445664 五、發明說明（1) 本發明係有關一種鎳-氫氧化鎳電極及其製法.。 鎳氫電池鎳正極之活性物氫氧化鎳N i ( Ο Η ) 2導電性 不佳，·現今所用來改善氫氧化鎳在正極中導電度的方法是 在電極中添加氧化鈷（CoO ).，藉由氧化鈷在電解液中溶 解、.沉積到最後充電的過程可在氫氧化鎳顆粒表面沉積一 層過氫氧化鈷（CoOOH )導電薄膜，.使電極内部形成網狀 的導電結構：而提高電極内部的導電度。然而，.添加氧化 鈷也有幾項缺點，.例如氧化鈷所溶解之二價鈷離子並不容 易沉積在氫氧化鎳顆粒和顆粒之接觸面：使得此接觸面不 易生成導電物質過氫氧化鈷，，而影響其導電度；並且氧化 鈷粉末在空氣中表面易氧化成C 〇3 04 :而阻礙氧化鈷在電極 液中溶解，.影響其效能。，雖然美國專利第5 5 1 4 4 9 7號專利 提出在氧化鈷粉末表面先披覆上含有-0H基的物質可以防 止氧化鈷氧化，.但卻也增加成本。. 美國第5 6 1 1 8 2 3號專利是對氫氧化鎳粉末提出一表面 無電鍍流程，、並且亦指出表面彼覆一鎳層有助於提高氫氧 化鎳的利用率，，但其所披覆的為一含有少量磷之鎳層：並 且在其電極中亦需添加氧化鈷才能使氫氧化鎳的利用率達 7 5 %以上。，但該方式仍然有上述添加氧化鈷的缺點。，發明 人等經長期研究，，發現可用氫氧化鎳表面披覆一純鎳之粉 末為鎳氫電池正極的活性物質；以取代電極中添加氧化鈷 來提高電極導電度。.此方法和前述專利不同點在於我們所 提出的彼覆層為純鎳，，而前述專利為一錄-麟合金，，此兩 種差異將造成導電度不同，，而有不一樣的氫氧化鎳利用445664 V. Description of the invention (1) The present invention relates to a nickel-nickel hydroxide electrode and a method for manufacturing the same. Nickel-hydrogen battery nickel cathode active material nickel hydroxide Ni (Η Η) 2 has poor electrical conductivity. The current method used to improve the conductivity of nickel hydroxide in the positive electrode is to add cobalt oxide (CoO) to the electrode., By dissolving cobalt oxide in the electrolyte and depositing it to the final charge, a layer of cobalt peroxide (CoOOH) conductive film can be deposited on the surface of nickel hydroxide particles to form a mesh-like conductive structure inside the electrode: improving the electrode Internal conductivity. However, the addition of cobalt oxide also has several disadvantages. For example, the divalent cobalt ions dissolved by cobalt oxide are not easily deposited on the contact surface of the nickel hydroxide particles and particles: making this contact surface difficult to generate a conductive substance, cobalt cobalt hydroxide, , And affect its conductivity; and the surface of the cobalt oxide powder in the air is easily oxidized to C 0 04: and hinder the dissolution of cobalt oxide in the electrode solution, affecting its efficiency. Although U.S. Patent No. 5 1 4 4 9 7 proposes that the surface of the cobalt oxide powder be coated with a substance containing -0H group to prevent the oxidation of cobalt oxide, it also increases the cost. . US Patent No. 5 6 1 8 2 3 proposed a surface electroless plating process for nickel hydroxide powder, and also pointed out that a nickel layer on the surface would help improve the utilization of nickel hydroxide, but its It is covered with a nickel layer containing a small amount of phosphorus: and cobalt oxide must be added to its electrodes to make the utilization rate of nickel hydroxide reach 75% or more. However, this method still has the above-mentioned disadvantages of adding cobalt oxide. After long-term research, the inventors found that the surface of nickel hydroxide can be coated with a powder of pure nickel as the active material of the positive electrode of a nickel-hydrogen battery; instead of adding cobalt oxide to the electrode, the conductivity of the electrode can be improved. The difference between this method and the aforementioned patent is that the coating we proposed is pure nickel, and the aforementioned patent is a Lu-Lin alloy. These two differences will cause different electrical conductivity and different hydroxides. Nickel utilization
