CN114031115B - 一种镁离子电池层状水钒铜矿正极材料的制备方法 - Google Patents
一种镁离子电池层状水钒铜矿正极材料的制备方法 Download PDFInfo
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- 229910001425 magnesium ion Inorganic materials 0.000 title claims abstract description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 71
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 title claims abstract description 69
- KPZUWETZTXCDED-UHFFFAOYSA-N [V].[Cu] Chemical compound [V].[Cu] KPZUWETZTXCDED-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000007774 positive electrode material Substances 0.000 title claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000010405 anode material Substances 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 11
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 9
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 9
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000004729 solvothermal method Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 229960003280 cupric chloride Drugs 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 230000002378 acidificating effect Effects 0.000 claims abstract description 3
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 17
- RPYFZMPJOHSVLD-UHFFFAOYSA-N copper vanadium Chemical compound [V][V][Cu] RPYFZMPJOHSVLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000004005 microsphere Substances 0.000 abstract description 7
- 239000010949 copper Substances 0.000 description 30
- 229910052802 copper Inorganic materials 0.000 description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 22
- 229910052799 carbon Inorganic materials 0.000 description 15
- 239000003792 electrolyte Substances 0.000 description 10
- 238000009792 diffusion process Methods 0.000 description 7
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- 238000012512 characterization method Methods 0.000 description 4
- 238000009831 deintercalation Methods 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
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- 230000014759 maintenance of location Effects 0.000 description 4
- 229910002473 Cu3V2O7(OH)2·2H2O Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
