CN1387269A - 一种单壁纳米碳管可充电池电极及其制备方法 - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 12
- 229910052799 carbon Inorganic materials 0.000 title claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 42
- 239000001257 hydrogen Substances 0.000 claims abstract description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- 239000006260 foam Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 239000002109 single walled nanotube Substances 0.000 claims description 46
- 238000002360 preparation method Methods 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 230000005518 electrochemistry Effects 0.000 abstract description 3
- 229910021392 nanocarbon Inorganic materials 0.000 abstract 4
- 238000002474 experimental method Methods 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 7
- 238000000748 compression moulding Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- 239000001996 bearing alloy Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 229910005438 FeTi Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
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- 229910052763 palladium Inorganic materials 0.000 description 1
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Abstract
一种单壁纳米碳管可充电池电极,其特征在于以氢电弧法制备的单壁纳米碳管作为电极的电化学储氢材料含量为10~98wt%,其余是作为骨架材料的泡沫镍及不可避免的杂质;电极的宏观密度为1000~6000kg/m3。其制备方法为首先采用专利申请号为99113021.9的氢电弧法制备平均直径在1.85nm的单壁纳米碳管;所制得的单壁纳米碳管不经提纯和任何处理直接压在泡沫镍上成型。本发明电极具有很高的电化学容量及很高的循环使用寿命。
Description
本发明涉电池技术,特别提供了一种新型的可充电池电极及其制备方法。
随着人类对矿物能源的过度开采与大量使用,矿物能源储备日渐短缺、环境污染日益严重,迫切要求一种新的替代能源。氢能具有零污染和可再生的独特优点,被认为是现有以碳为基础的能源工业最理想的替代者。但是阻碍氢能规模利用的主要障碍是缺乏一种方便、高效的储存系统,储氢材料正是在这样的背景下产生的,并得以迅猛发展。
1886年美国现代化学奠基人Thamas Graham发现金属钯能够大量吸氢。一个世纪以后,直到1968年美国Brookhaven国立研究所率先在储氢合金的研究上获得成功,发现了Mg2Ni合金也具有储氢性能。1970年荷兰菲利普研究所发现了LaNi5的储氢性能。与此同时,美国的Brookhaven国立研究所又发现了FeTi储氢合金,从而揭开了储氢合金研究的新篇章。其中研究较多、技术相对成熟的LaNi5已被成功应用于Ni-MH可充电池,其他合金材料的应用也在研究中,但金属合金储氢材料存在储氢容量低或放氢条件苛刻等问题,难以实现在燃料电池、高容量可充电池等氢能规模利用方面的应用。
本发明的目的在于提供一种单壁纳米碳管可充电池电极及其制备方法,其具有很高的电化学容量及很高的循环使用寿命。
本发明提供了一种单壁纳米碳管可充电池电极,其特征在于以氢电弧法制备的单壁纳米碳管作为电极的电化学储氢材料,含量为10~98wt.%,其余是作为骨架材料的泡沫镍及不可避免的杂质;电极的宏观密度为1000~6000kg/m3;
其中所述单壁纳米碳管平均直径在1.85nm,其纯度为50~75wt.%,Ni为10~20wt.%,Fe为1~5wt.%,Co为1~5wt.%,其它为石墨粉、无定形碳及不可避免的杂质。
本发明还提供上述单壁纳米碳管可充电池电极的制备方法,其特征在于:首先采用专利申请号为99113021.9的氢电弧法制备平均直径在1.85nm的单壁纳米碳管;所制得的单壁纳米碳管不经提纯和任何处理直接压在泡沫镍上成型。
本发明提供了一种新型的可充电池电极,即采用申请号为99113021.9的氢电弧法制备的单壁纳米碳管作为电极的电化学储氢材料,其平均直径大(1.85nm,其它研究者制备的样品平均直径一般为1.4nm),氢分子可以在单壁纳米碳管中大量凝聚,从而与现有的合金电极比具有很高的电化学储氢能力;另外采用申请号为99113021.9的氢电弧法制备的单壁纳米碳管,纯度可达50~75wt.%,每10~20根单壁纳米碳管聚集成束状,宏观定向成绳,长达数厘米,具有良好的导电性和成型性,因而可以不经过提纯和任何处理,不需粘结剂直接压制成电极。本发明中所用样品量大,下述实施例中所用样品的量均在50mg以上,实验数据重现性好。
