201012941 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，亦與儲氫合金之熔煉、機 械合成與活化前處理技術有關。 【先前技術】201012941 IX. Description of the invention: [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 the new energy technology. In addition, the viewpoint of the process technology to which the invention belongs is also related to the smelting, mechanical synthesis and pre-activation treatment techniques of hydrogen storage alloys. [Prior Art]
氫是一種最乾淨的能源能’因其副產品只有水。但在實際應用 上，因為氳氣之分子量太小，以至於儲存體積太過龐大，雖然 可採用超尚壓方式儲存，卻又引發安全上之疑慮。自從1969 年，由荷蘭Philips公司開發出AB5型LaNis儲氫合金以來， 由於此合金儲氳反應速度快、氫含量高、遲滯效應和反應熱效 應士丄平台壓力低而平直、活化容易，可以實現迅速安全的'儲 存氫氣’並經過一些，包括··以稀土混合金屬（鼬、齓）、取 代價格昂貴的純金屬La ’以及以Al、Co、Mn、Cu等元素部分 取代Ni，使得合金壽命延長、抗毒性與抗電解液腐蝕性增加 等改良後，很快商業化應用於Ni-MH電池。於此同時為了增加 電谷量與改善合金的儲氫性能’由美國〇v〇nic公司開發之八私 型儲氫合金也幾乎與ΑΒ5型儲氫合金同時問市，主要作為MH/Ni 電池之負極材料使用侧前大量應用在市鎳氫== AB2,氫合金，與義電池概，具有容量大、安全無毒和使 =哥命長等優點’然而作為運輸動力之雜·汽車用之儲氫 =嫌=量約^收一般商業儲氨合金，其儲存重量 另-方面’主要赠為轉電池賊 與^，雜具有材料價格優勢，但其 2到Gwt% ’並且很容易因氫氣不純 在，Γ比上具有更高容量的儲氫合金ί 1 V Cr為主的Bcc儲氫合金被美國專利第 201012941 6258184 號與第 6616891 號，以及在 Journal of Alloys andHydrogen is one of the cleanest energy sources' because its by-products only have water. However, in practical applications, because the molecular weight of helium is too small, the storage volume is too large, although it can be stored in excess pressure, but it raises safety concerns. Since the development of the AB5 LaNis hydrogen storage alloy by Philips in the Netherlands in 1969, the alloy has a high reaction rate, high hydrogen content, hysteresis effect and reaction heat effect. The pressure of the gentry platform is low and straight, and the activation is easy. Quick and safe 'storage of hydrogen' and some of it, including · replacing the expensive pure metal La ' with rare earth mixed metals (鼬, 齓), and partially replacing Ni with elements such as Al, Co, Mn, Cu, etc. After the improvement of elongation, anti-toxicity and anti-electrolyte corrosion, it was quickly applied to Ni-MH batteries. At the same time, in order to increase the amount of electricity and improve the hydrogen storage performance of the alloy, the eight private hydrogen storage alloy developed by the US 〇v〇nic company is also almost in contact with the ΑΒ5 type hydrogen storage alloy, mainly as a MH/Ni battery. The anode material is widely used in the city before the use of nickel-hydrogen == AB2, hydrogen alloy, and the battery, has the advantages of large capacity, safe and non-toxic, and makes the life of the brothers. However, as a transportation power, the hydrogen storage for automobiles = suspicion = quantity about ^ general commercial ammonia storage alloy, its storage weight another - aspect 'mainly for the battery thief and ^, miscellaneous has material price advantage, but its 2 to Gwt% ' and it is easy because hydrogen is not pure, The hydrogen storage alloy with a higher capacity than the upper one is a Bcc hydrogen storage alloy based on US Patent Nos. 201012941 6258184 and 6615891, and in the Journal of Alloys and
Compounds等期刊相關文獻陸續發表以來，由於其儲氫量相較 於習知之AB5或AB2具有跳躍式的進步（幾乎是兩倍以上），立 刻引起儲氫合金材料研究者與相關產業之注意。 但隨即在這些研究中，也很快發現這種以鈦叙鉻為主要元素之 BCC儲氫合金若與習知之AB5或AB2相比，其活化速度普遍很慢 也很困難。對於習知之ABs或AB2儲氫合金相當有用之傳統活 化處理方法’包括··以氫氟酸、硝酸或兩者之混合物進行所謂 化學法之酸洗製程（濕法），其主要目的是以腐蝕方式去除储 〇 氫合金表面容易形成氧化層；或是另一種在高溫、高壓之氫氣 氛下之進行之物理活化製程（乾法），也就是使儲氫合金因吸 氫體積膨脹’造成合金氫脆劈裂而產生新鮮的無氧化層表（界） 面’使其易於吸氫並增加吸氫速率。但這些對傳統儲氫合金相 當有效的處理方法，當各別甚至於兩者一起應用在BCC儲氫合 金時，經實際的測試卻發現，依舊難以使其順利活化並吸氫。 有時，甚至於在合金熔煉製程中，若真空度稍微差一點，所熔 配之儲氫合金根本完全無法活化，更不用提後續去做為儲存氫 之使用。