CN105355895A - 镍氢电池负极活性材料、镍氢电池负极的制备方法及应用 - Google Patents
镍氢电池负极活性材料、镍氢电池负极的制备方法及应用 Download PDFInfo
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- 239000011149 active material Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910052987 metal hydride Inorganic materials 0.000 title abstract 5
- 229910052759 nickel Inorganic materials 0.000 title abstract 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title abstract 5
- -1 nickel metal hydride Chemical class 0.000 title abstract 5
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims description 32
- 239000000956 alloy Substances 0.000 claims description 28
- 229910045601 alloy Inorganic materials 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 9
- 239000001996 bearing alloy Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910018095 Ni-MH Inorganic materials 0.000 claims description 6
- 229910018477 Ni—MH Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- 229910002640 NiOOH Inorganic materials 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000004080 punching Methods 0.000 claims description 3
- 239000006104 solid solution Substances 0.000 claims description 3
- 239000011258 core-shell material Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 238000007599 discharging Methods 0.000 abstract description 3
- 238000003723 Smelting Methods 0.000 abstract 2
- 238000011056 performance test Methods 0.000 abstract 1
- 238000004458 analytical method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- 229910000878 H alloy Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract
本发明公开了一种镍氢电池负极活性材料、镍氢电池负极的制备方法及应用。镍氢电池负极活性材料组成为Ti0.4Zr0.1V1.1Ni0.4Cr0.2Mn0.6，它是通过元素配比，并在熔炼炉中熔炼，并进行粉碎，然后制成模拟电池，进行电化学性能测试，结果表明在20℃下，放电电流密度600mA/g时，放电容量达到了245.1？mAh/g，高倍率放电能力（HRD）高达71.5%。
Description
技术领域
本发明涉及一种具有良好高倍率放电性能的镍氢电池负极活性材料以及应用。
背景技术
镍氢电池具有电化学比能量高、耐过充／放电性能好、无记忆效应和环境友好等优点，被称为高能绿色二次电池，已被广泛应用于各类数码产品、笔记本电脑和电动工具等。目前，随着国家大力推行低碳政策和节能减排措施，新能源汽车得到了更为广泛的关注，而作为过渡型产品的混合动力汽车是目前研究的一个热点，其中大多数混合动力汽车采用镍氢动力电池。作为镍氢电池负极活性物质的储氢材料的研究经历了AB5，AB2，AB型，AB3型等几个阶段，而Ｖ基固溶体储氢合金作为第三代新型储氢合金以其较高的理论储氢容量而得到了广泛的关注和研究。
目前的研究表明，一般的V基固溶体合金不具备电催化活性，研究表明在V基合金中添加适量的金属元素，可以在合金中形成第二相，并呈三维网状分布，这种结构作为电催化剂和微集流体可以改善其电化学活性和充放电能力，但目前V基储氢合金电极的高倍率放电性能普遍较差，为此需在这方面深入研究。
发明内容
为了克服现有技术的不足，本发明提供了一种镍氢电池负极活性材料、镍氢电池负极的制备方法及应用。
一种镍氢电池负极活性材料，V基固溶体储氢，元素组成为Ti0.4Zr0.1V1.1Ni0.4Cr0.2Mn0.6。
所述的镍氢电池负极活性材料，在20℃下，放电电流密度600mA/g时，放电容量达到了245.1mAh/g，高倍率放电能力（HRD）高达71.5%。
一种所述的镍氢电池负极的制备方法，负极活性材料Ti0.4Zr0.1V1.1Ni0.4Cr0.2Mn0.6合金由纯度≥99.9wt%的纯金属按组成配料，Ar气保护下，在真空电弧炉中熔炼而成，合金试样翻转重熔三次，以保证样品的均匀性；将铸态储氢合金机械粉碎成平均粒度180目的合金粉；称取0.75ｇ羰基Ni粉与0.15g储氢合金粉混合，装入钢模，在油压机上冷压成型制成直径10mm，厚度1mm的圆形负极片。
所述的Mn金属在高温易挥发，配料开始的时候比终产品实际组分含量多1wt%。
所述的油压机压力调节到12-14MPa，保压3min后取出圆形负极片。
一种采用所述的镍氢电池负极活性材料的镍氢电池，所述镍氢电池的负极采用所述的镍氢电池负极活性材料制备，正极为高容量的烧结式Ni(OH)2/NiOOH。
