- 作者: 薄善萍; 張簡貴明; 林泰璋
- 作者服務機構: 國立清華大學工業化學研究所
- 中文摘要: (一)預期目標 本計畫研究鎳鋅次電池中鋅極形狀變化之改進、組合隔離片材料之選擇及組合方法,以及探求非燒結鎳極之製造方法和所需之最適條件,以增進鎳鋅次電池之放電效率、穩定性和壽命。(二)結果 1.各項鋅極形狀變化之研究與改進實驗結果,顯示管狀鋅極形狀變化雖小,但鋅活性物之利用率太低。電鍍法所製之鋅極放電性能雖較佳,但形狀變化則較大。電池之電解液中添加 V 0 ,會使電池之放電性能劣化,鋅極之形狀變化加劇。添加過量的Pb0 (0.13 g/liter),會使電池性能劣化,但加適量的Pb0 (0.031 g/liter),可改善電池放電性能,但鋅極形狀變化加大。鋅極活性物中添加1.0 wt. % SnC1 ‧2H O或 TiO ,使鋅極表面易生鈍化現象,故放電量減少,但鋅極形狀變化小。鋅極活性物中添加1.0wt.%In O ,可改善電池放電性能,但鋅極形狀變化加大。電解液用氧化鋅溶液飽和,可改善鋅極之形狀變化。 2.隔離片之組合及材料選擇一研究結果證明,靠鋅極之表面加一層不織布,比直接加一層玻璃紙,放電性能差,鋅極形狀變化大。靠鋅極之表面宜加一層微孔性,低電阻的隔離膜,如玻璃紙(Cellophane)。 3.鎳電極之製造方法及最適宜條件--目前一般鎳電極的製造方法為燒結型,須以複雜的化學填注程序將 Ni(OH) 充填於多孔性之燒結鎳板中。此種方法程序複雜而且成本高。此一部份之研究是要探求一較簡單之非燒結型鎳極製造方法(即塗片法)。研究結果顯示非燒結型鎳極單位重量的容量較燒結型鎳極大,製造成本亦較低,適合於低速率放電。燒結型鎳極則機械強度好,表面積大,適於高速率放電,其單位體積之電容量大於非燒結型鎳極。 實驗結果顯示製造非燒結型鎳極之最適條件如下:鎳極活性物含50~60%(重量百分比)之 Ni(OH) ,30~40%之石墨為導電填充劑,10%之 Co(OH) 添加物,以及5%~7.5%之 PVC 或 PS 接著劑;極板製作施加壓力為140~500 lb/cm 。(三)結 論 組合隔離片靠近鋅極之-層最好使用玻璃紙等微孔性低電阻之薄膜,其放電量比多加一層不織布者大20%,且鋅極形狀變化較小。 用塗片法製造鋅極,活性物中可添加適量的 In 0 ,電解液中添加適當濃度之 Pb0,均可改善電池充放電性能。電解液用氧化鋅溶液飽和,可改善鋅極之形狀變化。 非燒結型鎳極之最適製造條件為活性物中含 50~60%之 Ni(OH) ,30~40%之石墨,10%之Co(0H) ;以及5~7.5%之 PS 或 PVC 為接著劑;施加壓力為 140~500 lb/cm ,非燒結型鎳極製作成本紙,程序簡單,可連續自動化生產,甚具發展潛力。‘(四)建 議 鎳鋅次電池之發展有進一步試驗研究的價值,先在研究室中對電池各部份作更深一層的改進研究,然後可製作模式電池,在電動車或其他設備中實地試用。 本文摘要 為改善鎳鋅電池中鋅極形狀變化的缺點,研究:(1)鋅極活性物及電解液添加物;(2)隔離膜組合方式;(3)製作方法對形狀變化的改善效果,以提高電池壽命及電池充放電性能。 實驗結果顯示: (1)管狀鋅極形狀變化小,但能量密度小。 (2)電鍍鋅極放電性能好,但形狀變化大。 (3)電解液添加 V 0 ,會使電池放電性能劣化,形狀變化加劇。添加過量的 Pb0 (1/8g/1),會使電池性能劣化,但適量的 Pb0 (1/82 g/1),可改善電池放電性能,但其形狀變化大。 (4)鋅極添加1% SnC1 ‧2H 0 或 TIN0 ,可使鋅表面積減少,易生鈍化現象,放電量小,但形狀變化小。 (5)鋅極添加1% In 0 ,可改善放電性能,但形狀變化大。 (6)用飽和氧化鋅溶液,可改善形狀變化。 (7)鋅極最內層包不織布,比直接包玻璃紙,放電性能差,形狀變化大。鋅極最內層宜包微孔性(micropore),低電阻的隔離膜,如玻璃紙(cellophane)。
- 英文摘要: The cycle life of nickel-zinc secondary bat-tery has been limited due to failures caused bythe shape change of zinc electrode and thepenetration of dendritic zinc through the separ-ators. The present method of the manufactureof nickel battery electrodes requires the use ofsintered porous nickel plaques and an involvedchemical impregnation process for incorporatingNi(OH) into these plaques. A simpler fabrica-tion process would be desirable. The present work was undertaken to correctthese deficiencies. The experimental results indicate that theextent of zinc electrode shape change can bereduced,but the coefficient of its use will be-come too low if tubular construction is used forpreparation of the zinc electrodes. The zincelectrodes fabricated by the electrodepositionmethod have better discharge performance, butthe extent of shape change they suffered is larger.Both thebattery discharge performance and thezinc electrode shape change will be worsened ifV 0 is added to the electrolyte. The batterydischarge performance can be improved, whereasthe electrode shape change will be aggravatedif the electrolyte is doped with Pb0 (0.031 g/liter).The zinc electrode surface can be made easilypassivated, the discharge capacity will be decrea-sed, and the extent of zinc electrode shape changewill be reduced if about 1.0 wt. % of SnCl ‧2H 0or TIN0 is added to the zinc active material.The battery discharge performance is improvedwhereas the extent of electrode shape change isincreased by the addition of about 1.0% In 0 to the electrolyte. The electrode shape changecan be mitigated by saturating the electrolytewith zinc oxide solution. If a layer of microporous, low resistancecellophane is added to the zinc electrode sideof the separator system in place of a layer ofnonwoven fabric, improved battery dischargeperformance as well as reduced electrode shapechange can be obtained. The capacity per unit weight of the non-sintered composite nickel electrodes is higherthan that found for sintered electrodes. Thecomposite electrodes have better performance atlow discharge rates, and the fabrication processfor such electrodes is simpler, and more econ-omic. However, the sintered electrodes havebetter mechanical strength, larger surface areaand higher capacity per unit volume of thenickel electrode, and better discharge performanceat high discharge rates. The optimum values parameters controllingthe fabrication of non-sintered nickel electrodesobtained by a fractorial experimental programwere: a nickel active material that contains50-60 wt. %Ni(OH) , 30-40% graphite, 10%Co(OH) , and 5-7.5% PVC or PS; and acompression of 900-3,200 psia applied to theelectrode.
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