201111520 六、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&械加工 與球磨活化前處理技術有關。 【先前技術】201111520 VI. Description of the invention: [Technical field to which the invention pertains] The technical field to which the present invention pertains 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 & [Prior Art]
近年來由於環保意識的抬頭與能源危機的影響，世界各國開始 發展替代能源。目前全世界使用的能源主要來自化石燃料，^ 其使用不可避免地污染環境，再加上其儲量有限，故尋找可再 生的綠色能源迫在眉睫。氫能作為一種儲量豐富、來源廣泛、 能量密度高的綠色能源及能源載體，正引起人們的廣泛關注。 氫能的開發和利用受到各國的高度重視，以期在21世紀中葉 進入“氫能經濟(hydrogeneco_y)，，時代。傳統儲氮方法有 兩種，-種方法是彻高壓鋼瓶（航瓶)來儲存氫氣，但鋼 ，瓦巧存氫氣的容積小，而且還有爆炸的危險；另一種方法是液 癌氫儲存’但液體儲存箱非常龐大，需要極好的絕熱裝置來隔 ，二近年來利^儲氫合金來儲存氫氣，金屬氫化物具有低壓儲 存局體積比及高儲存重量比的特性，且儲氫合金於吸氮過程為 放熱反應，故儲氫合金的開發具有常溫與低壓儲存的安全特 性1是^相當熱門的研究方向。國際能源署（IEA)提出的目 ，是儲氫f大於5mass %、並且放氫溫度低於(15{)〇c) 胥命超過1000次。 衣 目刖商用之儲氫合金以ABs型為主，但因儲氫量小，已不敷 求:而Μ型(MgNi)合金雖具有高儲氫量但其工作溫度往往都 H ’在應用上有了不少、限制。另一種BCC型合金因具有高儲 ，量及室溫吸放氫等特性備受重視，雖然其吸氫量可達 8wt%，但目含價昂之v金屬，同時其吸氫量仍然低於 %。 201111520 現今儲氫合金H簡金屬元纽氫競_ 5 _以上， =财的活性太大，表面易形雜錢分子崎之氧化層而影 響風原子於合金表_散轉，導致_不易贿化、吸放氣 動力差，吸放氫溫度過高，因此無法成為實用之儲A合金。為 降低其工作溫度，大部分研究主要是添加催化劑，例如Ni添 加，操作溫度在靴，但吸氫量降至3· 6㈣左右。後來陸 續有添加其他_三元素、微結構處理和表域理等方 善。 在曰本应島场的小島教朗隊巾，於氫賴巾添加微量過渡 金屬氧化物，再經球磨處理，特別著重在改善皮應速度之研 究。無添加物之氫化鎂，在氦氣流(即氫分壓為零)之條件下， 於37(TC開始放氫。而添加工m〇1%祕，經2〇 J、時球磨處理， 放氫溫度可降低i5(rc。添加_5之氫傾，再_ 22此之 脫氫處理’放氫溫度可再低溫化。除了 _5外，附、^、 等金屬奈雜子，或Ti〇2等氧化物添加，球雜之氫化鎮放氮 反應速度改善也有報導。雜這纽善方法或乡或少有些成 效’但因添加物屬於過渡元素氧化物，比重高整體儲氯量約達 4 mass%，因此大幅降低鎂合金原本之輕量化效果。 【發明内容】 相對於傳統所用之Nb〇5，Ni、Fe、Co等金屬奈米粒子或Ti〇2 201111520 氧化物之添加，因添加物比重高造成整體儲氫量之大幅下降， 本案發明人多次試驗後發現鎂合金原本吸放氫速度太慢的問 題，可以導入不同程度的塑性變形機制，例如冷軋，將原本粗 大之鎮合金產生微小晶粒和顆粒細化，並利用球磨機在球磨粉 化過程中同時添加石墨，與該合金共同球磨成粉狀储氫粉末來 降低其吸放氫溫度與提升吸放氫速度。 至於石墨最適宜之添加量相對於原儲氫合金之重量百分比則 介於3〜10 wt%。當石墨添加量小於3 wt%時，不足以使不易活 化鎂基儲氫合金使其能快速吸放氫，另外，由於石墨本身並不 吸氫，因此過多之石墨添加會損及整體之儲氫量，故石墨添加 量不宜超過10 wt%。 【實施例】 為方便實驗之進行，鎂合金直接選用商用之ZK6〇鎂合金 iMg_6mass%Zn_(X8mass%Zr)為儲氫材料，以石墨添加來改善 儲氫特性、吸放氫行為 '使用之ZK6〇合金板材，首先經軋延 率80%之冷軋延加工，再以銼刀銼削成顆粒。合金粉末之製備 方法分別為將銼刀銼削成顆粒置入球磨機，並添加石墨與該合 金顆粒共同封罐後球磨。其巾石墨添加量相對於原儲氫合金之 重量百分比分別為G，3 ’ 5與1〇 wt%。結果發現儲氫量與吸 放風速率最佳者為添加5 wf%之石墨。 第一圖為樣品C(添加5 mass%石墨當作催化劑共同球磨2〇小 201111520 時）’樣品B(未添加石墨球磨2〇小時）及樣品a(經刀銼削成 顆粒之冷軋延料)三種試樣之第一次活化差異。樣品C，本發 明例，在16min就開始有氫化反應。而樣品b大約在28min 開始有氫化反應，可是不顯著，必須在125min之後才比較明 顯’不過吸氫速率還是比添加石墨球磨2〇 h的樣品c慢許多。 另一方面’樣品A在1400 min才開始緩慢的氫化反應。添加 5 mass%石墨球磨2〇h的活化潛伏時間短，是因為經過球磨過 程’使氧化層剝離而在ZK60合金表面均勻的附著一層石墨， ^ 加速氫分子在表面解離成氫原子。 第二圖⑻與(b)分別樣品C (本發明）及樣品b (比較例）兩種 試樣經過10次循環吸放氫的數據。樣品c經過第一次的吸放 氫後就能完全的活化，第五次就能達到飽和吸氫量69 mass%，之後吸氫量就慢慢的下降，不過到了第1〇次還能維 持6.7 mass%以上的吸氫量。採用JIS金屬氫化物之氫化速率 測定法，以80%之飽和吸氫量為有效吸氫量，並計算出吸氫速 率。結果發現在5min就能達到80%之飽和吸氫量，有效吸氫 量為5·52 mass% ’而吸氫速率為1.104 mass〇/0/min，而大約在 30 min就能達到飽和吸風董。另·一方面，由圖（b)顯示樣s b 經過10次循環吸放氫還未能完全的活化’與習知結果一致。 根據本發明，Mg系儲氮合金藉由冷軋延或球磨機球磨，可知 ZK60合金經冷軋率80%之冷軋延加工’可獲得相當高之吸氮 201111520 量’現有儲氫合金中之最高吸氫量’ 4 mass%以上。再由添加 5 mass%石墨當作催化劑球磨20 h，第一次活化，在i6min就 開始有氫化反應。經過10次循環吸放氫的數據，添加5 mass% 石墨當作催化劑球磨20 h樣品經過第一次的吸放氫後就能完 全的活化’第五次就能達到飽和吸氫量6.9 mass%，之後吸氫 量就慢慢的下降，不過到了第1〇次還能維持6.7 mass%以上的 吸氫量。有效吸氫量為5.52 mass%，而吸氫速率為u〇4 mass%/min ’而大約在3〇 min就能達到飽和吸氫量。 綜上所述，本發明係實為一具有新穎性、進步性及可供產業利 用者，應符合我國專利法所規定之專利申請要件絲，爰依法 提出發明專利中請，祈釣局早日賜准專利，至感為禱。