Since the publication of related literatures such as Compounds, the hydrogen storage capacity has made a leap forward (almost twice as much) as the conventional AB5 or AB2, which has caused the attention of hydrogen storage alloy materials researchers and related industries. However, in these studies, it was soon found that such a BCC hydrogen storage alloy containing titanium chrome as a main element is generally slower in activation speed than conventional AB5 or AB2. A conventional activation treatment method that is quite useful for conventional ABs or AB2 hydrogen storage alloys' includes a so-called chemical acid pickling process (wet method) using hydrofluoric acid, nitric acid or a mixture of the two, the main purpose of which is to corrode The method of removing the surface of the hydrogen storage alloy is easy to form an oxide layer; or another physical activation process (dry method) under a high temperature and high pressure hydrogen atmosphere, that is, causing the hydrogen storage alloy to expand due to hydrogen absorption volume to cause alloy hydrogen Brittle cracking produces a fresh, non-oxidized surface (boundary surface) that makes it easy to absorb hydrogen and increase the rate of hydrogen absorption. However, these relatively effective treatment methods for conventional hydrogen storage alloys, when applied separately or in combination with BCC hydrogen storage alloys, have been tested and found to be difficult to activate and absorb hydrogen. Sometimes, even in the alloy melting process, if the degree of vacuum is slightly worse, the hydrogen storage alloy to be melted is completely incapable of activation, not to mention the subsequent use as a storage hydrogen.
，此問題習知之另一種有效做法乃是在真空熔煉製程以外，i 採用機械合金法（ΜΑ)與高能量球磨法（HEBM)。因為這兩^ f法可使合金化過程產生大量塑性變形、冷焊與破裂，導致4 米晶（nanocrystalline)合金生成，因此可增加吸放氫速^ 與改善活化問題。在許多研究中已證實機械合金法，可成功^ 備B^C儲氫合金，達到快速吸放氫解決活化困難的問題。j 而，^些以機械合金法或高能量球磨法製備之Β(χ儲氫合金 其儲氫量卻遠不及相同成份而以真空熔煉加上急速冷卻製寻 者。因此對於BCC高容量儲氫合金的實際商業化應用，業界! =何能有效的解決其活化醜又不損及其儲氫量，有強烈白 需求。 6 201012941 【發明内容】 ^對^輪賴之乾式與濕式活化製程， 發現在以τ!、v、Cr為主要元素的BCC =试驗後 是之前’若添加微量之金屬華)元素ί其;中或 =要= 行後續活化處理之高容量儲氫合金%全 素最適且之添加量相對於原儲氫合金之重乂卜（^)兀 0·05〜L0 wt%。當料Pd)添加量小於〇 〇5辦刀” 易活化之BCC儲氳合金活化，當添加量超’ ^=Another effective practice of this problem is to use mechanical alloying (ΜΑ) and high energy ball milling (HEBM) in addition to the vacuum melting process. Because these two methods can cause a large amount of plastic deformation, cold welding and cracking in the alloying process, resulting in the formation of a nanocrystalline alloy, it can increase the rate of hydrogen absorption and desorption and improve the activation problem. In many studies, the mechanical alloying method has been proven to successfully prepare B^C hydrogen storage alloys to achieve rapid hydrogen absorption and desorption to solve the problem of activation difficulties. j, some are prepared by mechanical alloying or high-energy ball milling. The hydrogen storage alloy has a much lower hydrogen storage capacity than the same component and is vacuum smelted with rapid cooling. Therefore, for BCC high-capacity hydrogen storage. The actual commercial application of alloys, the industry! = How can effectively solve its activation ugly without damaging its hydrogen storage capacity, there is a strong white demand. 6 201012941 [Summary of the invention] ^ Dry and wet activation process It is found that BCC with τ!, v, and Cr as the main elements is the previous 'if a small amount of metal is added'), and the medium or the = is required to be a high-capacity hydrogen storage alloy. The optimum amount of the element is relative to the weight of the original hydrogen storage alloy (^) 兀0·05~L0 wt%. When the amount of Pd) is less than 〇 〇5, the easy-activated BCC storage alloy is activated when the amount is exceeded.