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- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- -1 transition metal sulfides Chemical class 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- JZEGAFMGNJXHBZ-UHFFFAOYSA-N [Cu].[V].[Mg] Chemical compound [Cu].[V].[Mg] JZEGAFMGNJXHBZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
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- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910014079 Na—Mn—O Inorganic materials 0.000 description 1
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- 230000001351 cycling effect Effects 0.000 description 1
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
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- 238000001027 hydrothermal synthesis Methods 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
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- 238000013112 stability test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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Abstract
本发明公开了一种镁离子电池层状水钒铜矿正极材料的制备方法,包括如下步骤:步骤(1)将偏钒酸钠溶于水并调节pH为酸性,记为溶液A备用;步骤(2)将二水氯化铜溶于去离子水中,并向其中加入溶液A混合,记为溶液B备用;步骤(3)将苯甲酸溶于乙醇中,作为溶液C;步骤(4)将溶液B和溶液C混合,并加入DMF溶液,混合均匀后得到前驱体溶液;步骤(5)将所述前驱体溶液进行溶剂热反应,反应完成后洗涤干燥得到尺寸和形貌均一的水钒铜矿材料CuVOH。本发明采用简单的一步溶剂热法,合成了尺寸和形貌均一的微球水钒铜矿镁离子电池正极材料,使产品展现出良好的力学性能,制备工艺简便、成本低廉、电化学性能优异,具有广阔的应用前景。
Description
技术领域
本发明涉及镁离子电池技术领域,具体涉及一种镁离子电池层状水钒铜矿正极材料的制备方法。
背景技术
锂离子电池作为储能系统已广泛应用于便携式电子设备和电子汽车。然而,锂资源供应的局限性和高成本仍制约着锂资源的广泛应用。镁离子电池因其资源丰富、成本低、安全性高的特性,将有望取代昂贵的锂电。然而,镁离子在插层型电极材料中的活性中心较少,导致镁离子的储存能力有限,且本身高的电荷半径也将导致镁离子与正极基体之间强的静电相互作用,使镁离子的固体扩散动力学缓慢,极化较大,严重影响镁离子电池正极材料的电化学性能。镁离子电池虽然具有较高的能量密度(150~300 Wh·kg-1),但是其功率密度低(小于1 kW·kg-1),循环寿命差(通常小于1000圈)。这些都限制了镁离子电池技术的发展,急需制备高性能的镁离子电池正极材料以解决这些技术瓶颈问题。
目前,镁离子正极材料主要集中为过渡金属硫化物、过渡金属氧化物和聚阴离子型化合物这三大类。如专利CN 107946585 A 公开了一种水热-烧结法制备掺杂硼酸镁镁离子电池正极材料的方法,该正极材料虽然提高了材料的电子电导率和离子电导率,但是循环性能依然较差(容量保持率虽然有90%以上,但是仅做了20圈的循环),放电容量仍旧较低(0.1C下最高初始放电容量仅为150 mAh·g-1左右),非常低的能量密度(45 Wh·kg-1)和功率密度(0.15 kW·kg-1)。专利CN 111916700 A 公开了一种水热法制备纳米片和纳米线共混Na-Mn-O镁离子正极材料,该正极材料在50 mA·g-1时,得到最高初始放电容量为175mAh·g-1,虽然相比一些镁离子正极材料已经有了较大提升,但是还远远无法满足电化学储能要求。此外,这些正极材料均存在扩散动力学缓慢、比容量低、循环稳定性差及低功率密度的问题,仍然制约着镁离子电池的发展与应用。
发明内容