V ΛΑ5 66 ^ 五、發明說明（2) 率，，並且本發明也提出一適當有效的電極鎳含量，，而可完 全取代電極中所添加的氧化鈷，。 本發明所提出的鎳氫電池鎳正極活性物質t，可以不需 要添加氧化鈷；卻能使電極保有良好的導電性，，並且無添 加氧化鈷所造成的缺點。，此活性物質是以氫氧化鎳顆粒為 主體、表面包覆一層多孔純鎳金屬：幫助電極在進行充放 電時電子的傳遞，.以改進氫氧化鎳在電極中導電度不佳的 問題"除了解決電極導電度不佳的問題外，、此活性物質使 用於鎳正極在多項性質，.如高溫充放電：快速放電等均比— 傳統添加氧化鈷的正極有較優良的性能，.因此深具實際應 用的可行性。 利用無電鍍的方式將氫氧化鎳粉末表面披覆一純鎳 層i其處理前氫氧化鎳顆粒表面之形態如圖一之SEM圖所 示，.處理後之氫氧化鎳表面包覆一多孔緻密之純鎳層在 X R D (圖二）分析中顯示為鎳之（1 1 1 )結晶結構：此緻密 的純鎳層.在鎳正極内部扮演著無數個電子傳遞的橋樑，，可 降低電極内部的阻抗.。若以交流阻抗法（AC-Impedance method )量測不同組成電極内部阻抗，，其中測試電極面積 2 X 2 cm2，電極厚度約為0. 0 8 cm，則其阻抗分別為：純氫 * * « 氧化鎳正極：2Ω :添加15.0wt%CoO鎳正極：0·3Ω :表面 彼覆15.0wt%純錄正極：0.3Ω ;而電極中氫氧化鎳的利用 率（utilization)分別為52%、84%、86%。由以上數據顯 _ » · 示本發明之新材料-氫氧化鎳表面披覆純鎳層：不但能降 低電極内部阻抗，、提高電極内部活性物質利用率，.且其效V ΛΑ5 66 ^ 5. Description of the invention (2), and the present invention also proposes a suitable and effective electrode nickel content, which can completely replace the cobalt oxide added in the electrode. The nickel positive electrode active material t of the nickel-metal hydride battery provided by the present invention does not need to add cobalt oxide; however, it can maintain good conductivity of the electrode without the disadvantages caused by adding cobalt oxide. This active material is nickel hydroxide particles as the main body and the surface is coated with a layer of porous pure nickel metal: to help the electrode transfer electrons during charge and discharge, to improve the problem of poor conductivity of nickel hydroxide in the electrode " In addition to solving the problem of poor electrode conductivity, this active material is used in nickel cathodes in a number of properties, such as high temperature charge and discharge: fast discharge, etc. — traditional anodes with cobalt oxide have better performance, so deep With practical feasibility. The surface of the nickel hydroxide powder is coated with a pure nickel layer by electroless plating. The morphology of the surface of the nickel hydroxide particles before the treatment is shown in the SEM image of the first. The dense pure nickel layer shows the (1 1 1) crystal structure of nickel in XRD (Figure 2) analysis: This dense pure nickel layer acts as a bridge of numerous electron transfers inside the nickel positive electrode, which can reduce the interior of the electrode The impedance ... If the internal impedance of different composition electrodes is measured by the AC-Impedance method, where the test electrode area is 2 X 2 cm2 and the electrode thickness is about 0.08 cm, the impedances are: pure hydrogen * * « Nickel oxide positive electrode: 2Ω: 15.0wt% CoO nickel positive electrode: 0 · 3Ω: surface covered with 15.0wt% pure recorded positive electrode: 0.3Ω; and the utilization rate of nickel hydroxide in the electrode is 52% and 84%, respectively 86%. The above data shows that the new material of the present invention, nickel hydroxide, is coated with a pure nickel layer: it can not only reduce the internal resistance of the electrode, but also improve the utilization rate of the active material inside the electrode.
