CN113299897A - 一种Na3V2(PO4)3@C为正极材料的混合离子全电池 - Google Patents
一种Na3V2(PO4)3@C为正极材料的混合离子全电池 Download PDFInfo
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- 229910020650 Na3V2 Inorganic materials 0.000 title description 2
- 239000010405 anode material Substances 0.000 title description 2
- 239000003792 electrolyte Substances 0.000 claims abstract description 23
- 229910020657 Na3V2(PO4)3 Inorganic materials 0.000 claims abstract description 11
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 11
- 239000007774 positive electrode material Substances 0.000 claims abstract description 11
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 10
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 6
- 239000011734 sodium Substances 0.000 claims description 30
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 26
- 150000002500 ions Chemical class 0.000 claims description 26
- 229910052744 lithium Inorganic materials 0.000 claims description 24
- 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 17
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
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- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
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- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 3
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- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 2
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 claims description 2
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
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Abstract
本发明公开了一种Na3V2(PO4)3@C为正极材料的混合离子全电池。以Na3V2(PO4)3@C为正极，碳基材料为负极，锂/钠盐混合有机溶液为电解液；所述的电解液中锂盐和钠盐的摩尔比为1:0.25～2，电解液的浓度为0.5～3mol/L。该混合离子全电池具有优秀的稳定性及倍率性能，为商业全电池提供一种新的可能。
Description
技术领域
本发明属于锂/钠混合离子电池技术领域，具体涉及一种Na3V2(PO4)3@C为正极材料的混合离子全电池。
背景技术
随着科技的日益发展，电子移动设备、便携办公设备、通讯设备、电动交通工具等技术发展，对锂离子电池的需求日益提高，但金属锂在地球分布不均、储量低，导致锂离子电池价格高涨，限制了其未来在动力汽车和大规模储能领中的应用。因此，寻求一种新型低成本的电池替代锂离子电池成为人们亟需解决的问题。作为锂离子电池替代品的钠离子电池已显示出下一代电化学储能技术的巨大优势。与锂相比，钠资源丰富、分布均匀、易于开采，具有巨大的成本优势，并且，钠离子电池具有与锂离子电池一样的工作原理。但是，钠离子具有较大的离子半径，导致在正负极中嵌入/脱嵌阻力大，电极的可逆性差、不可逆容量损失大。在锂离子电池中已商业化的某些电极材料，如石墨、硅/碳复合材料，由于低的储钠容量，不适合于钠离子电池。在充分发挥锂离子电池优势的同时，克服钠离子电池的缺点是十分必要的。