以本发明电极作为工作电极,Hg/HgO作为参比电极,6MKOH为电解液,NiOH为辅助电极,然后进行电化学储氢实验,其电化学容量可达到503mAh/g(按活性物质单壁纳米碳管重量计算,下同),相当于气相储氢重量百分比为1.8wt.%,100个充放电循环后容量仍维持在最高容量的80%以上。可以预见如果优化单壁纳米碳管的制备工艺,制备出更高质量的单壁纳米碳管,优化单壁纳米碳管电极的成型条件和充放电制度,将更能展现单壁纳米碳管作为电化学储氢材料的美好前景。
下面通过实施例详述本发明。
附图1.单壁纳米碳管的电化学储氢实验示意图
附图2.单壁纳米碳管的透射电镜照片
附图3.单壁纳米碳管电极的电压与时间的曲线
附图4.单壁纳米碳管电极的循环寿命曲线
实施例1
电化学储氢实验如附图1。其中1为工作电极,2为参比电极,3为辅助电极。
取用专利号为99113021.9的方法制得的,平均直径大约为1.85nm的单壁纳米碳管300mg,未经处理直接以25mg泡沫镍为基体压制成型,密度为6000kg/cm3,所得到单壁纳米碳管电极用作工作电极,Hg/HgO作为参比电极,6MKOH为电解液,NiOH为辅助电极,电解池的温度为25℃。单壁纳米碳管电极的循环寿命实验以500mA/g的电流密度进行充放电,放电时截止电位为-0.4V(vs.Hg/HgO)。单壁纳米碳管的最高电化学储氢量为503.4mAh/g。
实施例2
电化学储氢实验如附图1。
取用专利号为99113021.9的方法制得的,平均直径大约为1.85nm的单壁纳米碳管200mg,未经处理直接以25mg泡沫镍为基体压制成型,密度为4000kg/cm3,所得到单壁纳米碳管电极用作工作电极,Hg/HgO作为参比电极,6MKOH为电解液,NiOH为辅助电极,电解池的温度为25℃。单壁纳米碳管电极的循环寿命实验以500mA/g的电流密度进行充放电,放电时截止电位为-0.4V(vs.Hg/HgO)。单壁纳米碳管的最高电化学储氢量为503mAh/g。
实施例3
电化学储氢实验如附图1。
取用专利号为99113021.9的方法制得的,平均直径大约为1.85nm的单壁纳米碳管160mg,未经处理直接以25mg泡沫镍为基体压制成型,密度为3500kg/cm3,所得到单壁纳米碳管电极用作工作电极,Hg/HgO作为参比电极,6MKOH为电解液,NiOH为辅助电极,电解池的温度为25℃。单壁纳米碳管电极的循环寿命实验以400mA/g的电流密度进行充放电,放电时截止电位为-0.4V(vs.Hg/HgO)。单壁纳米碳管的最高电化学储氢量为502.8mAh/g。
实施例4
电化学储氢实验如附图1。
取用专利号为99113021.9的方法制得的,平均直径大约为1.85nm的单壁纳米碳管100mg,未经处理直接以25mg泡沫镍为基体压制成型,密度为2000kg/cm3,所得到单壁纳米碳管电极用作工作电极,Hg/HgO作为参比电极,6MKOH为电解液,NiOH为辅助电极,电解池的温度为25℃。单壁纳米碳管电极的循环寿命实验以500mA/g的电流密度进行充放电,放电时截止电位为-0.4V(vs.Hg/HgO)。单壁纳米碳管的最高电化学储氢量为502mAh/g。。
实施例5
电化学储氢实验如附图1。
取用专利号为99113021.9的方法制得的,平均直径大约为1.85nm的单壁纳米碳管80mg,未经处理直接以25mg泡沫镍为基体压制成型,密度为2000kg/cm3,所得到单壁纳米碳管电极用作工作电极,Hg/HgO作为参比电极,6MKOH为电解液,NiOH为辅助电极,电解池的温度为25℃。单壁纳米碳管电极的循环寿命实验以500mA/g的电流密度进行充放电,放电时截止电位为-0.4V(vs.Hg/HgO)。单壁纳米碳管的最高电化学储氢量为501.3mAh/g。
实施例6
电化学储氢实验如附图1。
取用专利号为99113021.9的方法制得的,平均直径大约为1.85nm的单壁纳米碳管50mg,未经处理直接以25mg泡沫镍为基体压制成型,密度为3500kg/cm3,所得到单壁纳米碳管电极用作工作电极,Hg/HgO作为参比电极,6MKOH为电解液,NiOH为辅助电极,电解池的温度为25℃。单壁纳米碳管电极的循环寿命实验以500mA/g的电流密度进行充放电,放电时截止电位为-0.4V(vs.Hg/HgO)。单壁纳米碳管的最高电化学储氢量为501mAh/g。
Claims (4)
1、一种单壁纳米碳管可充电池电极,其特征在于以氢电弧法制备的单壁纳米碳管作为电极的电化学储氢材料。
2、按照权利要求1所述单壁纳米碳管可充电池电极,其特征在于:所述单壁纳米碳管的含量为10~98wt.%,其余是作为骨架材料的泡沫镍及不可避免的杂质;电极的宏观密度为1000~6000kg/m3。
3、按照权利要求1或2所述单壁纳米碳管可充电池电极,其特征在于:其中所述单壁纳米碳管平均直径在1.85nm,其纯度为50~75wt.%,Ni为10~20wt.%,Fe为1~5wt.%,Co为1~5wt.%,其它为石墨粉、无定形碳及不可避免的杂质。
4、一种权利要求1所述单壁纳米碳管可充电池电极的制备方法,其特征在于:首先采用专利申请号为99113021.9的氢电弧法制备平均直径在1.85nm的单壁纳米碳管;所制得的单壁纳米碳管不经提纯和任何处理直接压在泡沫镍上成型。
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CN106981624B (zh) * | 2017-05-24 | 2019-12-20 | 中国科学院过程工程研究所 | 一种简单高效制备锂硫电池正极极片的方法 |
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