200837200 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態儲存技 術。另就發明所屬之製程技術觀點，亦與儲氫合金之冶煉技術 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 規模使用石化能源下所產生之S〇2、c〇、NOx等有害人體與環产 物質，與排放大量二氧化礙造成之溫室效應，引^全球^氣^ 變遷等-㈣問題下’世界各國莫不致力於新能源科技之開 f。其中之氫能，因其啦品只有水沒有二氧狀，完全 ¥又不會造成溫室效應’已被國際能源總署規劃為未來主^ 一。但在實際應用上’因為氫氣之分子量太小，以至於儲 存體，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0 又 直到1980年代以後，可將氫以固態方式 ^後，終於解決氫的儲存密度與安全性上 ^之储風合金’無論是過渡金屬系AB2儲氫合金 壯 it施儲重量密度仍嫌太低，不到ί 4量 =，因此面谷赠氣合金之研發乃 其中之鎂系儲氫合金，由於具有儲㈡古、展之赵勢。 低廉之優點，因此被視為相#有發原料成本 因活性大，表面易形成阻礙f曰力，虱合金，但純鎂 於合金表面擴散速率，導致化層而影響氫原子 吸放氫溫編，目此力差， 針對純鎂吸放氯動力學^tf差貫的用門If t合 果，相之_叫犯====;; 5 200837200 最快、吸放氫性質最佳之儲氫合金。 但由於鎂（649°C)與鎳（1455°C)兩種金屬的熔點差異报大，易 造成熔解不均勻，導致儲氫合金成分不均勻之問題，且鎂的蒸 氣壓很高，易於熔融過程產生揮發，使初始配比成分產生嚴^ 偏差，造成過多的共晶結構與不會吸氫之々相MgNh生成。為 解決上述熔煉過程中成分產生嚴重偏差問題，新一代之真空& 應爐雖然裝設有線上檢測功能，然而對於Mg—Ni儲氫ϋ二 言，卻因相圖上之天然特性，使得Mg—Ni熔融液，即彳 精密之線上檢測功能，將成分準確控制在鎂與鎳原子比為2 ·200837200 IX. INSTRUCTIONS: [Technical field to which the invention belongs] The technical field to which this case belongs is mainly the hydrogen energy solid state storage technology of new energy technology. In addition, the viewpoint of the process technology to which the invention belongs is also related to the smelting technology of 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 produced by large-scale use of petrochemical energy, such as S〇2, c〇, NOx, etc. The greenhouse effect caused by oxidation is caused by the global ^ gas ^ change, etc. - (4) Under the question, 'the countries of the world are not committed to the opening of new energy technologies. Among them, the hydrogen energy, because its products are only water, there is no dioxin, and the full ¥ will not cause the greenhouse effect. ‘It has been planned by the International Energy Agency as the future master. But in practical applications, 'because the molecular weight of hydrogen is too small, so that the storage body is too large, although it can be stored in an ultra-high pressure mode, it raises doubts about safety. 0 Until the 1980s, hydrogen can be solid-state. ^ After finally, the storage density and safety of hydrogen are finally solved. Whether it is the transition metal system AB2 hydrogen storage alloy, the weight density of the storage is still too low, less than ί 4 =, so the face of the gift The development of gas alloys is one of the magnesium hydrogen storage alloys, which has the potential to store (2) ancient and exhibition. The advantage of low cost is therefore regarded as the phase of the raw material cost due to the high activity, the surface is easy to form a hindrance to the f曰 force, the bismuth alloy, but the diffusion rate of pure magnesium on the surface of the alloy, leading to the formation of the hydrogen atom , the purpose of this force difference, for the pure magnesium absorption and chlorine kinetics ^tf difference between the use of the door If t and fruit, the phase _ called criminal ====;; 5 200837200 the fastest, the best hydrogen absorption and release properties Hydrogen alloy. However, due to the large difference in melting point between magnesium (649 ° C) and nickel (1455 ° C), it is easy to