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1、摘 要锌镍二次电池具有容量大、比能量高、安全性好、工作电压高、无记忆效应、良好的高倍率放电性能、可大电流快速充放电、价格便宜的特点等，在电池的生产和使用过程对环境不产生污染，属于绿色电池。但是电池的循环性能太低。目前锌镍电池锌负极常用的活性物质为氧化锌，但是氧化锌在碱性电解质溶液中溶解度较高，在使用过程中，锌负极会出现形变，沉积生长出锌枝晶，甚至反生钝化，自放电等问题，这大大的降低了锌镍电池的循环性能。为了提高锌镍电池的电化学性能，除了在氧化锌、添加剂以及电解质溶液上的改进外，还可以通过寻找更有潜力的材料作为活性物质，减小锌负极的形变及锌枝晶的问题。本次实验通过低温固相合成的方法制备出了磷酸锌
2、钠，通过XDR和SEM的表征分析，自制出了具有六方晶系P6122空间群结构的手性磷酸锌钠( NaZnPO4H2O)。将自制的磷酸锌钠与不同含量的氧化锌通过物理混合作为活性物质制备成锌负极，进行了交流阻抗、循环伏安测试。结果表明添加氧化锌可以减小电化学反应阻抗，同时其中磷酸锌钠(75%)/氧化锌(25%)的电化学阻抗最小，数值为11.66。组装成模拟电池进行充放电性能测试。在80个循环之后，添加了25%氧化锌模拟电池的放电容量效率比其他的含量氧化锌的放电容量效率都高，依然有45%50%的放电容量效率。添加氧化铋之后的峰电位差均小于未添加氧化铋的峰电位差，氧化铋提高了锌镍电池的可逆性。增大了电化学
3、反映电阻。以较佳比中添加11%氧化铋为活性物质的模拟电池的循环寿命更稳定更持久。最高放电容量242.4mAh/g，保持率高。第200次循环时其放电容量依然有162mAh/g。随着循环次数的增加，在4mA充放电下，磷酸锌钠的容量逐渐下降，最后容量保持在80mAh/g左右，而在6mA充放电下，磷酸锌钠的容量没有出现很大波动，一直保持在100mAh/g左右。在第12个循环之后，6mA下充放电的放电容量都比4mA下充电的放电容量要高。与4mA的相比，磷酸锌钠在6mA充放电下有着更低的充电平台和更高的放电平台。从循环稳定性来看，磷酸锌钠在电流为6mA下充放电，其循环寿命更好。关键词：锌镍电池；锌负极；磷
4、酸锌钠；电化学性能ABSTRACTSecondary zinc nickel battery has high capacity, high specific energy, good safety, high working voltage, no memory effect, good high rate discharge performance, large current fast charge and discharge, cheap etc characteristic. Do not produce pollution to the environment at the pro
5、duction of the battery and using. It belongs to green Battery. But the cycle of the battery performance is too low. At present, zinc oxide is usually used as active material for zinc nickel zinc battery cathode, but zinc oxide is high solubility in the alkaline electrolyte solution. In the working,
6、zinc anode will be deformation. It wills dendrite growth with deposition of zinc, even passivity and self discharge. It will greatly reduce the zinc nickel battery cycle performance. In order to improve the electrochemical performance of zinc nickel battery. Except to improve zinc oxide, additive an
7、d electrolyte solution, it can also to find more potential materials as active material and reduce the deformation of zinc anode and the problem of zinc dendrite. This experiment using low temperature solid method to prepare sodium zinc phosphate and analysis it with X-ray diffraction and scanning e
8、lectron microscope. It can indicate the preparation of sodium zinc phosphate which is hexagonal system P6122 space group of chiral sodium zinc phosphate. Using sodium zinc phosphate and adding different content of bismuth oxide as the cathode active material to prepare of zinc anode. It conducts a A
9、C Impedance tester and cycling voltammeter. The results show that: adding bismuth oxide can reduce the electrochemical reaction impedance. At the same time sodium zinc phosphate and zinc oxide 75% than 25%, the electrochemical impedance is minimal. Value is 11.66 . Assembling simulation battery char
10、ge and discharge performance test. After 80 cycles, adding25% zinc oxide simulation of the battery discharge capacity efficiency than other discharge capacity of the content of zinc oxide efficiency is high, There are 45% 50% of the discharge capacity efficiency, After adding bismuth oxide of peak p
11、otential difference is less than the peak of not adding bismuth oxide potential difference. Adding bismuth oxide can improve the zinc nickel battery reversibility and increases the electrochemical reflect the resistance. By adding 11% better than the bismuth oxide as the active material simulation o
12、f the battery cycle life more stable and durable. The discharge capacity can reach 242.4 mAh/g and keep the high rate. When the 200th cycle its discharge capacity is still 162 mah/g, with the increase of cycling times, Under the 4 mA charge and discharge, the capacity of zinc phosphate sodium gradua
13、lly decline. The capacity to keep around 80 mah/g. And under the 6 mA charge and discharge, the capacity of zinc phosphate sodium did not appear a large fluctuations, it has remained at about 100 mah/g. After the 12th cycle, all the discharge capacity of the charge and discharge under 6mA discharge
14、capacity is higher than 4 mA , Compared with the 4 mA, sodium zinc phosphate at 6 mA charge and discharge with lower charging platform and higher discharge platform. From the cycle stability, sodium zinc phosphate under current is 6 mA charge and discharge, the cycle life is better.Keywords: Zn-Ni b
15、attery; zinc electrode; sodium zinc phosphate; electrochemical property目 次摘 要IABSTRACTI目 次II1 绪论11.1 锌镍电池发展历史11.2 锌镍电池的现状及其特点11.3 锌负极存在的问题21.3.1锌负极的形变及锌枝晶的形成21.3.2锌负极的钝化及腐蚀21.4 锌电极活性物质的研究进展21.4.1纳米氧化锌31.4.2锌酸钙41.4.3锌铝水滑石51.5 锌镍电池的工作原理52 实验内容与方法72.1 实验试剂与相关仪器72.1.1实验试剂72.1.2实验仪器72. 2 实验步骤82.2.1负极的制备82.2.2正极的制备82.3 电解质溶液的制备82.4 磷酸锌钠的的表征92.4.1XRD分析92.4.2SEM分析92.4 电化学性能测试92.4.3交流阻抗92.4.4循环伏安92.4.5充放电测试93 实验结果与讨论93.1 磷酸锌钠的表征93.1.1XRD分析93.1.2SEM分析103.2 磷酸锌钠中添加氧化锌113.2.1磷酸锌钠中添加不同含量氧化锌对锌负极交流阻抗的影响113.2.2磷酸锌钠中添加不同含量氧化锌对锌负极循环伏安的影响123.2.3磷酸锌钠中添加不同含量氧化锌对锌镍电池充放电性能的影响133.2.4磷酸锌钠中添加不同含量氧化锌对锌镍电池循环性能的影响153
