related to the hydrogen storage alloy; [Prior Art] With the growth of global petrochemical energy use, it will gradually deplete, and the harmful human and environmental substances such as S〇2, C0, N〇x generated under the large-scale use of petrochemical π source, and emissions Under the series of problems caused by the greenhouse effect caused by carbon dioxide and global climate change, the countries of the world are not committed to the development of new energy technologies. Among them, hydrogen energy, because its by-products only have no carbon dioxide, no pollution, and no greenhouse effect, has been planned by the International Energy Agency as the main energy source in the future. However, in practical applications, because the molecular weight of hydrogen is too small, the storage volume is too large, and although it can be stored in an ultra-high pressure mode, it raises safety concerns. "" Until the 1980s, hydrogen storage alloy products that can store hydrogen in a solid state have finally solved the problem of hydrogen storage density and safety. However, the current commercial hydrogen storage alloy, whether it is a transition metal type AB2 hydrogen storage alloy, or a rare earth metal hydrogen storage alloy, its hydrogen storage weight density is still too low, less than 2. 〇 weight percentage 'hence = capacity hydrogen storage The development of alloys is currently the trend of international development. Among them, the magnesium-line hydrogen alloy has the advantages of high hydrogen storage capacity, low quality and low cost of raw materials. Therefore, it is regarded as a hydrogen storage alloy with potential for development, but the pure lock activity is large, and the surface is easy to form hydrogen barrier. The molecular adsorption of the oxide layer affects the deceleration rate of hydrogen atoms on the surface of the alloy. It is activated, the hydrogen absorption and desorption is poor, and the hydrogen absorption and desorption temperature is too high, so it cannot be a practical hydrogen storage alloy. Aiming at the problem of poor kinetics of hydrogen absorption and desorption of pure magnesium, after many scholars have studied - Nine's found that the addition of nickel with catalytic effect can improve the rate of hydrogen absorption and desorption in Mg-Ni hydrogen storage alloys. The initial activation properties also have a catalytic effect. The 7-phase MgzNi is the hydrogen storage alloy with the best activation rate of 5 '9V- in the Mg-Ni hydrogen storage alloy system. ^于镁_. 〇与录(1455. The difference between the two metals is very large, easy to refine, the problem of uneven distribution of hydrogen storage alloys is uneven and the steam pressure of the town is very high. Ships produce strict g than the composition, and the difference 'causes too much eutectic structure and does not absorb hydrogen. The phase _h is generated. In order to solve the above problem, the process of the process towel is seriously deviated, and the new one is replaced by a vacuum. On the detection of Wei, fine for Mg_Ni hydrogen storage alloy, but due to the natural characteristics of the phase diagram, so that the Mg-Ni melt, even through the most sophisticated on-line detection function, accurately control the composition of the atomic ratio of magnesium to nickel In the case of 2:1, 100% pure 7-phase Mg2Ni is still not obtained after solidification. Because according to the equilibrium diagram of magnesium and Syrian binary, under this composition, it is earlier than the melting point temperature of Mg2Ni above 761 cr phase. MgNh, which has a melting point of 1147 °c, has been coagulated and precipitated. The composition of MgNh is much higher than that of MpNi of γ phase, which causes the remaining unsolidified Mg_Ni to melt, liquid deviation, and original magnesium. The ratio of nickel to nickel is 2: 77 phase Mg2Ni composition, State: This magnesium-rich Mg-Ni smelting melt, after cooling to below mi. 