雖然一般商用之儲氫合金目前主要都是以真空 作’惟本發明之活化方法並不限於熔煉製程。尤其 Ti、V、Cr為主要元素的BCC儲氫合金，因為具有高熔點、、言 活性之特性，無法以傳統之真空熔煉方式進行者，亦可採用= 械合金製程（例如：以粉末為原料進行球磨）來合成。此 要在球磨過程中摻入同樣劑量（〇·〇5〜1 .〇加％ )之把(pd)粉末^ 並與Ti、V、Cr粉末一同球磨，一樣可改善BCC儲氫合金 化性能。 ' 透過以下之實施例及比較例將能更清楚瞭解本發明之特點與 功效，使熟習本案發明相關技術者能據以實施。 【實施方式】 【比較例一】 將Ti~V_Cr BCC儲鼠合金原料，以成份為Ti、V、Cr元素在等 原子比之比例下置入可急冷之雙層水冷銅模坩鍋中，開始抽真 空至2*10_3 torr接著通入南純度氬氣至〇. 8 atm。然後以電 弧加熱方式熔煉，每次50秒並反覆翻面總共重熔六次以確保 合金之均勻。所熔鑄Ti-V-Cr BCC儲氫合金錠則以機械方式敲 201012941 碎至l-3mm大小的細顆粒作為後續吸放氫實驗用。依照習知的 經驗’儲氫合金因含有高活性元素，其表面非常容易形成氧化 層’此氧化層的形成會阻礙氫原子進入晶體的格隙位置。故習 知之AB5或ABZ儲氫合金在使用之前或是在進行儲氫量與所謂 吸放氫PCT曲線測試前，必須先經過活化前處理（酸洗過），如 此方可以順利吸氫並加速吸、放氫反應。 由於鈦與釩與氧的結合能力非常強，BCC儲氫合金比習知之AB5 ® 或Αβ2儲氫合金表面更容易生成氧化層，使得氫原子擴散至合 金内部變得困難，因此熔煉與碎化後iTi_v_CrBCC儲氫合金 細顆粒’也分別以配方為（A) M: M〇3: HF=3 : 2:1，（B) H2〇 : 祕〇3: HF = 6 : 1 : 1，（C) Μ : H·3: HF=6 : 2 : 1 以及⑻ H2〇 : 腿〇3: HF = 2 : 1 : 1之酸洗液’進行腐蝕時間分別為3〇秒分、 1分鐘及2分鐘之酸洗前處理（活化處理），以除去表面的氧 化層以利後續之吸放氫反應。 參然而經實際的吸放氫測試發現’應無論是以（A) h2〇 :腿〇3: HF=3 ： 2 ： 1 * (B) H2O ： H2NO3 ： HF=6 : 1 ： 1 > (C) H2O ： H2NO3 ： HF=6 · 2 : 1以及（D) H2〇 :腿〇3 : HF=2 : 1 : 1之酸洗液經過 30秒、1分鐘或2分鐘之酸洗活化前處理，當施以bar之 氫氣充氫，縱使持續一小時Ti-V-CrBCC儲氫合金最大儲氫量 仍小於0. 8 wt% ’遠低於其理論值，甚至連ABs或AB2儲氫合金 都不如。此結果顯示傳統酸洗活化方式依舊難以使以Ti-v_cr 組成為主之BCC儲氫合金消除粉體表面的雜質，產生完全之 201012941 吸氫反應。 【比較例二】 將Ti-V-Cr BCC儲氫合金原料，以成份為Ti、v、Cr元素在等 原子比之比例下置人可急冷之雙層水冷鋼_鍋中，開始抽真 空至2*10-3 torr接著通入高純度氬氣至〇 8 _。然後以電 弧加熱方式溶煉，每次50秒並反覆翻面總共重熔六次以確保 合金之均勻。所熔鑄Ti-V_CrBCC儲氫合金錠則以機械方式敲 碎至l-3inm大小的細顆粒作為後續吸放氫實驗用。熔煉後之 Ti-V-Cr BCC儲氫合金錠，依照習知的經驗，因含有高活性元 素，其表面非常容易形成氧化層，氧化層的形成會阻礙氩原子 進入晶體的格隙位置，因此在使用之前或是在進行儲氫量與所 謂吸放氫PCT曲線測試前，需要進行活化前處理。 由於先前之酸洗活化前處理（化學法）對於以以Ti-v~Cr為主 要組成之BCC儲氫合金效果非常有限，因此改以習知之另一 種也就是物理方式進行活化前處理：首先將碎化後之Ti_v_Cr BCC儲氳合金細顆粒放入合金槽内先抽真空至i〇-3torr以下 除氣30分鐘’再於常溫下通入20 bar的氫氣’升溫至4〇〇ι 並在10 bar的氫氣氛壓力下維持1小時，使表面氧化層進行 還原活化。然後在同樣之400°C釋放氫氣，當小於1 bar時在 啟動真空幫浦並抽真空至10-3t〇rr以下完成物理方式之活 化。然而當以Sievert方式測量Ti-V-Cr BCC儲氫合金儲氣 201012941 量時，發現其最大儲氫量未達〇· 6 wt%，遠低於其理論值，顯 示未達活化的目的。因此再將前述物理活化方式，重複循環兩 次、三次甚至五次，然而縱使持續一小時後量測到之Ti_v_Cr BCC儲氫合金最大儲氫量仍小於〇· 8 wt%，遠低於其理論值。 此結果亦顯示傳統物理之活化方式依舊難以使以Ti V Cr組 成為主之BCC儲氫合金消除粉體表面的雜質，產生完全之吸 氫反應。 φ 【比較例三】 將Ti-V-CrBCC儲氫合金原料，以成份為Ti、¥、&元素在等 原子比之比例下置入可急冷雙層水冷銅模坩鍋中後，開始抽真 空至2*1〇-3 torr接著通入高純度氬氣至〇·8 ati^然後以電 弧加熱方式溶煉，每次5〇秒並反覆翻面，共重熔六次以確保 σ金之均勻。所熔•Ti_v_CrBCC儲氫合金錠則以機械方式敲 碎至l-3mm大小的細顆粒作為後續實吸放氫驗用。對於熔煉後 參 表面容易形成氧化層之Ti—V-Cr BCC儲氫合金旋，則先以酸洗 活化别處理（化學法）再似物理活化法進行所謂活化前處理 以加速吸氫反應。其中之酸洗液配方為：⑴出〇 : 册 3 · 2 * 1 , (B) H2〇 ： H2NO3 ： HF=6 ： 1 ： 1 * (Ο H2O ： H2NO3 ： HF==6 : 2 : 1以及⑼h2〇 ·· _3 : HF=2 :丨：〗之酸洗液進 行腐钱時間㈣為3〇秒分與2分細除去表面的氧化層以利 後續之物理活化過程。 201012941 經過酸洗後的粉體立即烘乾，並放入合金槽内，合金槽内抽真 空至10-3torr以下除氣30分鐘，再於常溫下通入2〇 bar的 氫氣’升溫至400°C並在1〇 bar的氫氣氛壓力下維持1小時， 使表面氧化層進行還原活化。然後在同樣之4〇〇。(：釋放氫氣， 當小於1 bar時在啟動真空幫浦並抽真空至i〇-3torr以下完Although the general commercial hydrogen storage alloys are currently mainly vacuumed, the activation method of the present invention is not limited to the smelting process. In particular, BCC hydrogen storage alloys in which Ti, V, and Cr are the main elements are not able to be carried out by conventional vacuum melting because of their high melting point and active properties, and can also be processed by a mechanical alloy (for example, using powder as a raw material). Perform ball milling to synthesize. In this case, the same dose (〇·〇5~1.