A A5 6 6 ^ 五、 發明說明（3) 果 比 添 加 等 量 的 氧 化 銘 略佳％除 此 我們所提出的新材料尚 有 優 良 的 溫 使 用 性 能 。，由於鎳 正 極在充電時除了自身的 氧 化 反 應 外 ( 反 應 式1 ) .，尚伴隨- '競爭反應-氧氣生成反 應 ( 反 應 式 2 ) ! 當電極在高溫進行充電；此氧氣生成反 應 將 更 有 利 生 成 * 而 降 低充電效 率 。.本發明所提出的新材 料 由 於 在 氫 氧 化 鎳 表 面 坡覆一多 孔 緻密的純鎳層，.可以改 變 氧 氣 生 成 的 反 應 機 構 \拉大反 應 式（1 )和（2 )的電位 差 ί 而 具 有 較 尚 的 面 溫 充電效率 0 \ N i (OH) 2 + OH- —> Ni 00Η + Η20 + < 3' ( 1 ) 40H- —02 + 2H 20 + 4e' ----------(2) » 在 先 前 專 利 中 認 為 ，，氫氧化 鎳 表面彼覆錄-填含量在5 35 wt%可以改善電極導電度，，並且鎳-磷含量在15wt%以 上 可 使 氫 氧 化 鎳 利 用 率 達7 5%以」 L ·< >而本發明所提出的材 料 j ^ 當 純 鎳 含 量 為 11 .2 w t %時，氫氧化鎳利用率可達8 1 % « 效 果 明 顯 較 好 當 鎳 含 量大於1 1 %電極壽命可維持1 5 0次以 上 〇 我 們 也 發 現 « 由 於 鎳在充放 電 過程會氧化成氫氧化. 鎳 9 *當 鎳 含 量 太 少（< 9 2 w t % )，· 經 過幾次充放電後電極之 電 容 量 明 顯 下 降 * 顯 示 錄含量太 少 並不能提供較長的電極 壽 命 ° . 並 且 當 鎳 含 量 達2 4 w t %時. 氫氧化鎳利用率可達 100% *當 鎳 含 量 為3 1 .5 wt %時，.氫氧化鎳利用率達97% _，因 此 發 明 人 等 提 出 一 適 田 的純錄含 量 為 10wt% 至 35wt%，.以 11 w t % 至 3 2 w 1% 為 更 佳 ] 本 發 明 之 一 a 的 ，· 在提供一 種 鎳-氫氧化鎳電極。 本 發 明 之 另 的 ，在提供 種鎳-氫氧化鎳電極之 '1A A5 6 6 ^ V. Description of the invention (3) The fruit is slightly better than adding the same amount of oxidation inscription. In addition, the new material we proposed has excellent temperature performance. Since the nickel positive electrode is charged in addition to its own oxidation reaction (Reaction Equation 1), it is also accompanied by-'competition reaction-oxygen generation reaction (Reaction Equation 2)! When the electrode is charged at high temperature; this oxygen generation reaction will be more favorable Generates * and reduces charging efficiency. The new material proposed by the present invention has a porous and dense pure nickel layer on the surface of nickel hydroxide, which can change the reaction mechanism of oxygen generation and expand the potential difference between reaction equations (1) and (2). Charging efficiency at relatively high surface temperature 0 \ N i (OH) 2 + OH- — > Ni 00Η + Η20 + < 3 '(1) 40H- —02 + 2H 20 + 4e' ------- --- (2) »In the previous patents, it is believed that the nickel hydroxide surface covering-filling content of 5 35 wt% can improve the conductivity of the electrode, and the nickel-phosphorus content above 15 wt% can make nickel hydroxide The utilization rate is up to 75% with "L · < > and the material proposed by the present invention ^ When the pure nickel content is 11.2 wt%, the utilization rate of nickel hydroxide can reach 81%.« The effect is significantly better When the nickel content is more than 11%, the electrode life can be maintained more than 150 times. We also found that «Because nickel will oxidize to hydroxide during the charge and discharge process. Nickel 9 * When the nickel content is too small (< 9 2 wt%), · The capacitance of the electrode is significantly reduced after several charge and discharge * It is shown that too little recording content does not provide a long electrode life °. And when the nickel content reaches 24 wt%. The utilization rate of nickel hydroxide can reach 100%. * When the nickel content is 3 1.5 wt%. The utilization rate of nickel hydroxide is 97%. Therefore, the inventors have proposed that the content of pure content of Shida is 10wt% to 35wt%, and 11 wt% to 3 2 w 1% is more preferable. , · A nickel-nickel hydroxide electrode is provided. Another aspect of the present invention is to provide a '1