匚, according to the binary equilibrium phase diagram of magnesium and nickel, under this component, not only will generate T-phase MgWi, The eutectic temperature of 507C also gives the eutectic structure including the pure magnesium phase. That is to say, even in the case where the composition of the giant is completely in accordance with the ratio of the τ phase, the microscopic structure is in the 7-phase tear. The MgNh is doped with the cold phase and the pure magnesium solid solution phase. Therefore, the conventional smelting method cannot prepare a high-purity Mg2Ni hydrogen storage alloy with fast activation reaction rate and good hydrogen absorption and desorption properties. ^ [Summary of the Invention] In view of the above problems, the inventor of the present invention In particular, the principle of physical metallurgy segregation is used to continuously manufacture high-purity MpNi hydrogen storage alloys in a wide range of components and at low temperatures (far below the pure nickel) with a simple device. The magnesium metal block material is placed in a genus with a melting point exceeding the melting point of magnesium, and then the gas is checked, _ electric _ heating (four) Lai Yuan ^ ^ steel connected 1 and then _ powder slowly added to the smelt To the mechanical force lion and heating up, the ship melts liquid temperature The degree of liquid ^ conventional technology must be precisely and accurately controlled to control the accumulation of materials without the county's online inspection accounted for all ======,
Mg-516 wt% Nl (Mg-516 wt% Nl (
MgzNi儲氫合金，而無摻雜有任何其他雜相。 鎂：就是進行降溫，當符合上述寬廣成份範圍之熔融 Ϊϊί體1降至相圖中所對應之液相線溫度以下後，只須約 二、|加熱H功率，使鎂舰體溫度維持在難線溫度⑽ Μ7。，上日7夜相線溫度（視實際之組成而定，其範圍在761盘 H之間）以下之寬廣溫度區間。而高純度之^相_儲 ^金依照Mg-Ni相ϋ物理冶金之偏析原理，自動開始生成析 ，並且在此溫度範圍内’其純度與析出溫度完全無關。因此 本發明所採用之設備亦無須使用精確昂貴之溫控系統。至於 feN 1儲氫合金讀錄⑷量職_紐組成以及析出溫 度而定。，一般而言在符合本發明所述寬廣之成份與溫度條件範 圍内二當鎳的成份愈高與析出溫度愈低則高純度7相Mg2Ni的 析出i就愈多，詳細之析出數（重）量可依物理冶金之相圖 定理計算得知。 由於，本發明所析出之高純度7相Mg2Ni其鎳的成份（54 6 wt/〇尚於原本鎂鎳液體成份（i,e·鎳的重量百分比介於23 5 至50. 2)’因此隨著析出反應的不斷進行，根據質量不滅定律， 殘留之鎂鎳液體會越來越偏向富鎂組成。而鎳的密度（8,9 g/cm3)又遠大於鎂的密度（1,74g/cm3)，因此在固相 之組成密度遠大於液相組成比重之情況下，所析出之高純度丫 相MgzNi均沉在坩鍋底部。本發明則利用一種可以傾倒式之坤 1341869 之機構與裝置可以c二1=並本= 驗’以及在該轉驗内之一組授掉套之炫解 至少一組可控制溫度之加熱MgzNi hydrogen storage alloy without any other heterogeneous phases. Magnesium: It is to cool down. When the melting Ϊϊ body 1 that meets the above broad composition range falls below the liquidus temperature corresponding to the phase diagram, it only needs to heat the H power to maintain the magnesium hull temperature. Line temperature (10) Μ 7. The temperature range of the 7-night phase line of the previous day (depending on the actual composition, the range is between 761 and H). The high-purity phase-storage gold automatically starts to form and precipitate according to the segregation principle of Mg-Ni phase physics and metallurgy, and its purity is completely independent of the precipitation temperature in this temperature range. Therefore, the apparatus used in the present invention does not require the use of a precise and expensive temperature control system. As for the feN 1 hydrogen storage alloy read (4) depending on the composition of the job and the temperature of precipitation. Generally speaking, in the range of the broad composition and temperature conditions according to the present invention, the higher the composition of nickel and the