针对现有技术存在的上述不足,本发明的目的在于提供一种镁离子电池层状水钒铜矿正极材料的制备方法,以解决现有技术镁离子电池正极材料扩散动力学缓慢、比容低、循环稳定性差以及低功率密度的问题。
为了解决上述技术问题,本发明采用如下技术方案:
一种镁离子电池层状水钒铜矿正极材料的制备方法,包括如下步骤:
步骤(1)将偏钒酸钠溶于水并调节pH为酸性,记为溶液A备用;
步骤(2)将二水氯化铜溶于去离子水中,并向其中加入溶液A混合,记为溶液B备用;
步骤(3)将苯甲酸溶于乙醇中,作为溶液C;
步骤(4)将溶液B和溶液C混合,并加入DMF溶液,混合均匀后得到前驱体溶液;其中,偏钒酸钠、二水氯化铜和苯甲酸的摩尔比为1:(8~11):(17~22),水、乙醇和DMF的体积比为1:1:1;
步骤(5)将所述前驱体溶液进行溶剂热反应,反应完成后洗涤干燥得到尺寸和形貌均一的CuVOH。
本发明还提供了一种镁离子电池层状水钒铜矿正极材料的应用,采用本发明所述方法制备得到镁离子电池层状水钒铜矿正极材料,所述镁离子电池层状水钒铜矿正极材料应用于镁离子电池、锂离子电池、锌离子电池和钠离子电池的制备。
与现有技术相比,本发明具有如下有益效果:
1、本发明采用简单的一步溶剂热法,合成了尺寸和形貌均一的微球水钒铜矿镁离子电池正极材料,制备得到的水钒铜矿为不规则微球结构,表面不平整,具有不同程度的层状突起,不仅可以为宏观电子提供快速的电子传输途径,还可以改善电极和电解质之间的渗透性,使产品展现出良好的力学性能;并且,本发明所述正极材料的制备工艺简便、成本低廉、电化学性能优异,在镁离子电池领域具有广阔的应用前景。
2、本发明制备得到的是结晶水插入层间的层状化合物水钒铜矿(Cu3V2O7(OH)2·2H2O,简记为CuVOH,由V2O7柱和结晶水分子插入Cu3O6(OH)2层构成),利用层状化合物水钒铜矿的结晶水分子对其层间进行修饰,屏蔽客体镁离子与晶格骨架之间的强静电相互作用力而构建赝电容储镁机制,缩短镁离子在正极材料表面的扩散路径、改善镁离子嵌入/脱出的动力学行为,为镁离子提供结构稳定的快速嵌入/脱出通道,解决镁离子电池正极材料目前存在的扩散动力学缓慢和比容量低的难题;而且,由于水钒铜矿正极材料主要通过赝电容机制储电,将其与活性炭负极组装为镁离子电池时,还可改善电极和电解质之间的渗透性、提高正极材料的有效比表面积,从而提升正极材料的比容量、循环稳定性和电池的功率密度,进而获得高功率密度和较高能量密度的电容型镁离子电池,且其具有超长的循环寿命。
3、本发明制备的水钒铜矿为镁离子正极材料,活性炭为负极材料组装成扣式电池,表现出了高比容量(电流密度为0.25 A·g-1时,比容量为264 mAh·g-1 )、高倍率性能(6C时比容量保持45%);与碳负极组装的扣式电池,兼具高功率密度(30 kW·kg-1)、高能量密度(103.0 Wh·kg-1)和超长的的循环寿命(20000次循环后容量保持率为92%),库伦效率稳定在100%,展现出了优异的电化学性能。
附图说明
图1为实例1制备的水钒铜矿XRD分析图。
图2为实例1制备的水钒铜矿放大20000倍的SEM图。
图3为实例1制备的水钒铜矿放大50000倍的SEM图。
图4为实例2制备的水钒铜矿TEM图。
图5为实例1制备的水钒铜矿的N2吸附-解吸等温线和孔径分布曲线。
图6为三电极体系扫描速率为0.4、0.8、1和2 mV·s-1的循环伏安曲线。
图7为三电极体系电流密度为0.25-5 A·g-1的恒流充放电曲线。
图8为两电极体系电流密度为1-15 A·g-1的恒电流充放电曲线(a)和功率密度与能量密度的关系图(b)。
图9为两电极体系恒定电流密度为10 A·g-1循环稳定性测试图。
具体实施方式
下面将结合附图及实施例对本发明作进一步说明。本领域技术人员应当知晓,此处所描述的具体实施方式仅用于说明和解释本发明,并不用于限制本发明。因此,在不脱离权利要求的精神和范围的情况下,可以对上述实例进行替换和变更。
一、镁离子电池层状水钒铜矿正极材料的制备
实施例1
(1)将偏钒酸钠(NaVO3,13g)溶于120 mL去离子水并用1 M HCl调节pH至6,记为溶液A备用,二水氯化铜(CuCl2·2H2O,0.104g)溶于24 mL去离子水中,并向其中加入0.8 mL溶液A混合,记为溶液B备用,苯甲酸(C7H6O2,0.146g)溶于24 mL乙醇中,记为溶液C;将溶液B和溶液C混合于烧杯中,并加入24 mL DMF溶液,在磁力搅拌下均匀混合30 min,得到前驱体溶液;
(2)将得到的前驱体转移至100 mL内衬为聚四氟乙烯的不锈钢反应釜中,放入鼓风干燥箱中,升温至100 ℃,保温16 h后取出冷却至室温,即得到反应产物;将反应产物过滤,得到固体产物,分别用DMF和无水乙醇洗涤离心多次后干燥处理,得到水钒铜矿。
实施例2