ΛΑ5 66 A 五、發明說明（4) 製法。. 圖一為氫氧化鎳表面鍍鎳前（a)後（b)之SEM圖： 圖二為純氫氧化鎳與無電鍍鎳後之氫氧化鎳XRD圖.。 圖三為1 5 w t %鍵錄：添加氧化銘.和純氫氧化銻錄正極 充放電電位圖， 圖四為15wt%鍍鎳和添加15wt%CoO電極在不同溫度下 之電容量比較圖q 圖五為兩種不同電極在不同放電電流下的電容量比較 圖。. 圖六為不同鍍鎳和氧化鈷添加量對鍍鎳電極電容量影 響圖。‘ 圖七為低鍍鎳量電極電容量和充放電次數關係圖，。 本發明之鎳-氫氧化鎳電極：其係以鎳-氫氧化鎳粉末 塗佈於基材上，.其特徵在：，該鎳-氫氧化鎳粉末為氫氧化 鎳粉末表面彼覆一多孔緻密之鎳，.該鎳實質上為純鎳.，且 該鎳佔該鎳-氫氧化鎳粉末重量比為1 Owt%至3 5wt%,。 本發明之鎳-氫氧化鎳電極之製法，其包括： (1) 在氫氧化鎳粉末表面披覆一層鎳、，形成鎳-氫氧化 鎳粉末、其中該鎳的含量佔鎳-氫氧化鎳重量比為l〇wt %至 35wt% °· (2) 將步驟1之鎳-氫氧化鎳粉末塗佈於鎳基材表面。 本發明所謂粉末，.意指小於2 0 0微米（m i c r on )之細顆 粒 為進一步說明本發明，.茲以實施例說明如下：ΛΑ5 66 A 5. Description of the invention (4) Manufacturing method. Figure 1 shows the SEM images of (a) and (b) before nickel plating on the surface of nickel hydroxide: Figure 2 is the XRD pattern of nickel hydroxide after pure nickel hydroxide and electroless nickel plating. Figure 3 is a 15 wt% bond record: the addition of an oxide oxide. And pure antimony hydroxide record the positive and negative charge potentials. Figure 4 is a comparison of the capacitance of 15 wt% nickel plating and the addition of 15 wt% CoO electrodes at different temperatures. Five is a comparison chart of the capacitance of two different electrodes under different discharge currents. Figure 6 shows the effect of different nickel and cobalt oxide additions on the capacitance of nickel-plated electrodes. ‘Figure 7 shows the relationship between the capacitance of a low nickel plating electrode and the number of charge and discharge cycles. The nickel-nickel hydroxide electrode of the present invention is coated with a nickel-nickel hydroxide powder on a substrate. It is characterized in that the nickel-nickel hydroxide powder is a nickel hydroxide powder coated with a porous surface Dense nickel, the nickel is substantially pure nickel, and the weight ratio of the nickel to the nickel-nickel hydroxide powder is from 10 wt% to 35 wt%. The method for producing a nickel-nickel hydroxide electrode of the present invention comprises: (1) coating a surface of nickel hydroxide powder with nickel to form a nickel-nickel hydroxide powder, wherein the content of the nickel accounts for the weight of the nickel-nickel hydroxide; The ratio is 10 wt% to 35 wt%. (2) The nickel-nickel hydroxide powder of step 1 is coated on the surface of a nickel substrate. The so-called powder in the present invention means fine particles smaller than 200 micrometers (m i c r on). To further illustrate the present invention, the following examples are used to explain:
t 445 6S4 五、發明說明¢5) '~~-- 實施例一 取0 97g表面含μt 445 6S4 V. Description of the invention ¢ 5) '~~-Example 1 Take 0 97g surface with μ
^ ^ ,, , 、3 ib· 46wt% 純鎳之氫氧化錄·，0_ 03gPTFE 為黏結劑（binder )，斑、由这 / 、，丄 0 0 η她二、 ν，與適量之去離子水攪拌後均勻塗佈於 2 X 2 cm2 (雙面）的發泡锸 ^ ^ ^ , Λ L錦網上（規格為5 Ο 0 g / m2) ·，以兩噸的 壓力壓成約0.08cm厚的+ ^ , ^ Λ ^ r Λ 〇/ 、正極片，，此時正極片含純鎮量為 15.0wt%。.取一般市隹拍— .^ , N 錦氣電池負極為對應電極（counter e = ro e ’，Hg/Hg〇 為參考電極（ref er ence e l ec trode ). v，& 為隔離膜（seParator) : 31wt% 氫氧 化钟為電解液進行充放電測試。，電極以〇 . 2 c充電7小時.， 然後=0,. 2C放電至〇. 2V ν· s jjg/HgO :經幾次充放電待 其穩定後，，量測其電極電容量。.同樣分別取0 . 82g氫氧化 錄 *、〇.15g C〇0、0.03g PTFE 以及 〇.97g 氫氧化鎳 〇.〇3g PTFE 依上述方法製成正極片並進行電容量測試，。圖三為 經過3 0次充放電後，，三種不同電極之充放電電位與時間關 係圖從圖中可清楚看出本發明所提出的新材料為正極物 質，.其電容量和添加等量的氧化鈷電極相近’•但放電電位 卻較高。 實施例二 將實施一中15wt%表面含鎮之正極及添加15wt%氧化銘 正極分別於3 〇 t、4 0。(： ： 5 0 °C、. 6 0 °C恆溫下進行充放電.， 圖四為其不同充^電溫度與電極中氫氧化鎳比電容量 (specific capacity)關係圊，.圖中顯示表面含純鏡之正 極在不同溫度下所展現的電容量比添加氧化結之正極好·。^ ^ ,,,, 3 ib · 46wt% Hydrogen hydroxide of pure nickel, 0_03gPTFE as binder, spot, y / o, 丄 0 0 ηshe II, ν, and appropriate amount of deionized water After stirring, spread evenly on 2 X 2 cm2 (double-sided) foam 锸 ^ ^ ^, Λ L brocade (specified as 5 0 0 g / m2), and press it to a pressure of about 0.08cm with two tons of pressure. + ^, ^ Λ ^ r Λ 〇 /, the positive electrode sheet, at this time, the positive electrode sheet contains a pure ballast of 15.0wt%. Take the general market photo —. ^, N negative gas battery is the corresponding electrode (counter e = ro e ', Hg / Hg〇 is the reference electrode (ref er el ec trode). V, & is the insulation film ( seParator): 31wt% hydroxide hydroxide was used as the electrolyte for charge and discharge test. The electrode was charged at 0.2 c for 7 hours. Then, 0, 0.2 C was discharged to 0.2 V ν · s jjg / HgO: after several charges After the discharge is stabilized, measure the electrode capacitance. Similarly, take 0.82 g of hydroxide *, 0.15 g of C〇0, 0.03 g of PTFE, and 0.97 g of nickel hydroxide 0.03 g of PTFE as above. The method is to make a positive electrode sheet and conduct a capacitance test. Figure 3 shows the relationship between charge and discharge potential and time of three different electrodes after 30 charge and discharge cycles. The positive electrode material has the same capacitance and the same amount of cobalt oxide electrodes as the added amount, but the discharge potential is relatively high. In the second embodiment, 15% by weight of a positive electrode containing a town on the surface and 15% by weight of an oxidized positive electrode were added at 30%. t, 4 0. (:: 50 ° C,. 60 ° C charge and discharge at a constant temperature. Figure 4 is different ^ Electrical temperature nickel hydroxide electrode specific capacitance (specific capacity) relation pigsty, Figure shows a positive electrode containing the pure surface of the mirror at different temperatures to show the capacity ratio of n junction oxide is added in an excellent ·.