lower the precipitation temperature, the more precipitation of high-purity 7-phase Mg2Ni, and the detailed precipitation (weight). The amount can be calculated according to the phase diagram theorem of physical metallurgy. Because of the high purity 7 phase Mg2Ni precipitated in the present invention, the composition of nickel (54 6 wt / 〇 is still in the original magnesium nickel liquid component (i, e · nickel weight percentage between 23 5 to 50.2) The precipitation reaction continues, and according to the law of mass incompetence, the residual magnesium-nickel liquid will become more and more biased towards magnesium-rich composition, while the density of nickel (8,9 g/cm3) is much larger than the density of magnesium (1,74 g/cm3). Therefore, in the case where the composition density of the solid phase is much larger than the specific gravity of the liquid phase composition, the precipitated high-purity 丫 phase MgzNi is deposited at the bottom of the crucible. The present invention utilizes a mechanism and device capable of dumping the Kun 1341869. c 2 1 = 并 = = test 'and in one of the tests, the set of hands-off sets of the set of at least one set of controllable temperature heating
二空r，以及-組可將此兩_位置方:: f.，·且成之_廢液被傾倒在另—空賴t後，立刻啟動吊= ，’先將底部殘留有高純度r相固體啦^鈀 :離=座上之加熱器，再將盛有鎂鎳廢心= 该加熱㈣，打開氣密閉之熔解搶並立刻加人鎂原料加 ΐΞΓ ίίΐ先前方式再將純鎳粉徐徐加人盛有炫融鎂液ί 以機械力授掉與加熱升溫，使炼融液體溫度 合成均勾之單2相使錄粉全部充分轉，並與炫融鎮液體混 為方便吊掛作#，本發明姻之賴均财掛耳。Two empty r, and - group can be the two _ position side:: f., and into the _ waste liquid is dumped in another - empty t t, immediately start hang =, 'first leave the bottom of high purity r Phase solids ^ Palladium: from the heater on the seat, will be filled with magnesium nickel waste = the heating (four), open the gas-tight melting and grab and immediately add magnesium raw materials to add ΐΞΓ ίίΐ the previous way and then pure nickel powder slowly Adding people to have a bright molten magnesium liquid ί by mechanical force to give up and heating up, so that the temperature of the smelting liquid is synthesized into a single phase of 2, so that the recording powder is fully transferred, and mixed with the liquid of the smelting town for convenient hanging. The invention is based on the marriage of the marriage.
掛機構尚可設計具備有侧魏。其具體做法如下，例如ϊ採 =少三_三似上掛耳之賴’錢每各掛耳對應有獨立 之峨’就能在固定其巾兩條_，而單敬升其中-條 的情況下’使购產生傾斜。因此觸解出加熱器後，可在 ，解艙的任何適合的位置，運用吊掛機構之傾倒功^使盛有熔 =鎂液體之坩鍋傾斜，並將坩鍋内液體傾倒在另一獨立坩鍋 =續製造上與第-爐不_是，在第二爐以及之後的炫 、中]為了提咼高純度7相MgzNi儲氫合金之產量，所添加之 鎳的含量可從原本第一爐之23. 5至5〇· 2 wt%增加至54. 6 w伐 8 1341869 為二 持在錄含量為23. 5至5(J成份保 ，ϋ f ί f熔煉中打開氣密閉之熔解艙門進行加料或者是將 ===== 5可Z采:熔煉技藝人士所熟知之具以::室 加枓功mm猶縣驗，惟麟法會增加設備成 則是在氣ί，解射分隔出 -. " 、父換至，其中之氣密閉炫解艘與讨叙 *山^人讀室之間設置有—隔賴，使得進行新舊^鋼^ 交^作業時’氣密_:解搶仍可保持在真空或惰性保護 赋下。至於加制題，制樣可顧該賴進出之交換室 =。與先前所述方式唯—所不_是：在將原本加熱器 前’先在大氣中將下—爐次所欲添加的純 進行惰性_保護後，打開隔_並將此移；位 熱器内_傾倒口之正下方）並承接_廢液於=(加 ί了ίϊ動吊掛機構，紐底部殘留有高純度7_體Mg2Ni t合金之原有_吊離_基座上之加熱器，再將盛有純鎂 ，料與鎮鎮廢液之另一掛鋼吊入該加熱器内加熱至完全炫 =後循先前方式再將純鎳粉徐徐加人盛有關鎂液體之掛 ΐ =不斷施以機械力授拌與加熱升溫，使炫融液體溫度上= 社，錄粉全部充分溶解’並與溶融鎖液體混合成 ί句液再依相同步驟進行降溫，約略控制加熱器= 率，使鎮錄液體溫度維持在固相線溫度（5〇7它）以上，夜相 9 1341869 =際之組成而定，其範圍在761與5〇7ΐ之間)以 =則:在===== 純鎮原料，並赠狀枝讀赌，稍 ，於Mg—儲虱合金活性非常高，在高溫下空氣中非常斑 氧反應甚至於燃燒，劣化其性能並產生危險，因此必須乂 冷=後才能由真空或惰性保護氣氛下之祕搶内取出岸二 大量生產時’例如數百公斤或倾以上之炫煉，單靠靜置g 餘内待冷，或許冷卻速率有所不足，_關生產效(速）率。 本案發明人亦針對此點在熔解艙内待冷區内特別設計一具備 有冷=循環水之水冷魅，湘銅之良好散熱特性使内部盛有 固體向純度7相MgAi儲氫合金之坩鍋能快速冷卻。綜上所 述，本發明可以在寬廣的溫度與化學組成條件下，因此也無須 使用昂貴精密之設備就能完全不浪費，且連續不斷地產出具有 良好吸放氫動力學特性之高純度^•相Mg2Ni儲氫合金。而根據 發明說明書之記載，熟習本項技術者將可瞭解本發明之特點及 功效，並可據以實施。