锂/钠混合离子电池结合了锂离子电池和钠离子电池的各自优点，受到了广泛关注。锂/钠混合离子电池在充放电过程中，锂离子和钠离子分别仅在电池的一极与电解液之间移动，各行其是地统一于一个电池体中。对于锂/钠混合离子电池而言，如何设计并构建出一种电极材料及其电池，使其既能够展示出高的锂/钠离子存储能力，又能够体现出良好的循环稳定性，是当前锂/钠离子电池研究领域的热点和难点。
发明内容
本发明的目的旨在提供一种能优越的Na3V2(PO4)3@C材料锂/钠混合离子电池，Na3V2(PO4)3@C正极材料具有高工作电压、高比容量和优异的倍率循环性能，以锂/钠盐混合有机溶液为电解液可直接使用碳基材料为负极构建混合离子电池，实现锂/钠离子在电池中同时存储，提供高的能量密度和循环稳定性。
本发明具体通过以下技术方案实现：
一种Na3V2(PO4)3@C为正极材料的混合离子全电池，以Na3V2(PO4)3@C为正极，碳基材料为负极，锂/钠盐混合有机溶液为电解液；
所述的电解液中锂盐和钠盐的摩尔比为1:0.25～2，电解液的浓度为0.5～3mol/L。
所述的锂盐选自六氟磷酸锂、高氯酸锂、双草酸硼酸锂、二(三氟甲基磺酰)亚胺锂、二氟草酸硼酸锂、四氟硼酸锂、三氟甲磺酸锂中至少一种。优选的，所述的锂盐选自六氟磷酸锂、高氯酸锂、双草酸硼酸锂中至少一种。
所述的钠盐选自六氟磷酸钠、高氯酸钠、三氟甲基磺酸钠、双(三氟甲基磺酰基)亚胺钠、双氟磺酰亚胺钠、二氟-(草酸酯)硼酸钠中至少一种。优选的，所述的钠盐选自六氟磷酸钠、高氯酸钠中至少一种。
所述电解液的溶剂选自碳酸丙烯酯、碳酸乙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸亚乙烯酯、二甲醚、氟代碳酸乙烯酯中至少一种。
所述Na3V2(PO4)3@C通过以下方法制备：在乙二醇中依次加入聚乙烯吡咯烷酮、偏钒酸铵、二水合草酸磷酸二氢铵、碳酸钠和葡萄糖，恒温搅拌形成绿色溶液热反应，产物干燥后粉末经高温烧结即得。
所述的碳基材料选自石墨、硬碳、软碳和预锂化的碳材料中至少一种。
所述的全电池中负极与正极的容量比1.05～1.5。如果正极过量，在充电时，正极中出来的多余的锂离子无法进入负极，会在负极表面形成锂的沉积以致生成枝晶，使电池循环性能变差，也会造成电池内部短路，引发电池安全问题。因此一般碳材料负极锂电池中负极都会略多于正极，但也不能过量太多，过量太多会消耗正极中的锂，但本申请的电池是经过预处理的，避免了锂损耗问题；过多的负极会造成负极浪费，降低电池能量密度，提高电池成本。
本发明的有益效果为：
本发明采用性能优越的类球形Na3V2(PO4)3@C材料与碳基材料构建混合离子全电池，在特制的混合离子电解液中稳定性及倍率性能优秀，为商业全电池提供一种新的可能。
附图说明
图1是实施例1所制备的全电池专用Na3V2(PO4)3@C材料的扫描电镜图；
图2是实施例3所提供的锂/钠混合离子电池在0.1C倍率下的循环性能图；
图3是实施例4所提供的锂/钠混合离子电池在0.1C倍率下的循环性能图；
图4是实施例5所所提供的锂/钠混合离子电池在0.1C和5C倍率下的循环性能图。
具体实施方式
下面将结合本发明具体的实施例，对本发明技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1Na3V2(PO4)3@C制备
制备Na3V2(PO4)3@C粉末：首先，我们将一定量的聚乙烯吡咯烷酮(PVP)溶解于乙二醇中。然后，按照化学式Na3V2(PO4)3@C中Na、V、P的化学计量摩尔比依次加入偏钒酸铵、二水合草酸磷酸二氢铵、碳酸钠和葡萄糖，恒温搅拌形成绿色溶液，将所得的溶液经溶剂热反应后，经干燥得到绿色粉末。最后，将所得的绿色粉末前驱体高温烧结制备出黑色粉末状Na3V2(PO4)3@C样品。
样品的形貌经扫描电镜分析可知，如图1所示，Na3V2(PO4)3@C样品为类球状颗粒，大小在500nm左右。
实施例2锂/钠盐混合有机电解液的配置
在手套箱中按摩尔比1:0.25～2称量LiPF6和NaPF6，倒入体积比1:1:1的EC、DEC、EMC溶剂中，在50℃温度下进行磁力搅拌至完全溶解为无色透明溶液，分别配置出浓度为0.5-3mol/L的电解液。
实施例3全电池制备
按照质量比8:1:1称取Na3V2(PO4)3@C粉末，超级碳和粘结剂PVDF，然后加入适量的1-甲基-2吡咯烷酮(NMP)，混合均匀后制成电极浆料，均匀涂布在铝箔上，真空烘干后冲裁成10mm的圆形电极片。
使用所得电极片为工作电极，Celgard 2325微孔聚丙烯膜为隔膜，金属锂/钠合金薄片为负极，实施例2配置的0.5M混合离子电解液，在氩气保护下的手套箱中组装CR2032扣式电池。
在0.1C倍率下进行充放电测试，如图2和表1所示，首次放电容量为113.6mAh/g，20次循环后容量保持率为95.13％。
实施例4全电池制备