In recent years, due to the rise of environmental awareness and the impact of the energy crisis, countries around the world have begun to develop alternative energy sources. At present, the energy used in the world mainly comes from fossil fuels, and its use inevitably pollutes the environment. Coupled with its limited reserves, it is extremely urgent to find renewable green energy. As a kind of green energy and energy carrier with abundant reserves, wide sources and high energy density, hydrogen energy is attracting widespread attention. The development and utilization of hydrogen energy has been highly valued by all countries, with a view to entering the hydrogen energy economy (hydrogeneco_y) in the middle of the 21st century. There are two traditional methods of nitrogen storage. The method is to store high pressure cylinders (air bottles). Hydrogen, but steel, watts of hydrogen storage volume is small, and there is a danger of explosion; another method is liquid cancer hydrogen storage 'but the liquid storage box is very large, requires excellent insulation device to separate, two recent years ^ The hydrogen storage alloy stores hydrogen, the metal hydride has the characteristics of low volume storage volume ratio and high storage weight ratio, and the hydrogen storage alloy is exothermic in the nitrogen absorption process, so the development of the hydrogen storage alloy has the safety characteristics of normal temperature and low pressure storage. 1 is a very popular research direction. The International Energy Agency (IEA) proposes that the hydrogen storage f is greater than 5 mass% and the hydrogen release temperature is lower than (15{)〇c). The life expectancy exceeds 1000 times. The hydrogen storage alloy is mainly ABs type, but because of the small amount of hydrogen storage, it is not enough: while the MgNi alloy has high hydrogen storage capacity, its working temperature is often H'. , restrictions. Another type of BCC The alloy has attracted much attention due to its high storage capacity, capacity and hydrogen absorption and desorption at room temperature. Although its hydrogen absorption capacity can reach 8wt%, it also has a high price of v metal, and its hydrogen absorption is still less than %. 201111520 Hydrogen storage alloy H simple metal element New Zealand hydrogen _ 5 _ above, = wealth of activity is too large, the surface of the shape of the money crystal molecules of the oxide layer and affect the wind atom in the alloy table _ scatter, resulting in _ not easy to bribe, suck The deflation power is poor, and the hydrogen absorption and desorption temperature is too high, so it cannot be a practical storage alloy A. In order to reduce its working temperature, most of the research is mainly to add a catalyst, such as Ni addition, the operating temperature is in the boot, but the hydrogen absorption is reduced. 3·6(4). Later, there are other additions to the other three elements, micro-structure treatment and surface theory. In the small island of the island, the island is taught to add a trace of transition metal oxides to the hydrogen napkin. After ball milling, special emphasis is placed on the study of improving the speed of the skin. The magnesium hydride without additives is decomposed at 37 (TC) under the conditions of helium gas flow (ie, hydrogen partial pressure is zero). % secret, after 2〇J, time ball mill treatment, hydrogen release temperature can be reduced i 5 (rc. Add _5 of hydrogen to pour, and then _ 22 dehydrogenation treatment] The hydrogen release temperature can be further reduced. In addition to _5, attached, ^, and other metal naphtha, or Ti〇2 oxide Addition, the improvement of the hydrogenation