本发明的有益效果是通过合理的元素配比，制备出了高倍率放电性能优良的镍氢电池负极活性材料，在20℃下，放电电流密度600mA/g时，放电容量达到了245.1mAh/g，高倍率放电能力（HRD）达到了71.5%。
附图说明
图1为放电电流密度与放电容量（a部分）和HRD（b部分）之间的关系（20℃）；
图2为Ti0.4Zr0.1V1.1Ni0.4Cr0.2Mn0.6合金的XRD图谱。由图可见该合金由BCC结构的主相和C14Laves型结构的第二相组成；
图3为Ti0.4Zr0.1V1.1Ni0.4Cr0.2Mn0.6合金的扫描电镜图片。由图可见该合金由两相组成，这与XRD分析的结果基本一致。第二相C14Laves相沿着BCC主相的晶界析出，形成网状结构，这一结构可在充放电过程中，起到电催化相和微集流体的作用。
具体实施方式
Ti0.4Zr0.1V1.1Ni0.4Cr0.2Mn0.6合金由纯金属（纯度≥99.9wt%）按组成配料（由于锰在高温易挥发，所以配料的时候比实际含量多1wt%），在真空电弧炉中（Ar气保护下）熔炼而成，合金试样翻转重熔多次（一般3次），以保证样品的均匀性。将铸态储氢合金机械粉碎成平均粒度180目的合金粉。称取0.75ｇ羰基Ni粉与0.15g储氢合金粉混合，装入钢模，在油压机上冷压成型（压力调节到12-14MPa，保压3min后取出），制成直径约10mm，厚度约1mm的圆形电极片。
本发明合金组成与本研究组在2014年发表于材料科学与工程学报的《Ti0.4Zr0.1V1.1Mn0.5Ni0.4Crx(x=0,0.1,0.2,0.3)储氢合金的微观结构和电化学性能》中的Ti0.4Zr0.1V1.1Mn0.5Ni0.4Cr0.2合金的组成较为相似，比较而言，本发明Ti0.4Zr0.1V1.1Ni0.4Cr0.2Mn0.6合金在放电电流密度为480mA/g时，高倍率放电性能HRD为78.6%高于Ti0.4Zr0.1V1.1Mn0.5Ni0.4Cr0.2合金的70.7％，并在放电电流密度为600mA/g时仍能达到71.5%。但Ti0.4Zr0.1V1.1Mn0.8Ni0.4Cr0.2合金的高倍率放电性能已大幅下降（具体数据未公开），故Ti0.4Zr0.1V1.1Ni0.4Cr0.2Mn0.6合金的组成配比更有利于合金的高倍率放电性能。
储氢电极合金的电化学性能测试在开口三电极系统中进行，其中负极为待测的储氢合金电极，正极为高容量的烧结式Ni(OH)2/NiOOH，其电化学容量远高于研究电极的理论容量，参比电极为Hg/HgO，电解液是6mol/L的KOH溶液，在正极与负极室之间设有隔膜，以防止正极上产生的氧气扩散到储氢合金电极表面。组成模拟电池后，将其置于20℃恒温水浴中进行测试。储氢电极的电化学性能测试采用恒电流充放电方法进行，充电电流密度为60mA/g，截至电压为0.8V，测试仪器为DC-５型电池测试仪，并与计算机进行连接，测试结果由计算机自动采集并记录。结果如图1所示。在20℃下，放电电流密度600mA/g时，放电容量达到了245.1mAh/g，高倍率放电能力（HRD）达到了71.5%。
合金物相分析在日本产的D/max-2500/pcX-射线衍射仪上进行，Cu-Kα辐射，阶梯扫描参数为4°/min，40KV，200mA。合金的分析图谱如图2所示。
合金的表面形貌分析由日本产的KYKY-2800型扫描电子显微镜完成。分析结果如图3所示。
Claims (6)
1.一种镍氢电池负极活性材料，其特征是：V基固溶体储氢，元素组成为Ti0.4Zr0.1V1.1Ni0.4Cr0.2Mn0.6。
2.根据权利要求1所述的镍氢电池负极活性材料，其特征是：在20℃下，放电电流密度600mA/g时，放电容量达到了245.1mAh/g，高倍率放电能力（HRD）高达71.5%。
3.一种根据权利要求1所述的镍氢电池负极的制备方法，其特征是：负极活性材料Ti0.4Zr0.1V1.1Ni0.4Cr0.2Mn0.6合金由纯度≥99.9wt%的纯金属按组成配料，Ar气保护下，在真空电弧炉中熔炼而成，合金试样翻转重熔三次，以保证样品的均匀性；将铸态储氢合金机械粉碎成平均粒度180目的合金粉；称取0.75ｇ羰基Ni粉与0.15g储氢合金粉混合，装入钢模，在油压机上冷压成型制成直径10mm，厚度1mm的圆形负极片。
4.根据权利要求1所述的制备方法，其特征是：所述的Mn金属在高温易挥发，配料开始的时候比终产品实际组分含量多1wt%。
5.根据权利要求1所述的制备方法，其特征是：所述的油压机压力调节到12-14MPa，保压3min后取出圆形负极片。
6.一种采用权利要求1所述的镍氢电池负极活性材料的镍氢电池，其特征是：所述镍氢电池的负极采用所述的镍氢电池负极活性材料制备，正极为高容量的烧结式Ni(OH)2/NiOOH。
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| CN114725363A (zh) * | 2022-04-13 | 2022-07-08 | 浙江水利水电学院 | 一种镍氢电池负极用v基储氢合金及其制备方法和应用 |
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Non-Patent Citations (2)
| Title |
|---|
| 杭州明: "Ti0.4Zr0.1V1.1Ni0.4CrxMn0.5 (x=0,0.1,0.2,0.3)储氢合金的微观结构和电化学性能", 《材料科学与工程学报》 * |
| 杭州明: "V基固溶体合金结构和电化学性能研究", 《中国优秀硕士学位论文全文数据库》 * |
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| CN114725363A (zh) * | 2022-04-13 | 2022-07-08 | 浙江水利水电学院 | 一种镍氢电池负极用v基储氢合金及其制备方法和应用 |
| CN114725363B (zh) * | 2022-04-13 | 2024-03-26 | 浙江水利水电学院 | 一种镍氢电池负极用v基储氢合金及其制备方法和应用 |
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