按照质量比8:1:1称取石墨粉末，超级碳和粘结剂PVDF，然后加入适量的1-甲基-2吡咯烷酮(NMP)，混合均匀后制成电极浆料，均匀涂布在铝箔上，真空烘干后冲裁成15mm的圆形电极片，该电极片用作负极。
实施例3制备的电极片用作正极，Celgard 2325微孔聚丙烯膜为隔膜，采用实施例2配置的0.5M混合离子电解液，在氩气保护下的手套箱中组装CR2032扣式电池。
在0.1C倍率下进行充放电测试，如图3和表1所示，全电池首次可逆容量为85mAh/g，20次循环后容量保持率为94.11％。
实施例5全电池制备
按照实施例3制备正极，将经预锂化后的石墨电极用负极，实施例2配置的2M混合物离子电解液，组装成锂/钠混合离子电池。
经恒电流充放电测试电化学性能，如图4和表1所示，全电池在0.1C倍率下，首次可逆容量为108mAh/g，库伦效率为95％，经过50次循环后，容量保持率为95％。在5C倍率下，电池的可逆容量为102.4mAh/g，50次循环后容量保持率103.9％。
对比例1
按照实施例3制备正极片，Celgard 2325微孔聚丙烯膜为隔膜，金属锂片为负极，电解液为1M LiPF6/EC+DEC(体积比为1:1)，在氩气保护下的手套箱中组装CR2032扣式电池。
在0.1C倍率下进行恒电流充放电测试，如表1所示，Na3V2(PO4)3@C电极经50次循环后，容量保持为81mAh/g。
对比例2
按照实施例3制备正极片，Celgard 2325微孔聚丙烯膜为隔膜，金属钠片为负极，电解液为1M NaPF6/EC+DEC(体积比为1:1)，在氩气保护下的手套箱中组装CR2032扣式电池。
在0.1C倍率下进行恒电流充放电测试，如表1所示，Na3V2(PO4)3@C电极经50次循环后，容量保持为90mAh/g。、
对比例3
按照实施例4制备石墨负极片，Celgard 2325微孔聚丙烯膜为隔膜，金属锂片为对电极，电解液为1M LiPF6/EC:DEC(1:1)，在氩气保护下的手套箱中组装CR2032扣式电池。经恒电流充放电测试电化学性能，如表1所示，在0.1C倍率下，100次循环后，可逆容量为340mAh/g。
表1实施例与对比例的电化学测试结果
尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实例进行多种变化、修改、替换和变型，本发明的范围由所附权利要求及其等同物限定。
Claims (8)
1.一种Na3V2(PO4)3@C为正极材料的混合离子全电池，其特征在于，以Na3V2(PO4)3@C为正极，碳基材料为负极，锂/钠盐混合有机溶液为电解液；所述的电解液中锂盐和钠盐的摩尔比为1:0.25～2，电解液的浓度为0.5～3mol/L。
2.根据权利要求1所述的一种Na3V2(PO4)3@C为正极材料的混合离子全电池，其特征在于，所述的锂盐选自六氟磷酸锂、高氯酸锂、双草酸硼酸锂、二(三氟甲基磺酰)亚胺锂、二氟草酸硼酸锂、四氟硼酸锂、三氟甲磺酸锂中至少一种。
3.根据权利要求1所述的一种Na3V2(PO4)3@C为正极材料的混合离子全电池，其特征在于，所述的钠盐选自六氟磷酸钠、高氯酸钠、三氟甲基磺酸钠、双(三氟甲基磺酰基)亚胺钠、双氟磺酰亚胺钠、二氟-(草酸酯)硼酸钠中至少一种。
4.根据权利要求1所述的一种Na3V2(PO4)3@C为正极材料的混合离子全电池，其特征在于，所述电解液的溶剂选自碳酸丙烯酯、碳酸乙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸亚乙烯酯、二甲醚、氟代碳酸乙烯酯中至少一种。
5.根据权利要求1所述的一种Na3V2(PO4)3@C为正极材料的混合离子全电池，其特征在于，所述Na3V2(PO4)3@C通过以下方法制备：在乙二醇中依次加入聚乙烯吡咯烷酮、偏钒酸铵、二水合草酸磷酸二氢铵、碳酸钠和葡萄糖，恒温搅拌形成绿色溶液热反应，产物干燥后粉末经高温烧结即得。
6.根据权利要求1所述的一种Na3V2(PO4)3@C为正极材料的混合离子全电池，其特征在于，所述的碳基材料选自石墨、硬碳、软碳和预锂化的碳材料中至少一种。
7.根据权利要求1所述的一种Na3V2(PO4)3@C为正极材料的混合离子全电池，其特征在于，所述的全电池中负极与正极的容量比1.05～1.5。
8.权利要求1中所述的电解液，其特征在于，用于锂/钠混合离子电池，所述的电解液中锂盐和钠盐的摩尔比为1:0.25～2，电解液的浓度为0.5～3mol/L。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113735092A (zh) * | 2021-11-04 | 2021-12-03 | 中博龙辉装备集团股份有限公司 | 一种磷酸钒钠碳复合材料及其制备方法和应用 |
| CN113937336A (zh) * | 2021-09-20 | 2022-01-14 | 复旦大学 | 基于磷酸铁锂正极与锡碳负极的宽温混合离子电池 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080153002A1 (en) * | 2006-11-27 | 2008-06-26 | Nazar Linda Faye | Mixed Lithium/Sodium Ion Iron Fluorophosphate Cathodes for Lithium Ion Batteries |