(1)将偏钒酸钠(NaVO3,13g)溶于120 mL去离子水并用1 M HCl调节pH至6,记为溶液A备用,二水氯化铜(CuCl2·2H2O,0.104g)溶于24 mL去离子水中,并向其中加入1 mL溶液A混合,记为溶液B备用,苯甲酸(C7H6O2,0.146g)溶于24 mL乙醇中,记为溶液C;将二分之一的溶液B先和溶液C混合于烧杯中,并加入24 mL DMF溶液,在磁力搅拌下均匀混合20 min后,再将另一半的溶液B加入至混合溶液中,继续磁力搅拌30 min,最终得到前驱体溶液;
(2)将得到的前驱体转移至100 mL内衬为聚四氟乙烯的不锈钢反应釜中,放入鼓风干燥箱中,升温至100 ℃,保温16 h后取出冷却至室温,即得到反应产物;将反应产物过滤,得到固体产物,分别用DMF和无水乙醇洗涤离心多次后干燥处理,得到水钒铜矿。
实施例3~7
本实施例水钒铜矿的制备方法和实施例1相同,不同点在于,溶液C中苯甲酸的浓度分别为0.017 mol/L、0.033 mol/L、0.067 mol/L、0.083 mol/L、0.1 mol/L。
二、制备的层状水钒铜矿的结构表征
(1)XRD表征
图1是实施例1制备的层状水钒铜矿的XRD分析图,与标准卡片做对比,所得的所有衍射峰与单斜晶体Cu3V2O7(OH)2·2H2O标准峰高度重合,表明所制备的产物为相纯的Cu3V2O7(OH)2·2H2O。
将实施例2~7制备的水钒铜矿按照相同的方法进行检测,结果与实施例1的结果基本一致。
(2)SEM和TEM表征
图2和图3为实施例1制备的水钒铜矿在不同放大倍数下的扫描电镜图,由图可以看出,本发明制备的水钒铜矿为直径为1.5~1.6 μm的不规则微球结构,且表面不平整,具有不同程度的层状凸起。对水钒铜矿进行透射及高分辨透射分析,图4a可以看出样品的阴影明暗程度不一,球体中间存在很多空隙,这表明微球在生长过程中是由不同程度大小的纳米颗粒堆积生长而成。从图4c中可以看到清晰的晶格条纹,说明样品结晶性良好;该图中的相邻晶格条纹间距为0.51 nm,与XRD分析中Cu3V2O7(OH)2·2H2O晶体(110)晶面的晶面间距一致。对水钒铜矿进行EDS元素分析,可以看出元素Cu、V和O均匀的分布于晶体。
(3)BET及孔径分布表征
水钒铜矿正极材料的N2吸附-解吸等温线和孔径分布曲线的结果如图5所示,由图可知,属于IUPAC分类中的IV型等温线,BET比表面积为13.81 m2 g-1。吸附/脱附等温线在相对压力为0.4~0.9范围内均出现了H3型回滞环,说明样品中的孔隙是由片状或板状粒子堆积成的狭缝或裂缝形孔。由水钒铜矿的孔径分布图可知,存在少量直径约3 nm的微孔以及大量直径约105 nm的大孔,平均孔径为66.02 nm,总孔容为0.42 cm3 g-1,这种特殊的多级孔结构不仅可以为宏观电子提供快速的电子传输途径,而且还可以改善电极和电解质之间的渗透性,有望展现出良好的电化学性能。
三、制备的层状水钒铜矿电化学性能测试
将实施例1中制备的层状水钒铜矿、导电剂乙炔黑和粘接剂聚偏二氟乙烯(PVDF)按照质量比8:1:1加入到N-甲基吡咯烷酮(NMP)溶液中,研磨混合至浆料,将其均匀的涂抹于1×1.5 cm长方形的碳布电极上,涂覆面积为1 cm2,在80 ºC的真空干燥箱中干燥24 h即得镁离子电池的正极极片。
本发明的电化学性能测试将先采用三电极体系,分别以水钒铜矿电极作为工作电极,石墨片作为对电极,饱和甘汞电极(SCE)作为参比电极,以0.5 M MgCl2 作为电解液对水钒铜矿正极材料进行电化学性能测试。然后在扣式两电极体系中,以水钒铜矿负载于碳布为正极,活性炭负载于碳布为负极,0.5 mol/L MgCl2 为电解液,玻璃纤维滤纸为隔膜组装于CR2430型纽扣电池中。进一步对水钒铜矿正极材料组装成器件测试其电化学性能。均使用电化学工作站(CHI660E)进行循环伏安(CV)、恒电流充放电(GCD)测试。
(1)循环伏安曲线-三电极
图6显示了水钒铜矿电极在0.5 M MgCl2溶液中的循环伏安图(CV曲线),在扫描速率为0.4、0.8、1和2 mV s-1,电压窗口为-0.8~0.8 V范围内研究了镁离子的插入和脱出行为。CV曲线并不是一个标准矩形,呈现出宽的氧化还原峰,分别位于0.5 V和-0.2 V,电化学反应式如下:
Cu3V2O7(OH)2·2H2O + xMg2+ + xe- = MgxCu3V2O7(OH)2·2H2O (1)
水钒铜矿是一种具有结构水的层状晶体,非常有利于镁离子的传输,式(1)中的x表示嵌入水钒铜矿层间的镁离子的摩尔数。
(2)恒电流充放电-三电极
图8为水钒铜矿电极材料在0.5 M MgCl2电解液中,不同电流密度下的恒电流充放电曲线(GCD)。可以看出,电压与时间呈非线性关系,说明在充放电过程中发生了氧化还原反应,归因于发生在材料表面或近表面的法拉第赝电容机制,这与CV曲线的分析结果相一致。如图6所示,随着电流密度的增加,其比容量呈降低的趋势,当电流密度为0.25 A g-1时,得到最高的放电比容量为264 mAh g-1,展现出了显著的储电容量优势。
(3)恒电流充放电和Ragon图-两电极