cause uneven melting, resulting in uneven hydrogen storage alloy composition, and the vapor pressure of magnesium is very high and easy to melt. The process produces volatilization, which causes the initial proportioning component to produce a sharp deviation, resulting in excessive eutectic structure and MgNh formation in the 々 phase which does not absorb hydrogen. In order to solve the problem of serious deviation of the components in the above smelting process, the new generation vacuum & furnace has an on-line detection function, but for the Mg-Ni hydrogen storage ϋ, the natural characteristics of the phase diagram make Mg —Ni melt, which is the on-line detection function of 彳, accurately controls the composition of the atomic ratio of magnesium to nickel to 2 ·
1之情況下，凝固後仍然無法得到100%純的7相Mg2Ni。w · 因為根據鎂與鎳之二元平衡相圖，在此一成份下，早在古於 761°c r相MgWi之熔點溫度以上，熔點114rt不會吸氡:j 相MgNh已先行凝固析出。又因為石相之％^2其組成^比 相之MgWi含有較高之Νι，因此造成其餘尚未凝固之啦―則产 液偏，原本鎂與鎳原子比為2 : 1之7相MgWi組成，成為 畐鎂狀悲。此一富鎂狀態Mg-Ni溶融液，在降溫至低於mi 後，根據鎂與鎳之二元平衡相圖，在此一成份下，不僅會生 r相之MgWi ’在507 C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^相之比 下，其微觀之組織結構卻是在r相之处撕中摻雜有冷相之 與純鎂固溶相。所以傳統熔煉法無法製備活化反應 快、吸放氫性質佳之高純度啦撕儲氫合金。 “ 【發明内容】 有鑑^上述問題，本案發明人特別利用物理冶金之偏析原理， 在二〒廣之成份範圍中’且在低溫低於純鎳之熔點）下， 以間早的裝置來連續製造高純度_i儲氫合金。其具 為先將純鎂金屬塊原料置入一個熔點超過鎂熔點之金屬坩 内，然後在惰性氣氛保護下，利用電阻爐之加熱器將純鎂原料 6 200837200 完全?^接下來再將純錄粉徐徐加入盛有熔融鎂液體 上升至以機械力授拌與加熱升溫，使炼融液體溫度 人成灼勺之罝以使錄粉全部充分炼解’並與溶融鎂液體混 tut她於f知技賴精鮮確地控制溶融 ίϊί ϊί ^ ’本之裝£與綠卻無鮮設精密之線上檢 紐液之紐，只要所添加之鎳，其添加量 ί巧量百分比介於23.5至5°·2就能保證得 组成為Mg-54. 6 wt% Ni(也就是鎮與鎳原子比為2 ^純的T相Μ祕儲氫合金，而無摻雜有任何其他雜相。 是進行降溫’當符合上述寬廣成份範圍之炫融 ^鎳液體 >皿度降至相圖中所對應之液相線溫度以下後，只須約 ，控制加熱器功率’使鎂舰體溫度維持在_線溫度⑽ snt上^夜相線溫度（視實際之組成而定，其範圍在761與 之間）以下之寬廣溫度區間。而高純度之㈠目％2Ni儲 ，'盘依照Mg-Ni相圖物理冶金之偏析原理，自動開始生成析 ，亚且在此溫度範m其純度與析出溫度完全無關。因此 本發明所採狀設備亦無須錢精確昂貴之溫控純。至於In the case of 1, it is still impossible to obtain 100% pure 7-phase Mg2Ni after solidification. w · Because according to the binary equilibrium phase diagram of magnesium and nickel, under this component, as early as the melting point temperature of the 761 °c r phase MgWi, the melting point 114rt does not suck: j phase MgNh has been coagulated and precipitated first. And because of the composition of the stone phase%^2, the MgWi of the phase has a higher Νι, so the rest has not yet solidified, and the production liquid is biased. The original magnesium to nickel atomic ratio is 2:1 and 7 phase MgWi. Become a sorrowful magnesium. According to the binary equilibrium phase diagram of magnesium and nickel, the Mg-Ni molten solution in the magnesium-rich state is cooled by the binary equilibrium diagram of magnesium and nickel. Under this composition, not only the Mg-phase Mn of the Mg-phase 507 C is generated. The temperature also gives a eutectic structure including the pure magnesium phase. That is to say, even in the case where the composition of the macroscopic composition is completely in accordance with the phase ratio, the microscopic structure is that the r phase is doped with a cold phase and a pure magnesium solid solution phase. Therefore, the conventional smelting method cannot prepare a high-purity tear-trap hydrogen storage alloy with fast activation reaction