| JP2014063709A (ja) * | 2012-02-29 | 2014-04-10 | Sekisui Chem Co Ltd | リチウムイオン二次電池 |
| CN106935802A (zh) * | 2017-05-18 | 2017-07-07 | 中国科学院长春应用化学研究所 | 一种金属‑氧气二次电池 |
| CN108321442A (zh) * | 2018-01-08 | 2018-07-24 | 中国科学技术大学 | 混合水系离子电池及其应用 |
| CN108336353A (zh) * | 2018-01-05 | 2018-07-27 | 东北师范大学 | 一类混合锂/钠离子电池 |
| CN112531165A (zh) * | 2020-11-23 | 2021-03-19 | 东北师范大学 | 一种碱金属负极复合保护膜及其制备方法、碱金属负极和碱金属二次电池 |
-
2021
- 2021-06-02 CN CN202110614329.7A patent/CN113299897B/zh active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080153002A1 (en) * | 2006-11-27 | 2008-06-26 | Nazar Linda Faye | Mixed Lithium/Sodium Ion Iron Fluorophosphate Cathodes for Lithium Ion Batteries |
| JP2014063709A (ja) * | 2012-02-29 | 2014-04-10 | Sekisui Chem Co Ltd | リチウムイオン二次電池 |
| CN106935802A (zh) * | 2017-05-18 | 2017-07-07 | 中国科学院长春应用化学研究所 | 一种金属‑氧气二次电池 |
| CN108336353A (zh) * | 2018-01-05 | 2018-07-27 | 东北师范大学 | 一类混合锂/钠离子电池 |
| CN108321442A (zh) * | 2018-01-08 | 2018-07-24 | 中国科学技术大学 | 混合水系离子电池及其应用 |
| CN112531165A (zh) * | 2020-11-23 | 2021-03-19 | 东北师范大学 | 一种碱金属负极复合保护膜及其制备方法、碱金属负极和碱金属二次电池 |
Non-Patent Citations (6)
| Title |
|---|
| KE DU等: "Na3V2(PO4)3 as cathode material for hybrid lithium ion batteries", 《JOURNAL OF POWER SOURCES》 * |
| KE DU等: "Na3V2(PO4)3 as cathode material for hybrid lithium ion batteries", 《JOURNAL OF POWER SOURCES》, vol. 223, 26 September 2012 (2012-09-26), pages 284 - 288 * |
| 张起豪: "磷酸钒钠/碳复合正极材料的研究", 《中国优秀硕士学位论文全文数据库电子期刊工程科技Ⅰ辑》 * |
| 张起豪: "磷酸钒钠/碳复合正极材料的研究", 《中国优秀硕士学位论文全文数据库电子期刊工程科技Ⅰ辑》, no. 9, 15 September 2019 (2019-09-15), pages 47 - 55 * |
| 郭晋芝: "高性能聚阴离子型钒基钠电正极材料的设计制备与性能研究", 《中国博士学位论文全文数据库电子期刊工程科技Ⅰ辑》 * |
| 郭晋芝: "高性能聚阴离子型钒基钠电正极材料的设计制备与性能研究", 《中国博士学位论文全文数据库电子期刊工程科技Ⅰ辑》, no. 9, 15 September 2019 (2019-09-15), pages 52 - 60 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113937336A (zh) * | 2021-09-20 | 2022-01-14 | 复旦大学 | 基于磷酸铁锂正极与锡碳负极的宽温混合离子电池 |
| CN113735092A (zh) * | 2021-11-04 | 2021-12-03 | 中博龙辉装备集团股份有限公司 | 一种磷酸钒钠碳复合材料及其制备方法和应用 |
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