rate of the hydrogenation of the ball, and the improvement of the nitrogen reaction rate. It is reported that the New Zealand method or the township has little effect. But because the additive belongs to the transition element oxide, the specific gravity is as high as 4 mass%, so the total chlorine storage is about 4 mass%. Significantly reduce the original lightweight effect of the magnesium alloy. [Summary of the Invention] Compared with the conventionally used Nb〇5, the addition of metal nanoparticles such as Ni, Fe, Co or Ti〇2 201111520 oxide, due to the high specific gravity of the additive The amount of hydrogen storage has dropped drastically. The inventors of this case have found that the magnesium alloy has a too slow rate of hydrogen absorption and desorption. It can introduce different degrees of plastic deformation mechanism, such as cold rolling, to produce fine grains of the original coarse alloy. And the particles are refined, and the ball mill is used to simultaneously add graphite in the ball milling process, and the alloy is ball-milled into a powdery hydrogen storage powder to reduce the hydrogen absorption and desorption temperature and increase the hydrogen absorption and desorption rate. As for the optimum amount of graphite added, the weight percentage of the original hydrogen storage alloy is between 3 and 10 wt%. When the amount of graphite added is less than 3 wt%, it is not enough to make it difficult to activate the magnesium-based hydrogen storage alloy to rapidly absorb and release hydrogen. In addition, since graphite itself does not absorb hydrogen, excessive graphite addition may damage the overall hydrogen storage. The amount of graphite should not exceed 10 wt%. [Examples] In order to facilitate the experiment, the magnesium alloy was directly selected from commercial ZK6 bismuth magnesium alloy iMg_6mass%Zn_(X8mass%Zr) as hydrogen storage material, and graphite was added to improve hydrogen storage characteristics and hydrogen absorption and desorption behavior. The bismuth alloy sheet is first processed by cold rolling at a rolling rate of 80%, and then smashed into granules by a trowel. The preparation method of the alloy powder is that the boring tool is diced into pellets and placed in a ball mill, and graphite and the alloy granules are added together to seal the tank and then ball milled. The amount of graphite added by the towel relative to the original hydrogen storage alloy is G, 3 ′ 5 and 1 〇 wt%, respectively. As a result, it was found that the best hydrogen storage amount and air absorption rate were 5 wf% of graphite added. The first picture shows sample C (addition of 5 mass% graphite as a catalyst for common ball milling 2 〇 small 201111520) 'sample B (no graphite ball milled for 2 hours) and sample a (cold rolling granules cold rolling extension) The first activation difference of the three samples. Sample C, in the present example, started to have a hydrogenation reaction at 16 minutes. While sample b started to hydrogenate at about 28 minutes, it was not significant and had to be apparent after 125 minutes. However, the rate of hydrogen absorption was still much slower than that of sample c with graphite ball milled 2 〇 h. On the other hand, Sample A began a slow hydrogenation reaction at 1400 min. The addition of 5 