〇%) of the (pd) powder ^ is added in the ball milling process and ball-milled together with the Ti, V, and Cr powders to improve the hydrogen storage alloying properties of the BCC. The features and functions of the present invention will be more clearly understood from the following examples and comparative examples, so that those skilled in the art of the invention can practice. [Embodiment] [Comparative Example 1] Ti~V_Cr BCC storage alloy raw materials are placed in a quenchable double-layer water-cooled copper mold crucible with a ratio of Ti, V, and Cr in an atomic ratio. Vacuum the mixture to 2*10_3 torr and then pass the southern purity argon to 〇. 8 atm. It is then smelted by arc heating for a total of 50 seconds and repeated reversal six times to ensure uniformity of the alloy. The cast Ti-V-Cr BCC hydrogen storage alloy ingot was mechanically knocked down by 201012941 to fine particles of l-3mm size for subsequent hydrogen absorption and desorption experiments. According to the conventional experience, the hydrogen storage alloy is highly susceptible to the formation of an oxide layer due to the presence of highly active elements. The formation of this oxide layer hinders the entry of hydrogen atoms into the lattice gap of the crystal. Therefore, the conventional AB5 or ABZ hydrogen storage alloy must be pre-activated (acid washed) before use or before the so-called hydrogen storage and PCT curve test, so that it can smoothly absorb hydrogen and accelerate absorption. , hydrogen release reaction. Due to the strong binding ability of titanium and vanadium to oxygen, BCC hydrogen storage alloys are more likely to form an oxide layer than the surface of conventional AB5 ® or Αβ 2 hydrogen storage alloys, making it difficult for hydrogen atoms to diffuse into the interior of the alloy, so after smelting and fragmentation The iTi_v_CrBCC hydrogen storage alloy fine particles 'is also formulated as (A) M: M〇3: HF=3: 2:1, (B) H2〇: Tip 3: HF = 6 : 1 : 1, (C) Μ : H·3: HF=6 : 2 : 1 and (8) H2〇: Leg 〇 3: HF = 2 : 1 : 1 pickling liquid 'corrosion time is 3 〇 seconds, 1 minute and 2 minutes respectively Pre-pickling treatment (activation treatment) to remove the oxide layer on the surface for subsequent hydrogen absorption and desorption reactions. However, the actual hydrogen absorption and desorption test found that 'should be (A) h2 〇: leg 〇 3: HF = 3 : 2 : 1 * (B) H2O : H2NO3 : HF = 6 : 1 : 1 > C) H2O: H2NO3: HF=6 · 2 : 1 and (D) H2〇: Leg 〇 3 : HF=2 : 1 : 1 pickling solution after 30 seconds, 1 minute or 2 minutes of pickling activation pretreatment When hydrogen is applied to the hydrogen of bar, the maximum hydrogen storage capacity of the Ti-V-CrBCC hydrogen storage alloy is still less than 0.8% by weight for a period of one hour. Even far below its theoretical value, even the ABs or AB2 hydrogen storage alloys are Not as good. This result shows that the traditional pickling activation method is still difficult to eliminate the impurity on the surface of the powder by the BCC hydrogen storage alloy mainly composed of Ti-v_cr, and the complete hydrogen absorption reaction of 201012941 is produced. [Comparative Example 2] The Ti-V-Cr BCC hydrogen storage alloy raw material was placed in a double-layer water-cooled steel pot with a composition of Ti, v, and Cr at a ratio of equal atomic ratio, and vacuuming was started. 2*10-3 torr then passes high purity argon to 〇8 _. It is then fused by arc heating, re-melting six times each time for 50 seconds and repeatedly turning over to ensure uniformity of the alloy. The cast Ti-V_CrBCC hydrogen storage alloy ingot was mechanically crushed to fine particles of l-3 inm size for subsequent hydrogen absorption and desorption experiments. The smelted Ti-V-Cr BCC hydrogen storage alloy ingot, according to the conventional experience, because of the high active element, the surface of the Ti-V-Cr BCC hydrogen storage alloy is very easy to form an oxide layer, and the formation of the oxide layer hinders