A Solid‐State Galvanic Cell with Fluoride‐Conducting Electrolytes
A Solid‐State Galvanic Cell with Fluoride‐Conducting Electrolytes
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具有氟化物导电电解质的固态原电池
DOI：
10.1149/1.2132694
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发表时间：
1976
期刊：
影响因子：
--
通讯作者：
J. Schoonman
中科院分区：
文献类型：
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作者：
J. Schoonman
生物09F2。S_2和~-PbF_2：AgF是适用于原电池的氟离子导电电解质。介绍了一种制备Pb/~-PbF_2：AgF/BiO_0. ogF 2。s2/Bi的关系。根据电池反应3 Pb + 2BiF--> 3 PbF 2 Jr 2Bi计算的开路电压为0.33 V，与理论值雅阁。电池在29，8~ 176 ℃温度范围内放电，电流密度为12-63 mA/m2.短路电流范围为15.7至386 mA/m 2。在几天的时间内获得了相对恒定的负载电路电压。在最近的文献中，具有萤石或tysonite结构的氟化物导体的电性能受到了相当大的关注（1-8）。这些材料中的一些目前用作固体电解质。PbF 2已成功地用作薄膜原电池中的固体电解质（5）。薄膜原电池Pb/PbF 2/CuF 2（PbF 2）/Cu已通过真空蒸发（5）制造。然而，CuF 2在室温下是高电阻材料。为了提高导电性，CuF 2与PbF 2共沉积。这又导致开路电压（OCV）低于0.70 V的理论OCV。CuF 2和特别是AgF都对空气中的水分具有反应性。因此，需要特别的预防措施以避免薄膜（5）起泡。Kennedy和Miles（6）测试了氟化钾掺杂的~-PbF 2作为原电池中的电解质，CuF 2或AgF作为阴极材料。分别实现了0.70和1.30 V的开路电压，但当置于负载和电流下时，电池电势迅速下降。这种差的性能可能是由于形成了由低电导率纯a-PbF 2（6）组成的阳极钝化层。最近，我们报道了与泰森石相关的BiOzF 3 -2x（x：0.09，~ 0.1）（9）的固体电解质性质。电导率是离子型的，并且在环境温度下超过未掺杂的~-PbF 2的电导率。当~-PbF_2掺杂一价阳离子时，电导率显著增加。然后，如在BiOzF-2~ 9 BiOxF-2x中，通过氟离子空位发生质量传输，以及掺杂有单价阳离子的~-PbF_2表现出这样的电导率值，使得不需要极薄的膜。因此，可以避免通过繁琐的真空蒸发技术制造原电池。此外，这两种氟化物在空气中非常稳定。
BiOo. 09F2. s2 and~-PbF2: AgF are suitable fluoride conducting electrolytes for application in galvanic cells. A simple fabrication method for the cell Pb/~-PbF2: AgF/BiO0. ogF2. s2/Bi is described. Open-circuit voltages are in accord with a theoretical value of 0.33 V based on the cell reaction 3Pb+ 2BiF~--> 3PbF2 Jr 2Bi. Cells were discharged in the temperature region 29, 8~ 176 with current densities of 12-63 mA/m 2. Short-circuit currents range from 15.7 to 386 mA/m 2. Relatively constant load-circuit voltages were attained over periods of days.The electrical properties of fluoride conductors with fluorite or tysonite structure have received considerable interest in the recent literature (1-8). Some of these materials are presently used as solid electrolytes. PbF2 has been applied successfully as a solid electrolyte in a thin film galvanic cell (5). Thin film galvanic cells Pb/PbF2/CuF2 (PbF2)/Cu have been fabricated by vacuum evaporation (5). CuF2 is, however, a highly resistive material at room temperature. In order to improve the conductivity CuF2 was codeposited with PbF2. This in turn leads to an open-circuit voltage (OCV) lower than the theoretical OCV of 0.70 V. Both CuF2, and especially AgF are reactive toward moisture in air. Special precautions are, therefore, needed to avoid blistering of thin films (5). Kennedy and Miles (6) have tested potassium fluoride-doped~-PbF2 as an electrolyte in galvanic cells with CuF2 or AgF as cathode materials. Open-circuit voltages of 0.70 and 1.30 V, respectively, were achieved, but the cell potentials fell rapidly when placed under load and current drawn. This poor performance could be due to the formation of an anode passivation layer consisting of low conductivity pure a-PbF2 (6). Recently, we have reported on solid electrolyte properties of tysonite-related BiOzF3-2x (x: 0.09,~ 0.1)(9). The conductivity is ionic and exceeds at ambient temperatures the conductivity of undoped~-PbF2. When~-PbF2 is doped with monovalent cations the conductivity substantially increases. Mass transport then occurs via fluoride ion vacancies as in BiOzFs-2~ 9 BiOxF~-2x, as well as~-PbF2 doped with monovalent cations exhibit such conductivity values that extremely thin films are not required. Fabrication of galvanic cells by tedious vacuum evaporation techniques can therefore be avoided. Moreover, both fluorides are quite stable in air.