mass% graphite ball mill 2 〇h has a short activation latency because the oxide layer is peeled off during the ball milling process and a layer of graphite is uniformly deposited on the surface of the ZK60 alloy. ^ Accelerate the dissociation of hydrogen molecules on the surface into hydrogen atoms. In the second graphs (8) and (b), the samples of sample C (present invention) and sample b (comparative example) were subjected to hydrogen absorption and desorption for 10 cycles. Sample c can be fully activated after the first hydrogen absorption and desorption. The fifth time, the saturated hydrogen absorption can reach 69 mass%, and then the hydrogen absorption will slowly decrease, but it will be maintained in the first time. 6.7 The amount of hydrogen absorbed by mass% or more. Using the hydrogenation rate measurement method of JIS metal hydride, the saturated hydrogen absorption amount of 80% was taken as the effective hydrogen absorption amount, and the hydrogen absorption rate was calculated. It was found that 80% of saturated hydrogen absorption can be achieved in 5 minutes, the effective hydrogen absorption is 5.52 mass%' and the hydrogen absorption rate is 1.104 mass〇/0/min, and saturated suction can be achieved in about 30 minutes. Dong. On the other hand, it is shown in Figure (b) that the sample s b has not been fully activated by 10 cycles of hydrogen absorption and desorption, which is consistent with the conventional results. According to the present invention, the Mg-based nitrogen storage alloy is ball-milled by cold rolling or ball milling, and it can be known that the cold rolling process of the ZK60 alloy by cold rolling rate of '80% can obtain a relatively high nitrogen absorption 201111520' the highest among the existing hydrogen storage alloys. The amount of hydrogen absorption is '4 mass% or more. Then, 5 mass% of graphite was added as a catalyst for 20 h, and the first activation was carried out, and hydrogenation was started at i6 min. After 10 cycles of hydrogen absorption and desorption, 5 mass% graphite was added as a catalyst for 20 h. The sample was completely activated after the first hydrogen absorption and desorption. The fifth time, the saturated hydrogen absorption was 6.9 mass%. After that, the amount of hydrogen absorbed slowly decreased, but it was able to maintain a hydrogen absorption of 6.7 mass% or more in the first pass. The effective hydrogen absorption is 5.52 mass%, and the hydrogen absorption rate is u〇4 mass%/min', and the saturated hydrogen absorption can be achieved at about 3 〇 min. In summary, the present invention is a novelty, progressive and available for industrial use, and should comply with the patent application requirements stipulated in the Patent Law of China, and the invention patent is filed according to law. Quasi-patent, to the feeling of prayer.
【圖式簡單說明】 第一圖：本發明與習知储氫合金之活化速率差異圖； 第二圖：本發明與習知儲氫合金之循觀放氫曲線圖，⑻添加 5Wt%石墨（本發明），)未添加石墨（習知)。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing the difference in activation rate between the present invention and a conventional hydrogen storage alloy; FIG. 2 is a graph showing the apparent hydrogen evolution curve of the present invention and a conventional hydrogen storage alloy, and (8) adding 5 wt% graphite ( The present invention),) no graphite is added (conventional).