The hanging mechanism can still be designed to have a side Wei. The specific practices are as follows, for example, ϊ = = = 三 三 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The next 'make a purchase tilt. Therefore, after the heater is decoupled, the tilting function of the hanging mechanism can be used at any suitable position of the unloading mechanism to tilt the crucible containing the molten metal solution, and the liquid in the crucible is dumped in another independent manner. Shabu-shabu = continued manufacturing and the first furnace not _ Yes, in the second furnace and after the Hyun, Zhong] In order to improve the production of high-purity 7-phase MgzNi hydrogen storage alloy, the added nickel content can be from the original The furnace is 23. 5 to 5 〇 · 2 wt% increased to 54. 6 w fell 8 1341869 for the second holding in the content of 23. 5 to 5 (J composition, ϋ f ί f smelting open airtight melting chamber The door is filled or it will be ===== 5 can be taken: the smelting artisan is familiar with:: room plus gonggong mm juxian county inspection, but the lining method will increase the equipment into the gas, resolving Separate out -. ", the father changed to, which is the airtight closed and the boat and the discussion of the * mountain ^ people reading room between the set - estrangement, so that the new and old ^ steel ^ when the work ^ airtight _ : The robbing can still be maintained under the vacuum or inert protection. As for the addition of the title, the sample preparation can take care of the exchange room that is in and out of the room =. The method described above is only _ is: in the original Before the device, 'first in the atmosphere, the next to the furnace, the pure inertity _ protection, open the partition _ and move this; the heater inside the _ dumping mouth directly below) and take _ waste liquid = ( Plus ϊ ϊ 吊 吊 , , , 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽A hanging steel is hoisted into the heater to heat up to full brightness = after the previous method, the pure nickel powder is slowly added to the hanging of the magnesium liquid. The mechanical force is continuously applied to the mixing and heating to increase the temperature of the molten liquid. Above = society, the recording powder is fully dissolved 'and mixed with the molten lock liquid into ί sentence liquid and then cooled according to the same steps, roughly control the heater = rate, so that the town recording liquid temperature is maintained at the solidus line temperature (5 〇 7 it Above, the night phase 9 1341869 = the composition of the interval, the range is between 761 and 5〇7ΐ) = = then: in the ===== pure town raw materials, and gifted to read the bet, slightly, in Mg - The storage alloy has a very high activity. At high temperatures, the air is very plaque-oxygen or even burns, deteriorating its performance and posing a hazard. After simmering = after the vacuum or inert protection atmosphere, the second batch of production can be taken out. For example, hundreds of kilograms or more of the sleek, only by standing still, waiting for the cold, perhaps the cooling rate is insufficient. , _ off production efficiency (speed) rate. The inventor of this case also specially designed a water-cooling charm with cold=circulating water in the cooling zone in the melting chamber. The good heat dissipation characteristics of Xiangtong copper make the inside contain the solid to the purity of the 7-phase MgAi hydrogen storage alloy. Can cool quickly. In summary, the present invention can be used under a wide range of temperature and chemical composition conditions, so that it can be completely wasted without using expensive and sophisticated equipment, and continuously produces high purity with good hydrogen absorption and desorption kinetics. Phase Mg2Ni hydrogen storage alloy. Those skilled in the art will be able to understand the features and functions of the present invention in light of the teachings herein.