the entry of the argon atoms into the lattice gap of the crystal. Pre-activation treatment is required prior to use or prior to testing for hydrogen storage and so-called hydrogen absorption and desorption hydrogen PCT curves. Since the previous pickling activation pretreatment (chemical method) has a very limited effect on the BCC hydrogen storage alloy with Ti-v~Cr as the main component, it is also known that the other is the physical pre-activation treatment: first After the crushed Ti_v_Cr BCC storage alloy fine particles are placed in the alloy tank, first evacuate to i〇-3torr and degas for 30 minutes 'and then enter 20 bar of hydrogen at normal temperature' to raise to 4〇〇ι and at 10 The bar was maintained under hydrogen atmosphere pressure for 1 hour to effect reduction reduction of the surface oxide layer. The hydrogen is then released at the same 400 ° C. When less than 1 bar, the vacuum pump is started and evacuated to below 10 -3 t rr to complete the physical mode of activation. However, when the amount of Ti-V-Cr BCC hydrogen storage alloy gas storage 201012941 was measured by Sievert method, it was found that the maximum hydrogen storage capacity did not reach 〇·6 wt%, which was much lower than its theoretical value, indicating that the activation was not achieved. Therefore, the above physical activation mode is repeated twice, three times or even five times. However, even after one hour of continuous measurement, the maximum hydrogen storage capacity of the Ti_v_Cr BCC hydrogen storage alloy is still less than 〇·8 wt%, which is far lower than its theory. value. This result also shows that the activation mode of the conventional physics is still difficult to eliminate the impurities on the surface of the powder by the BCC hydrogen storage alloy in which the Ti V Cr group is the main, thereby generating a complete hydrogen absorption reaction. Φ [Comparative Example 3] The Ti-V-CrBCC hydrogen storage alloy raw material is placed in a quenchable double-layer water-cooled copper mold crucible at a ratio of equal ratio of Ti, ¥, & Vacuum to 2*1〇-3 torr and then pass high-purity argon to 〇·8 ati^ and then smelt by arc heating, each time 5 〇 seconds and turn over again, re-melting six times to ensure σ gold Evenly. The molten Ti_v_CrBCC hydrogen storage alloy ingot is mechanically broken to a fine particle of l-3 mm size for subsequent physical hydrogen absorption and desorption. For the Ti-V-Cr BCC hydrogen storage alloy which is easy to form an oxide layer after the smelting, the so-called pre-activation treatment is carried out by acid washing and activation (chemical method) and physical activation to accelerate the hydrogen absorption reaction. The formula of the pickling solution is: (1) 〇: Booklet 3 · 2 * 1 , (B) H2〇: H2NO3 : HF=6 : 1 : 1 * (Ο H2O : H2NO3 : HF==6 : 2 : 1 and (9) h2〇·· _3 : HF=2 :丨:〗 The pickling solution is subjected to the rotted time (4) for 3 〇 seconds and 2 minutes to remove the oxide layer on the surface for subsequent physical activation. 201012941 After pickling The powder is immediately dried and placed in an alloy bath. The alloy tank is evacuated to a temperature of 10-3 torr for 30 minutes, and then a hydrogen gas of 2 〇bar is introduced at room temperature to raise the temperature to 400 ° C and at 1 〇 bar. The hydrogen atmosphere is maintained under pressure for 1 hour to reductively activate the surface oxide layer, and then in the same 4 Torr. (: Release hydrogen, when less than 1 bar, start the vacuum pump and evacuate to below i〇-3torr
