A Superior Low-Cost Cathode for a Na-Ion Battery
A Superior Low-Cost Cathode for a Na-Ion Battery
复制标题
用于钠离子电池的优质低成本阴极。
DOI：
10.1002/anie.201206854
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发表时间：
2013-01-01
影响因子：
16.6
通讯作者：
Goodenough, John B.
中科院分区：
文献类型：
--
作者：
Wang, Long;Lu, Yuhao;Goodenough, John B.
全球的优先事项是开发低成本、高效的非高峰电力和由化石燃料(如风能、太阳能、核能)以外的能源产生的电能的存储。[1]可充电电池提供高效的电能存储(EES)，但用于手持设备的锂离子电池对于大规模EES来说过于昂贵。与李娜不同的是，纳在世界各地都很容易买到，因此比李娜便宜得多。然而，现有的钠/S[2]和斑马(钠/氯化镍)[3]电池是在250至3508摄氏度的熔融电极上运行的。因此，开发一种高能量密度、低成本、能够高倍率放电/充电的室温可充电钠离子电池(SIB)是一种巨大的动机。到目前为止，室温可充电电池已被用作正极氧化物主体，工作离子H+或Li+可以在有限的固溶体范围内可逆地插入/提取。这两个工作离子能够在具有紧密堆积的氧离子阵列的主机中作为移动客体。然而，Na+太大，在氧离子密集的宿主中不能充分移动；它需要具有更大间隙空间的宿主骨架。虽然Na+在氧化物钙钛矿中被12个氧离子稳定配位，例如NaxWO_3青铜，但在由4个氧离子配位的共享面上，这些位置之间的Na+转移需要太高的活化能。σ键上O-2p轨道阻碍了Na的运动。O_2~+离子被(CN)~+离子取代会削弱与Na的结合；因此，Na~+转移的活化能大大降低，这使得六氰基钙钛矿作为可充电SIB的阴极主体的探索很有吸引力。报道了一种含低成本阳离子的六氰基铁酸锰钠盐(NMHFC)的合成路线。
A global priority is the development of low-cost, efficient storage of off-peak electric power and of electrical energy generated by energy sources other than fossil fuels (eg wind, solar, nuclear).[1] The rechargeable battery offers efficient electrical energy storage (EES), but the Li-ion battery used in hand-held devices is too expensive for large-scale EES. Unlike Li, Na is readily available worldwide and therefore much less costly than Li. However, the existing Na/S [2] and Zebra (Na/NiCl2)[3] batteries are operating on molten electrodes at 250 to 3508C. Therefore, there is a huge incentive to develop a room-temperature rechargeable, low-cost Na-ion battery (SIB) of high energy density capable of discharge/charge at a high rate.To date, room-temperature rechargeable batteries have used as cathode oxide hosts into/from which the working ion, H+ or Li+, can be inserted/extracted reversibly over a limited solid-solution range. These two working ions are able to be mobile guests in a host having a close-packed oxide-ion array. However, Na+ is too large to be sufficiently mobile in a host with close-packed oxide ions; it needs a host framework with a larger interstitial space. Although Na+ is stable coordinated by 12 oxide ions in an oxoperovskite, for example, the NaxWO3 bronze, too high an activation energy is required for Na+ transfer between these sites across a shared face coordinated by four oxide ions. The O-2p orbitals that σ bond to the Na impede its motion. Replacement of the O2À ions by (CN) À ions weakens bonding to the Na; the activation energy for Na+ transfer is, therefore, strongly reduced, which makes attractive exploration of hexacyanoperovskites as cathode hosts for a rechargeable SIB. We report a synthesis route for a sodium manganese hexacyanoferrate (NMHFC) containing low-cost cations, and we