密封锌镍电池产业化关键问题的研究

【作者】 胡俊；

【导师】 杨占红；

【作者基本信息】 中南大学 ， 应用化学， 2009， 硕士

【摘要】 本论文简要回顾了化学电源和锌镍电池的发展历史,重点阐述了二次锌镍电池的特点、主要存在的问题及相关解决途径、发展状况和未来的市场前景。研究了锌负极添加剂与电解液无机类添加剂对密封锌镍电池的电化学性能和循环使用寿命的影响。TEM测试考察了表面包覆有氧化铟和二氧化硅的氧化锌的形貌,XRD分析证实了氧化锌表面包覆物为氧化铟和二氧化硅,极化曲线和充放电测试研究了包覆后的氧化锌的电化学性能。通过锌负极的制备工艺性与充放电测试对负极粘结剂进行了研究,考察了电解液的组成成分与电解液的浓度对锌镍电池的循环寿命与自放电性能的影响,还考察了锌镍电池的装配比、正负极极片尺寸、集流体与外壳等工艺对锌镍电池性能的影响。对不同的锌负极添加剂的研究表明,添加三聚磷酸钠+全氟表面活性剂、三聚磷酸钠+十二烷基苯磺酸钠、三聚磷酸钠+全氟表面活性剂的锌负极的放电性能有所提高,其中采用全氟表面活性剂与十二烷基苯磺酸钠复配的电池表现出较好的充放电循环性能。对不同的电解液无机添加剂的研究表明,电解液中分别添加适量亚硫酸钠、四硼酸钠和磷酸氢二钠,能够有效改善电池的充放电性能,提高电池的容量保持率。同时添加适量磷酸氢二钠和亚硫酸钠很好的抑制了锌的溶解腐蚀,减少了锌负极形变,延缓了锌负极的钝化。采用化学沉积法制备了表面包覆有氧化铟、二氧化硅的氧化锌。XRD证实了表面包覆物为氧化铟、二氧化硅。TEM图像显示了样品形貌的变化。极化曲线和充放电测试表明包覆后的氧化锌具有较好的耐腐蚀性和电化学性能。对锌负极的粘合剂的研究发现,采用0.4%的羟丙基甲基纤维素(HPMC)与1.5%的丁苯橡胶(SBR)粘合剂的锌镍电池具有更长的循环寿命和更好的存储性能。对电解液的组成的实验表明,采用KOH、NaOH、LiOH的三元电解液提高了电池的充放电效率,延长了电池的循环寿命,提高了电池的荷电保持能力,但增大了密封锌镍电池的内阻。对电解液的浓度的实验表明,采用浓度为7 mol/L的电解液的电池充电时的极化较小,放电效率较高,同时延长了锌镍电池的循环寿命。本实验对锌镍电池的工艺进行了初步研究。研究表明,采用88%的装配比,能降低电池充电时的极化和电池的内阻。正负极极片尺寸在宽度保持一致的情况下,提高了负极活性物质的利用率,有效的延长了锌镍电池的循环寿命,在最终容量衰减到初始容量的80%时,循环寿命达到了328次。在负极集流体铜网的尾部焊接铜箔和在钢壳上镀铜均能提高电池的荷电保持率,相比之下,在钢壳上镀铜的效果更好,设计容量为400 mAh的电池在高温50℃下存储7天后放电容量达到311.306 mAh,自放电率降低到22.17%。更多还原

【Abstract】 The history of chemical power sources and the Zn-Ni battery was reviewed in this paper, focusing on the characteristics, development, future market prospects, the problems existed and the way to solve those problems of the rechargeable Zn-Ni battery. Effects of the zinc anode additives and electrolyte inorganic additives on electrochemical performance and cycle life of Ni/Zn battery were studied by charge-discharge test.The particle morphology of the surface of zinc oxide coating indium oxide and silica was tested by TEM,the zinc oxide surface coating material for indium oxide and silicon dioxide was confirmed by XRD analysis,the e -lectrochemical properties of zinc oxide after coating was studied by polarization curve and charge-discharge tests.The bind of zinc anode have been studied through the prepation process of zinc anode and charge-discharge tests,the composition of the electrolyte and electrolyte concentration on the cycle and self-discharge performance have been examined,also assembly ratio,piece size, collection of fluid and the shell on the nickel-zinc battery performance.Different zinc anode additive have shown that adding sodium tripolyphosphate + perfluorinated surfactants, sodium tripolyphosphate + sodium dodecylbenzene sulfonate, sodium tripolyphosphate + perfluorinated surfactants increased zinc anode discharge performance. perfluorinated surfactants and sodium dodecylbenzene sulfonate have behaved a better charge-discharge performance.Different inorganic additives in electrolyte have shown that adding the proper amount of sodium sulfite,sodium tetraborate and disodium hydrogen phosphate to the electrolyte can effectively improve the battery charge and discharge performance and the battery capacity retention.adding the proper amount of disodium hydrogen phosphate and sodium sulfite inhibits zinc corrosion,reduces the deformation of zinc anode and slowed the passivation of zinc anode.Zinc oxide coated indium oxide or silicon dioxide were prepared by chemical deposition.The surface coating indium oxide or silicon dioxide was confirmed by XRD.TEM images show the changes for the morphology of the sample. Polarization curves and charge-discharge tests show that the zinc oxide coated has good corrosion resistance and electrochemical performance.The studies on the adhesive of zinc anode have found that using 0.4% hydroxypropyl methyl cellulose (HPMC) and 1.5% of the styrene-butadiene rubber (SBR) has a longer cycle life and better storage performance for Zn-Ni battery.The experiments about the electrolyte composition show that the use of KOH,NaOH,LiOH electrolyte improved charge-discharge efficiency, extended cycle life,improved charge to maintain capacity,but increased resistance of nickel-zinc battery.The concentration of electrolyte experiments showed that the concentration of 7mol/L of electrolyte behaves smaller charge polarization ,more efficient discharge and better cycle life.This experiment on nickel-zinc battery technology was studied preliminary.Results shows that 88 percent of the assembly can reduce charging polarization and resistance.The same width size of positive and negative piece increased utilization of active material,extended cycle life which ac hieved 328 times when the final capacity faded to the initial capacity of 80 percent.Welding copper at the rear of copper net and plating copper on steel shell can improve the rate of keeping charge , plating copper on steel shell has better effect, discharge capacity can reach 311.306 mAh,self-dis charge rate reduced to 22.17 percent when a battery designed for 400mAh under 50℃stored for 7 days.更多还原