成物理方式之活化。然而當以Sievert方式測量Ti-V-Cr BCC 儲氫合金之儲氫量時’縱使持續一小時發現其最大儲氫量仍未 眷 達〇.8wt% ’遠低於其理論值，顯示習知之物理加上化學活化 方式對於以Ti-V-Cr為主要成份之bCC儲氫合金效果極其有 限。 【實施例一】 將Ti-V-Cr BCC儲氫合金原料與微量之金屬鈀(pd)元素，以成 份為Τι、V、Cr元素在等原子比之比例，並摻入〇. 〇3wt% (3〇〇 ppm)之金屬鈀(IM)元素情況下，置入可急冷雙層水冷銅模坩 Φ 鋼中後’開始抽真空至_—3 tor接著通入高純度氬氣至 0· 8 atm。然後以電弧加熱方式熔煉，每次5〇秒並反覆翻面， 共重熔六次以確保合金之均勻。所熔鑄Ti_V Cr BCC儲氫合金 鍵則以機械方式敲碎至卜3mm大小的細顆粒作為後續吸放氮 實驗用。 此含有0.03wt%金屬纪之Ti-V-Cr Bcc健氫合金，在完全不做 物理或是化學（酸洗）活化的方式下，直接以如㈣方式 測量其儲氫量時，發現在常溫43 bar之氮氣壓力下，此合金 11 201012941 可快速吸虱’並且在10分鐘内儲氮量就可達到3.㈣，接近 其理論值’顯示添加微量之金屬把㈣元素在打―BCC儲 氫合金中，則可制完全不需要進行後續活化處理之高容量儲 氫合金。 【實施例二】 將Ti-V-Cr BCC儲氫合金原料與微量之金屬鈀㈣元素，以成 份為Ti、V、Cr元素在等原子比之比例，並摻入〇· 〇5_ (5〇〇 e ppm)之金屬把㈣元素情況下’置入可急冷雙層水冷銅模掛 鋼中後’開始抽真空至2*i〇-3 t〇rr接著通入高純度氬氣至 0.8 atm。然後以電弧加熱方式熔煉，每次5〇秒並反覆翻面， 共重熔六次以確保合金之均勻。所熔鑄1>丨4_(：1^(：(：儲氫合金 旋則以機械方式敲碎至卜3mm大小的細顆粒作為後續吸放氫 實驗用。 此含有0.05wt%金屬鈀之Ti-V-Cr BCC儲氫合金，在完全不做 ❹ 物理或是化學（酸洗）活化的方式下，直接以Sievert方式 測量其儲氫量時，發現在常溫18 bar之氫氣壓力下，此合金 可快速吸氫，並且在5分鐘内儲氫量就可達到&物伙，接近 其理論值，顯示添加微量之金屬鈀(Pd)元素在Ti-V-Cr BCC儲 氮合金中’則可得到完全不需要進行後續活化處理之高容量儲 氫合金。 【實施例三】 將Ti-V-Cr BCC儲氫合金原料與微量之金屬鈀(Pd)元素，以成 12 201012941 份為Ti、V、Cr元素在等原子比之比例，並摻入〇. 5wt%之金 屬把㈣元素情況下，置入可急冷雙層水冷銅模職中後，開 始抽真空至2*10-3 torr接著通入高純度氩氣至〇 8 atm。然 後以電弧加熱方式熔煉，每次50秒並反覆翻面，共重熔六次 以確保合金之均勻。所熔鑄Ti_v__Cr BCC儲氫合金鍵則以機械 方式敲碎至1-3麵大小的細顆粒作為後續吸放氫實驗用。 此含有0. 5wt%金屬鈀之Ti-V-Cr BCC儲氫合金，在完全不做 ❹ 物理或是化學（酸洗）活化的方式下，直接以Sievert方式 測量其儲氫量時’發現在常溫6 bar之氫氣壓力下，此合金可 快速吸氫，並且在5分鐘内儲氫量就可達到3.45wt% ,接近其 理淪值，顯示添加微量之金屬鈀(Pd)元素在Ti_V Cr BCC儲氫 合金中’則可得到完全不需要進行後續活化處理之高容量儲氫 合金。 【實施例四】 參 將Ti_V-Cr BCC儲氫合金原料與微量之金屬鈀(pd)元素，以成 份為Ti、V、Cr元素在等原子比之比例，並摻入丨.〇wt%之金 屬鈀(Pd)元素情況下’置入可急冷雙層水冷銅模坩鍋中後，開 始抽真空至2氺10-3 torr接著通入高純度氬氣至〇. 8 atm。然 後以電弧加熱方式熔煉，每次5〇秒並反覆翻面，共重熔六次 以確保合金之均勻。所熔鑄^4_(：1^(：(：儲氫合金錠則以機械 方式敲碎至l-3mm大小的細顆粒作為後續吸放氫實驗用。 此含有1· Owt%金屬鈀之Ti_V_Cr BCC儲氫合金，在完全不做 13 201012941 物理或是化學（酸洗）活化的方式下，直接以Sievert方式 測量其儲氫量時’發現在常溫5. 8 bar之氫氣麗力下，此合金 可快速吸氫，並且在5分鐘内儲氫量就可達到3.㈣。顯示 添加微量之金屬le(Pd)元素在Ti-v-cr BCC儲氫合金中，可得 到;^全不需要進行後續活化處理之高容量儲氣合金。 【實施例五】 將Ti-V-Cr BCC儲氫合金原料與微量之金屬鈀㈣元素，以成 ❷ 份為Ti、V、元素在等原子比之_，並摻人3. Qwt%之金 屬把(Pd)元素情況下’置入可急冷雙層水冷銅模掛鋼中後，開 始抽真空至2__3 tQrr接著私高純度氬氣至Q· 8 _。然 後以電狐加熱方式熔煉，每次5〇秒並反覆翻面，共重溶六次 以確保合金之均句。所料Ti+CrBCC儲氫合金錠則以機械 方式敲碎至1-3麵大小的細顆粒作為後續吸放氫實驗用。 此含有3· Owt%金屬把之Ti-V-Cr BCC儲氫合金，在完全不做 參 物理或是化學（酸洗）活化的方式下，直接以Sievert方式 測量其儲氫量時，發現在常溫4. 6 bar之氫氣壓力下，此合金 可快速吸氫’並且在5分軸儲氫量就可制丨.8禮。，但維 持30分鐘後儲氫量仍為L 8 wt%，顯示添加金屬鈀㈣元素雖 可使Ti-V-CrBCC聽合金完全不需要進行傳統之後續活化處 理，惟添加量亦不宜過多否則會犧牲儲氫量。 從實施例一至實施例五可發現在Ti__v—Cr Β(χ儲氫合金中添加 201012941 金屬鈀(Pd)元素對原本不易活化之BCC儲氫合金有顯著之改盖 效果。然而當lB(Pd)添加量小於〇〇5 wt%時，需要較高的氫 氣壓力才能使BCC儲氫合金活化與吸氫，當添加量超過 wt%時，BCC儲氫合金雖然不需要進行後續活化處理就可以直 接吸氫，但其儲氫量卻會急遽下降。就實用性而言，一般充氣 壓力宜低於20 bar，館氫量也至少要大於& 〇 _，因脉元Activated by physical means. However, when the hydrogen storage capacity of Ti-V-Cr BCC hydrogen storage alloy was measured by Sievert method, it was found that its maximum hydrogen storage capacity did not reach 〇.8wt% 'well far below its theoretical value even for one hour. Physical plus chemical activation is extremely limited for bCC hydrogen storage alloys with Ti-V-Cr as the main component. [Example 1] Ti-V-Cr BCC hydrogen storage alloy raw material and a trace amount of metal palladium (pd) element, the composition of the elements of Τι, V, Cr in an atomic ratio, and incorporated into 〇. 