CN107681141A - 一种碳包覆硼酸镍纳米棒的钠离子电池负极材料 - Google Patents
一种碳包覆硼酸镍纳米棒的钠离子电池负极材料 Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 33
- 239000011248 coating agent Substances 0.000 title claims abstract description 31
- 238000000576 coating method Methods 0.000 title claims abstract description 31
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000004327 boric acid Substances 0.000 title claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 13
- 239000010405 anode material Substances 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 12
- 239000002086 nanomaterial Substances 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- HKFZDVPCCOOGEV-UHFFFAOYSA-N nickel(3+);borate Chemical compound [Ni+3].[O-]B([O-])[O-] HKFZDVPCCOOGEV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002608 ionic liquid Substances 0.000 claims abstract description 5
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 11
- 229910001415 sodium ion Inorganic materials 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000003814 drug Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- -1 1- butyl -3- methylimidazole dicyandiamide salt Chemical class 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical class [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229920000084 Gum arabic Polymers 0.000 claims description 2
- 235000010489 acacia gum Nutrition 0.000 claims description 2
- 239000000205 acacia gum Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 244000171897 Acacia nilotica subsp nilotica Species 0.000 claims 1
- 229940079593 drug Drugs 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 abstract 1
- 229940078494 nickel acetate Drugs 0.000 abstract 1
- 230000008901 benefit Effects 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 244000215068 Acacia senegal Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- BXNRPWOFOQNQDE-UHFFFAOYSA-N boric acid;nickel Chemical compound [Ni].OB(O)O BXNRPWOFOQNQDE-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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Abstract
本发明属于电池材料技术领域,具体涉及一种碳包覆硼酸镍纳米棒的钠离子电池负极材料。其中碳包覆硼酸镍纳米棒的制备具体为:将乙酸镍、硼酸、柠檬酸溶解混合,放入恒温干燥箱中,100‑200℃恒温8‑12 h,将得到的粉末煅烧得到Ni3B2O6纳米棒材料;再将其与离子液体充分混合,放入管式炉中Ar氛围下反应,得到了黑色粉末,用HCl清洗除去单质镍;干燥,得到碳包覆的硼酸镍纳米材料。本发明制得的材料具有相对较高的比容量和优异的循环稳定性,其成本低、纯度高、性能优异,可以大量合成,具有很好的应用前景。
Description
技术领域
本发明属于电池材料技术领域,具体涉及一种碳包覆硼酸镍纳米棒的钠离子电池负极材料。
背景技术
钠是地球上储量较丰富的元素之一,与锂的化学性能类似,因此也可以适用锂离子电池体系。钠离子电池相比锂离子电池有诸多优点,如成本低,安全性好,随着研究的深入,钠离子电池越来越具有成本效益,并有望在未来取代锂离子电池而被广泛应用。当前,钠离子电池因缺乏匹配合适的负极材料而制约其实际应用,开发性能优异的钠离子电池负极材料是当前该领域的研究热点和重点。
发明内容
本发明的目的在于提供一种新型的钠离子电池负极材料碳包覆硼酸镍纳米棒,这种材料具有较高的储钠容量和优异的倍率性能,具有良好的应用价值。
为实现上述目的,本发明采用如下技术方案:
Ni3B2O6纳米材料的制备:将0.5-0.8 g乙酸镍、0.1-0.3 g硼酸、2-4 g柠檬酸溶解在40-70 ml的去离子水中,磁力搅拌2-5 h之后将装有该溶液的烧杯放入恒温干燥箱中,100-200℃恒温8-12 h,反应结束后将得到的粉末放入马弗炉中600-800℃煅烧2-6 h后得到Ni3B2O6纳米棒材料。
碳包覆Ni3B2O6纳米材料的制备:将得到的Ni3B2O6材料1-3 g与离子液体(1-丁基-3-甲基咪唑双氰胺盐)100-700 µL进行充分混合,再将其研磨好的样品放入管式炉中Ar氛围下400-700℃保温2-5 h,反应结束后得到了黑色粉末,收集该粉末用1-3 M的HCl清洗1h,除去单质镍;最后将样品干燥,得到的最终为黑色的样品就是碳包覆的硼酸镍纳米材料。