and good hydrogen absorption and desorption properties. [Summary of the Invention] In view of the above problems, the inventors of the present invention particularly utilized the principle of segregation of physical metallurgy, in the range of the composition of Erqiguang, and at a low temperature lower than the melting point of pure nickel, with continuous devices. Manufacture of high-purity _i hydrogen storage alloy. The raw material of the pure magnesium metal block is first placed in a metal crucible having a melting point exceeding the melting point of magnesium, and then the pure magnesium raw material is used in the heater of the electric resistance furnace under the protection of an inert atmosphere 6 200837200 Completely? ^ Next, the purely recorded powder is slowly added to the molten magnesium liquid to rise to mechanical heating and heating, so that the temperature of the smelting liquid becomes a scoop to make the recording powder fully refining' and Molten magnesium liquid mixed tut her in the f-technical control of the freshly controlled melting ίϊί ϊί ^ 'The original and the green but no fresh precision on the line of New Zealand, as long as the added nickel, its added amount ί The percentage of the amount of 23.5 to 5 ° · 2 can be guaranteed to be Mg-54. 6 wt% Ni (that is, the town-to-nickel atomic ratio is 2 ^ pure T-phase hydrogen storage alloy, without doping There are any other miscellaneous phases. Is it to cool down' when the above width is met The composition of the range of melting ^ nickel liquid> After the dish temperature drops below the liquidus temperature corresponding to the phase diagram, only need to control the heater power 'to maintain the magnesium hull temperature at _ line temperature (10) snt ^ The temperature of the night phase line (depending on the actual composition, the range is between 761 and Between) and the wide temperature range below. The high purity (1) mesh %2Ni storage, 'disc according to the principle of segregation of physical metallurgy of Mg-Ni phase diagram, The formation of the precipitation is automatically started, and the purity of the temperature is completely independent of the precipitation temperature. Therefore, the equipment of the invention does not need to be precise and expensive to control the temperature.
MgW儲氫合金之析出數（重）量則視鎂鎳液體組成以及析出溫 ^而定…般而言在符合本發明所述寬廣之成份與溫度條件範 ，内:當鎳的成份愈高與析出溫度愈低則高純度0啦撕的 ί出f ί愈多’詳細之析出數(重〉量可依物理冶金之相圖槓桿 疋理计鼻付知。 由於;k本發明所析出之尚純度r才目Μ满其錄的成份⑸6 wt%)高於原本鎂鎳液體成份（i e.鎳的重量百分比介於23 5 至5 0. 2)’因此隨著析$反應的顿崎，根據質量不滅定律， 殘留之液體會越來越偏向富鎮組成。而鎳的密度（8 9 g/cm3)又遠大於鎂的密度（丨.74 g/cm3)，因此在固相τ _%2Μ 之組成密度A大於液相組成比重之情況下，所析出之高純度^ 相MgAi均沉在坩鍋底部。本發明則利用一種可以傾倒式之坩 200837200 鍋基座設計，將上半部富鎂組成之鎂鎳液體排除，而 在坩鍋底部之固相即為高純度單一 r相之％2則儲 召 本發明另-重大技術上突破則是將原本排除之廢液，^二 ^機構與裝置可以重新回收再，並進而開發出 製造高純度鎂鎳儲氫合金之方法與裝置。盆星體7j運、、只 針對廢液重新回收部分，除了前述之一套可'完全=ατ·: 搶，以及在該溶解臉内之一組授拌機構、一貫穿氣二二二二解 =粉末加料管與至少一組可控制溫度之加熱器以:二;： 熱器内之義外，尚包括絲該加熱器内之掛鋼傾力口 二空職’、以及-組可將此兩_位置互調之吊掛方2 鎂組成之鎮鎳廢液被傾倒在另一空掛銷中後 = :先將，留有高純度r相固體_儲氫 該加熱器内，打開氣密閉之炫解艙並立刻加入鎮 二=二;目使錄粉全部充分轉’並絲融鎮液體混 為方便吊掛作業，本發明所用之掛 掛機構尚可設計具備有傾倒功能且體、I ς b外，該吊 的情況下，使條絞繩，而單獨提升其中一條 =液體之物m， 錄的含㈣财第-叙议5至5r2 8 200837200 的r相為2:1的組成），而仍然能獲得完全純 因i =且無推雜有任何其他之雜相。