〇 3wt% (3〇〇ppm) of metal palladium (IM) element, after being placed in a quenchable double-layer water-cooled copper mold 坩Φ steel, 'start vacuuming to _-3 tor and then pass high-purity argon to 0·8 Atm. Then, it is smelted by arc heating, each time for 5 sec seconds and repeatedly turned over, and re-melted six times to ensure uniformity of the alloy. The cast Ti_V Cr BCC hydrogen storage alloy bond was mechanically broken to a fine particle of 3 mm size for subsequent nitrogen absorption experiments. The Ti-V-Cr Bcc hydrogen-rich alloy containing 0.03 wt% of metal is found to be at room temperature by directly measuring the hydrogen storage amount as in (4) mode without physical or chemical (acid wash) activation. Under the nitrogen pressure of 43 bar, this alloy 11 201012941 can quickly suck 'and the nitrogen storage capacity can reach 3. (4) in 10 minutes, close to its theoretical value 'showing the addition of trace amount of metal to the (four) element in the "BCC hydrogen storage" In the alloy, a high-capacity hydrogen storage alloy that does not require subsequent activation treatment can be produced. [Example 2] Ti-V-Cr BCC hydrogen storage alloy raw material and a trace amount of metal palladium (four) elements, with the composition of Ti, V, Cr elements in the ratio of equiatomic ratio, and incorporated into 〇· 〇5_ (5〇 The metal of 〇e ppm) is placed in the quenchable double-layer water-cooled copper mold steel after the element (4), and the vacuum is started to 2*i〇-3 t〇rr and then high-purity argon is introduced to 0.8 atm. Then, it is smelted by arc heating, each time for 5 sec seconds and repeatedly turned over, and re-melted six times to ensure uniformity of the alloy. The cast 1>丨4_(:1^(:(: hydrogen storage alloy is mechanically broken to a fine particle of 3 mm size for subsequent hydrogen absorption experiments. This Ti-V containing 0.05 wt% metal palladium) -Cr BCC hydrogen storage alloy, when it is directly measured by Sievert method in the absence of physical or chemical (acid wash) activation, it is found that the alloy can be quickly heated at a hydrogen pressure of 18 bar at normal temperature. Hydrogen absorption, and the amount of hydrogen stored in 5 minutes can reach & object, close to its theoretical value, showing that the addition of trace amounts of metal palladium (Pd) elements in Ti-V-Cr BCC nitrogen storage alloys can be completely A high-capacity hydrogen storage alloy that does not require subsequent activation treatment. [Example 3] The Ti-V-Cr BCC hydrogen storage alloy raw material and a trace amount of metal palladium (Pd) element are made into 12 201012941 parts as Ti, V, Cr. The ratio of the element in the equiatomic ratio is incorporated into 〇. 5wt% of the metal (4) element, after being placed in the quenchable double-layer water-cooled copper mold, the vacuum is started to 2*10-3 torr and then the high Purity argon to 〇 8 atm. Then smelt in an arc heating manner for 50 seconds and flip over. 5wt%金属金属的Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti -V-Cr BCC hydrogen storage alloy, when it is not subjected to physical or chemical (pickling) activation, the hydrogen storage capacity is measured directly in Sievert mode, and the alloy is found under a hydrogen pressure of 6 bar at normal temperature. It can absorb hydrogen quickly, and the hydrogen storage capacity can reach 3.45wt% in 5 minutes, which is close to its theoretical value. It shows that the addition of trace amount of metal palladium (Pd) element in Ti_V Cr BCC hydrogen storage alloy can be completely absent. A high-capacity hydrogen storage alloy that requires subsequent activation treatment. [Example 4] The Ti_V-Cr BCC hydrogen storage alloy raw material and a trace amount of metal palladium (pd) element are used in the atomic ratio of Ti, V, and Cr elements. The ratio, and incorporation of 金属.