钠离子电池组装:按质量比计,碳包覆Ni3B2O6纳米棒:阿拉伯树胶GA:乙炔黑=75-80:10-20:10-15,混合研磨后均匀地涂在1.2 cm2的铜片上做正极,负极为金属钠,电解质是1M NaClO4的EC+DEC (EC/ DEC=1/1 v/v) 溶液;电池组装在氩气保护下手套箱里进行,其中氧气和水分含量均低于1ppm。
本发明的显著优点在于:
本发明提供了一种新型材料碳包覆Ni3B2O6纳米棒在钠离子电池负极材料中的应用,并表现出相对较高的比容量和优异的循环稳定性。其成本低、纯度高、性能优异,可以大量合成,具有很好的应用前景。
附图说明
图1为碳包覆硼酸镍纳米棒的XRD图;
图2中a图为纯硼酸镍粉末SEM图;b图为碳包覆硼酸镍纳米棒SEM图;
图3为碳包覆硼酸镍纳米棒钠离子电池充放电曲线;
图4为碳包覆硼酸镍纳米棒钠离子电池倍率性能图。
具体实施方式
为进一步公开而不是限制本发明,以下结合实例对本发明作进一步的详细说明。
实施例1
Ni3B2O6纳米棒的制备:将0.5-0.8 g乙酸镍、0.1-0.3 g硼酸、2-4 g柠檬酸溶解在40-70ml的去离子水中,磁力搅拌2-5 h之后将装有该溶液的烧杯放入恒温干燥箱中,100-200℃恒温8-12 h,反应结束后将得到的粉末放入马弗炉中600-800℃煅烧2-6 h后得到Ni3B2O6纳米棒材料。
碳包覆Ni3B2O6纳米材料的制备:将得到的Ni3B2O6材料1-3 g与离子液体1-丁基-3-甲基咪唑双氰胺盐100-700 µL进行充分混合,再将其研磨好的药品放入管式炉中Ar氛围下400-700℃保温2-5 h,反应结束后得到了黑色粉末,收集该粉末用1-3 M的HCl清洗1 h,除去单质镍;最后将药品干燥,得到的最终为黑色的药品就是碳包覆的硼酸镍纳米材料。
钠离子电池组装:碳包覆Ni3B2O6纳米棒:GA:乙炔黑=75-80:10-20:10-15混合研磨后均匀地涂在1.2 cm2的铜片上做正极,负极为金属钠,电解质是1M NaClO4的EC+DEC(EC/ DEC=1/1 v/v) 溶液;电池组装在氩气保护下手套箱里进行,其中氧气和水分含量均低于1ppm。
图1为本发明碳包覆硼酸镍XRD图,各个峰都与硼酸镍XRD标准卡片(JCPDS card22-0745)一致,说明该材料为纯相的Ni3B2O6。图2为Ni3B2O6碳包覆前后的SEM图。从图2中a图可以看出该材料呈纳米棒状,长度为300 nm~800 nm。从图2中b图可以清晰地看到纳米棒上有包覆了一层碳,这说明碳均匀地包覆在Ni3B2O6纳米棒上。图3是该材料组装而成的钠离子电池在100 mAg-1的充放电曲线,其首次放电容量达655 mAhg-1,首次充电容量达429 mAhg-1,其库伦效率达到65.4%。图4是碳包覆Ni3B2O6纳米棒的倍率性能图,在电流密度为100、200、500、1000和2000 mAg-1的电流密度下,对应的充电容量为429、370、334、290和220mAhg-1。由此可看出该材料表现出了相对较高的比容量,以及其良好的倍率性能。当再次回到100 mAg-1时,其容量再次回复到420 mAhg-1。这也说明了经过碳包覆以后,其稳定性得到了很大提高。通过此方法合成出来的碳包覆Ni3B2O6纳米棒,作为钠离子电池负极材料,结果表明其具有良好的性能。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (5)
1.一种碳包覆硼酸镍纳米棒的钠离子电池负极材料,其特征在于:具体制备步骤为:
(1)Ni3B2O6纳米材料的制备:将0.5-0.8 g乙酸镍、0.1-0.3 g硼酸、2-4 g柠檬酸溶解在40-70 ml的去离子水中,磁力搅拌2-5 h之后将装有该溶液的烧杯放入恒温干燥箱中反应,反应结束后将得到的粉末放入马弗炉中600-800℃煅烧2-6 h后得到Ni3B2O6纳米棒材料;
(2)碳包覆Ni3B2O6纳米材料的制备:将得到的Ni3B2O6材料1-3 g与离子液体100-700 µL进行充分混合,再将其研磨好的药品放入管式炉中Ar氛围下煅烧,反应结束后得到了黑色粉末,收集该粉末用1-3 M的HCl清洗1 h,除去单质镍;最后将药品干燥,得到的最终为黑色的药品就是碳包覆的硼酸镍纳米材料;
(3)钠离子电池组装:按质量比计,碳包覆Ni3B2O6纳米粒子:阿拉伯树胶GA:乙炔黑=75-80:10-20:10-15,然后混合研磨后均匀地涂在1.2 cm2的铜片上做正极,负极为金属钠,电解质是1M NaClO4的EC+DEC溶液;电池组装在氩气保护下手套箱里进行,其中氧气和水分含量均低于1ppm。
2.根据权利要求1所述的一种碳包覆硼酸镍纳米棒的钠离子电池负极材料,其特征在于:步骤(1)中恒温干燥箱内反应条件为:100-200℃恒温8-12 h。
3.根据权利要求1所述的一种碳包覆硼酸镍纳米棒的钠离子电池负极材料,其特征在于:步骤(2)中的离子液体为1-丁基-3-甲基咪唑双氰胺盐。
4.根据权利要求1所述的一种碳包覆硼酸镍纳米棒的钠离子电池负极材料,其特征在于:步骤(2)中在管式炉中煅烧条件为400-700℃,反应2-5 h。
5.根据权利要求1所述的一种碳包覆硼酸镍纳米棒的钠离子电池负极材料,其特征在于:步骤(3)中EC与DEC的体积比为1:1。
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Cited By (4)
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CN108987712A (zh) * | 2018-07-20 | 2018-12-11 | 福建师范大学 | 一种新型的钠离子电池负极材料的制备方法 |
CN110459737A (zh) * | 2018-05-07 | 2019-11-15 | 福建师范大学 | 一种核壳结构的碳包覆硼酸亚铁的制备方法及其应用 |
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CN115893439A (zh) * | 2022-11-30 | 2023-04-04 | 海南大学 | 一种通过不同pH的水溶液浸泡提升电化学性能的LiBC电极材料及其方法 |
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CN115893439A (zh) * | 2022-11-30 | 2023-04-04 | 海南大学 | 一种通过不同pH的水溶液浸泡提升电化学性能的LiBC电极材料及其方法 |
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