Λ45 66 4 五、發明說明（6) 實施例三 將實施二兩種不同電極以1 / 3 C充電4. 2小時，並分別 以 1/3 C、l/2 C、1C、2C 放電至0.2V v.s. Hg/HgO > 量測 其充電容量.，圖五為其不同放電電流下之電容量比較圖·， 由圖中可看出表面含純鎳之正極其大電流放電性能比添加 氧化钻之正極優良。 * 實施例四 依據實施例一中之正極製法及電容量測試方法分別製 作表面坡覆純鎳重量比6. 5 .、9. 2 : 1 1 . 2 .、1 5. 6 ,、1 8. 6 : 2 3. 9 .、3 1 . 5 wt %正極以及添加氧化鈷重量比5、8 ' 1 0、 * * · 1 2、. 1 5 w t %正極測試其電容量其結果如圖六所示，.由圖中 可看出表面彼覆純鏡重量比大於llwt%時，，其電容量比添 加等量氧化敍之正極好.。 實施例五 將實施例四中披覆純鎳重量為6. 5 \ 9 . 2 : 11. 2 w t %之 正極進行充放電壽命測試.。圖七顯示當純鎳含量為6. 5 .、 9 . 2 w t %時，.電極之比電容量經3 0次充放電後明顯下降.，而 鎳含量1 1 . 2 wt %的正極經1 5 0次充放電後，.亦能維持其比電 容量丨 i以上五個實施例可知：以表面坡覆一純鎳層的氫氧 化鎳為活性物質之正極，，當純鎳含量大於1 1 w t %以上時.，Λ45 66 4 V. Description of the invention (6) In the third embodiment, two or two different electrodes are charged at 1/3 C for 4.2 hours, and discharged at 1/3 C, 1/2 C, 1C, and 2C to 0.2. V vs Hg / HgO > Measure its charging capacity. Figure 5 is a comparison of the capacitance under different discharge currents. From the figure, it can be seen that the positive current discharge performance of the cathode containing pure nickel on the surface is higher than that of the oxide diamond The positive electrode is excellent. * Example 4 According to the positive electrode manufacturing method and the capacitance test method in Example 1, the weight ratios of the pure nickel on the surface of the slope are 6.5, 9.2: 1 1.2, 15.6, 18. 6: 2 3. 9., 3 1.5 wt% positive electrode and the weight ratio of added cobalt oxide 5, 8 '1 0, * * · 1 2.. 1 5 wt% positive electrode to test its capacitance. The results are shown in Figure 6. It can be seen from the figure that when the weight ratio of the pure mirror on the surface is greater than llwt%, the capacitance is better than the positive electrode with the same amount of oxidation. Embodiment 5 The positive electrode covered in Example 4 with a weight of pure nickel of 6. 5 \ 9. 2: 11. 2 w t% was subjected to charge and discharge life test. Figure 7 shows that when the pure nickel content was 6.5, 9.2 wt%, the specific capacitance of the electrode decreased significantly after 30 charge and discharge cycles, and the positive electrode with a nickel content of 11.2 wt% passed 1 After 50 charges and discharges, the specific capacitance can also be maintained. In the above five examples, it can be known that the nickel hydroxide with a pure nickel layer on the surface slope is used as the positive electrode of the active material. Above wt%.,
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