這是 精密準確地;成為良好的成份調整劑，使得在無須 :在錄含使顯錄液之成份保 氣密閉之溶解艙門進行加料或者是將 業日才目r _儲氯合金之原掛銷取出之作 之二-欠純煉技藝人士所熟知之具有二次加料室 本。4力此之真空職爐來解決，惟此做法會增加設備成 二=氣密，中分隔出 氣氛下解齡可健在真技惰性保護 鎂爐2職;加的純 之正下方)並承接鎂鎳廢液於其中。 另—賴吊人該加熱器内加熱至^1 ί ^c,xl ? 均句之單一液相。美液體混合成 率’使_液體溫度維持在固相線溫度皿⑽。熱= 9 200837200 線溫度（視實際之組成而定，其範圍在761與5〇7^之間）以 間。而高純度之❻_儲氫合金依照％-Ni相 圖t理/口孟之偏析原理，自動開始生成析出。 f置在-旁，底部殘留有高純度r相固體Mg2Ni儲見合 ^有·_可在冷卻後，同樣透過職進出之交換室 ΐίΐ搶之真空或惰性保護氣氛下，輕易取出。將底部殘留之 ^i相固體fg2Nl儲氣合金敲除收集後，原掛鋼則可加人 由於Μ、ΐ並？前述方式送人_艙，不斷地依次循環利用。 !儲虱合金活性非常高，在高溫下㈣中 於燃燒，劣化其性能並產生危險，因此必須要t 二Αΐ由真空或惰性保護氣氛下之溶解艙内取出。考慮到 里生產時，例如數百公斤或倾以上 ^ ίΞϊί ’或許冷卻速率有所不足，因而限制生產 明人亦針對此點在溶解搶内待冷區内特別設計一 水之水冷銅座，利關之良好散熱特性使内部盛有 、〒體，純度r相_i儲氫合金之掛鋼能快速冷卻。綜上 Ϊ用在絲的溫度與化學組祕件下，目此也無須 叩禮$之設備絲完全不㈣，且連續 有 ίr ^ %2ni ° 功效，並^項技術者將可暸解本發明之特點及The amount of precipitation (heavy) of the MgW hydrogen storage alloy depends on the magnesium nickel liquid composition and the precipitation temperature. Generally speaking, in accordance with the broad composition and temperature conditions of the present invention, the higher the composition of nickel is The lower the precipitation temperature, the higher the purity, the higher the purity, the more the f ί, the more the detailed number of precipitation (heavy) can be based on the physical metallurgy phase diagram, the lever calculus is known. Because; k is the purity of the invention r only to see the recorded ingredients (5) 6 wt%) higher than the original magnesium nickel liquid composition (i e. nickel weight percentage between 23 5 to 5 0. 2) 'So with the analysis of the $ reaction of the Nazaki, according to The law of mass immortality, the residual liquid will be more and more biased towards the rich town. The density of nickel (8 9 g/cm3) is much larger than the density of magnesium (丨.74 g/cm3). Therefore, when the composition density A of the solid phase τ _% 2 大于 is larger than the specific gravity of the liquid phase, the precipitate is precipitated. The high purity ^ phase MgAi is deposited at the bottom of the crucible. The invention utilizes a tiltable 坩200837200 pot base design to exclude the magnesium-nickel liquid in the upper part of the magnesium-rich composition, and the solid phase at the bottom of the crucible is the high-purity single-phase phase. Another major technical breakthrough of the present invention is that the waste liquid which was originally excluded, the mechanism and the device can be recycled, and a method and a device for manufacturing a high-purity magnesium-nickel hydrogen storage alloy are further developed. The basin star body 7j is transported, and only the waste liquid is recovered. In addition to the aforementioned one set, it can be 'completely=ατ·: grab, and one group of mixing mechanism in the dissolved face, one through the gas two two two two solution= The powder feeding tube and at least one set of temperature-controllable heaters are: 2;: outside the heat exchanger, the wire is also included in the heater, and the group can be used for both _ Position intermodulation hanging side 2 Magnesium composition of the town nickel waste liquid is dumped in another empty pin = = first, leaving high purity r phase solid _ hydrogen storage inside the heater, open the airtight Decommissioning and immediately join the town two = two; the purpose is to fully record the recording powder and the silk mixing liquid is mixed for convenient hanging operation, the hanging mechanism used in the invention can be designed to have a dumping function and body, I ς b In addition, in the case of the hoist, the strips are twisted, and one of them is separately lifted = the liquid of the liquid m, and the recorded r (phase 4) of the 5th to 5r2 8 200837200 is composed of 2:1, and It is still possible to obtain the pure factor i = and there is no other miscellaneous phase. This is precisely and accurately; it becomes a good ingredient adjuster, so that it is not necessary to: feed the dissolved compartment door that contains the components of the recording liquid, or it will be the original of the industry. The second step of the pin-out process is known to those skilled in the art of smelting. 4 force this vacuum furnace to solve, but this practice will increase the equipment into two = airtight, separated in the atmosphere under the atmosphere can be in the real-life inertia protection magnesium furnace 2; plus pure under the) and undertake magnesium Nickel waste liquid is contained therein. In addition, Lai Hanger heats the heater to a single liquid phase of ^1 ί ^c, xl ? The US liquid mixing rate is such that the _ liquid temperature is maintained at the solidus temperature vessel (10). Heat = 9 200837200 Line temperature (depending on the actual composition, the range is between 761 and 5〇7^). The high-purity ❻ _ hydrogen storage alloy automatically begins to form and precipitate according to the segregation principle of the %-Ni phase diagram. f is placed at the side, and there is a high-purity r-phase solid at the bottom. The Mg2Ni is found in the mixture. After cooling, it can be easily taken out through the vacuum chamber or inert protective atmosphere of the exchange chamber. After knocking out the remaining ^i phase solid fg2Nl gas storage alloy at the bottom, the original hanging steel can be added because of Μ, ΐ and? The above method is sent to the cabin, and is continuously recycled. The storage alloy is very active and burns at high temperatures (4), degrading its performance and posing a hazard. Therefore, it must be removed from the dissolution chamber under vacuum or an inert protective atmosphere. Considering the production, for example, hundreds of kilograms or more ^ ίΞϊί ' Perhaps the cooling rate is insufficient, so the production limit is also targeted at this point in the dissolution of the cold zone to design a water-cooled copper seat, Li Guan The good heat dissipation characteristics enable the interior to contain and the body, and the purity of the r phase _i hydrogen storage alloy can be quickly cooled. In summary, it is used in the temperature of the wire and the secrets of the chemical group. Therefore, it is not necessary to use the device wire at all (4), and there is continuous ίr ^ %2ni ° effect, and the technician will understand the present invention. Features and