〇wt% of metal palladium (Pd) element, after being placed in a quenchable double-layer water-cooled copper mold crucible, start vacuuming to 2氺10-3 torr and then pass high purity Argon to 〇. 8 atm. Then smelt by arc heating, 5 sec each time Repeatedly turning over and remelting six times to ensure uniformity of the alloy. The cast ^4_(:1^(:(: hydrogen storage alloy ingot is mechanically broken to fine particles of l-3mm size for subsequent hydrogen absorption and desorption) The Ti_V_Cr BCC hydrogen storage alloy containing 1·Owt% metal palladium is found in the method of physical or chemical (pickling) activation at 13 201012941, and the hydrogen storage amount is directly measured by Sievert method. Under the hydrogen pressure of 5. 8 bar at room temperature, the alloy can absorb hydrogen rapidly, and the hydrogen storage capacity can reach 3. (4) within 5 minutes. It is shown that the addition of a trace amount of metal le(Pd) element in the Ti-v-cr BCC hydrogen storage alloy can be obtained; a high-capacity gas storage alloy which does not require subsequent activation treatment. [Example 5] The Ti-V-Cr BCC hydrogen storage alloy raw material and a trace amount of the metal palladium (tetra) element, the ruthenium is Ti, V, the element is in an equiatomic ratio, and the metal is doped with 3. Qwt% After placing the (Pd) element in the quenched double-layer water-cooled copper mold steel, the vacuum is started to 2__3 tQrr and then the private high-purity argon gas is supplied to Q·8 _. Then, it is smelted by electric fox heating method, and it is turned over every 5 sec seconds and re-dissolved six times to ensure the uniformity of the alloy. The Ti+CrBCC hydrogen storage alloy ingot was mechanically crushed to fine particles of 1-3 size for subsequent hydrogen absorption and desorption experiments. The Ti-V-Cr BCC hydrogen storage alloy containing 3·Owt% of the metal is directly measured by Sievert in the manner of no physical or chemical (acid wash) activation. Under the hydrogen pressure of 4. 6 bar at normal temperature, the alloy can quickly absorb hydrogen' and can store hydrogen in the 5-axis. However, after 30 minutes of maintenance, the hydrogen storage capacity is still L 8 wt%, indicating that the addition of metal palladium (tetra) element can make the Ti-V-CrBCC alloy not need to be subjected to the traditional subsequent activation treatment, but the addition amount should not be too much. Sacrifice hydrogen storage. From Example 1 to Example 5, it can be found that the addition of 201012941 metallic palladium (Pd) element to Ti__v-Cr Β (χ hydrogen storage alloy has a significant effect on the BCC hydrogen storage alloy which is not easily activated. However, when lB(Pd) When the addition amount is less than 〇〇5 wt%, a higher hydrogen pressure is required to activate and absorb hydrogen of the BCC hydrogen storage alloy. When the added amount exceeds wt%, the BCC hydrogen storage alloy can be directly sucked up without subsequent activation treatment. Hydrogen, but its hydrogen storage capacity will drop sharply. In terms of practicality, the general inflation pressure should be lower than 20 bar, and the hydrogen content of the museum should be at least greater than & 〇_, due to the pulse element
素最適宜之添加量相對於氫合金之重量百分比介於 。透過發明說明書之記載，熟習本項技術者將可 ^本發明之_及功效，並可據以實施。 財—具林難、紗财可供產業利 提出二國專利法所規定之專利中請要件無疑，麦依法 k出發明專利申請’析狗局早曰賜准專利，至感為禱。The optimum amount of addition is relative to the weight percentage of the hydrogen alloy. Through the description of the invention, those skilled in the art will be able to implement the invention and the utility thereof. Wealth--------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
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