图8a为水钒铜矿//活性炭全电池在0.5 M MgCl2电解液中,不同电流密度下的恒电流充放电曲线(GCD)。可以看出,电压与时间呈非线性关系,不同于理想的EDLC,在EDLC中没有大量的阳离子插入,只有纯物理吸附,将会产生完美的三角形轮廓的充放电曲线。说明在充放电过程中发生了氧化还原反应,归因于发生在材料表面或近表面的法拉第赝电容机制。如图7所示,在电流密度为1、1.5和2 A g-1时,水钒铜矿//活性炭的可逆容量分别为111.12、93.70和85.20 mAh g-1,当电流密度达到15 A g-1时,可逆容量保持在22.50 mAh g-1,表明镁离子在该材料的插入和脱出具有良好可逆性、电极材料在充放电过程中具有良好的结构稳定性。水钒铜矿//活性炭全电池的不同电流密度下GCD曲线近似对称,这表明了水钒铜矿//活性炭具有良好的速率性能和可逆性。图8b是水钒铜矿//活性炭全电池在0.5 MMgCl2电解液中的能量密度和功率密度关系图(Ragone曲线),当电流密度为1 A g-1时,能量密度为103.0 Wh kg-1,展现了2 kW kg-1的超高功率密度;在超大电流密度15 A g-1时具有30 W kg-1的功率密度,此时能量密度仍然有22.3 Wh kg-1,表明水钒铜矿正极材料在0.5 MMgCl2电解液中优异的电化学性能。图8还展示了一些其他报道中的镁离子电池,例如Mg-OMS-2/Graphene//AC(能量密度为46.9 Wh kg-1时功率密度为60.2 W kg-1)、Na0.61Fe[Fe(CN)6]0.94//Mg3Bi2(能量密度为81.2 Wh kg-1时功率密度为195.4 W kg-1)、Prussian bluenickel//Polyimide(能量密度为45.6 Wh kg-1时功率密度为182.7 W kg-1),与这些镁离子电池相比,本发明制备的水钒铜矿与活性炭组装的镁离子电池具有非常高的能量密度和功率密度。
(4)循环稳定性测试-两电极
将水钒铜矿//活性炭全电池在10 A g-1的电流密度、电压窗口为0~0.82 V进行恒电流充放电循环20000次,测试其稳定性。图9为不同循环次数下的比容量和库伦效率。经过20000次循环后容量的保持率为92%,其库伦效率稳定在100%,说明本发明制备的水钒铜矿作为正极材料具有较好的循环稳定性,镁离子在水钒铜矿结构的插入和脱出是高度可逆的,这得益于水钒铜矿具有适于镁离子插入/脱出的大孔和层状结构。
本发明采用简单的一步溶剂热法,合成了尺寸和形貌均一的微球水钒铜矿镁离子电池正极材料,制备得到的水钒铜矿为不规则微球结构,表面不平整,具有不同程度的层状突起,不仅可以为宏观电子提供快速的电子传输途径,还可以改善电极和电解质之间的渗透性,使产品展现出良好的力学性能;并且,本发明所述正极材料的制备工艺简便、成本低廉、电化学性能优异,在镁离子电池领域具有广阔的应用前景。本发明制备得到的是结晶水插入层间的层状化合物水钒铜矿(Cu3V2O7(OH)2·2H2O,简记为CuVOH,由V2O7柱和结晶水分子插入Cu3O6(OH)2层构成),利用层状化合物水钒铜矿的结晶水分子对其层间进行修饰,屏蔽客体镁离子与晶格骨架之间的强静电相互作用力而构建赝电容储镁机制,缩短镁离子在正极材料表面的扩散路径、改善镁离子嵌入/脱出的动力学行为,为镁离子提供结构稳定的快速嵌入/脱出通道,解决镁离子电池正极材料目前存在的扩散动力学缓慢和比容量低的难题;而且,由于水钒铜矿正极材料主要通过赝电容机制储电,将其与活性炭负极组装为镁离子电池时,还可改善电极和电解质之间的渗透性、提高正极材料的有效比表面积,从而提升正极材料的比容量、循环稳定性和电池的功率密度,进而获得高功率密度和较高能量密度的电容型镁离子电池,且其具有超长的循环寿命。本发明制备的水钒铜矿为镁离子正极材料,活性炭为负极材料组装成扣式电池,表现出了高比容量(电流密度为0.25 A·g-1时,比容量为264 mAh·g-1 )、高倍率性能(6C时比容量保持45%);与碳负极组装的扣式电池,兼具高功率密度(30 kW·kg-1)、高能量密度(103.0 Wh·kg-1)和超长的的循环寿命(20000次循环后容量保持率为92%),库伦效率稳定在100%,展现出了优异的电化学性能。
最后需要说明的是,以上实施例仅用以说明本发明的技术方案而非限制技术方案,本领域的普通技术人员应当理解,那些对本发明的技术方案进行修改或者等同替换,而不脱离本技术方案的宗旨和范围,均应涵盖在本发明的权利要求范围当中。
Claims (10)
1.一种镁离子电池层状水钒铜矿正极材料的制备方法,其特征在于,包括如下步骤:
步骤(1)将偏钒酸钠溶于水并调节pH为酸性,记为溶液A备用;
步骤(2)将二水氯化铜溶于去离子水中,并向其中加入溶液A混合,记为溶液B备用;
步骤(3)将苯甲酸溶于乙醇中,作为溶液C;
步骤(4)将溶液B和溶液C混合,并加入DMF溶液,混合均匀后得到前驱体溶液;其中,偏钒酸钠、二水氯化铜和苯甲酸的摩尔比为1:(8~11):(17~22),水、乙醇和DMF的体积比为1:1:1;
步骤(5)将所述前驱体溶液进行溶剂热反应,反应完成后洗涤干燥得到尺寸和形貌均一的水钒铜矿材料CuVOH。
2.根据权利要求1所述镁离子电池层状水钒铜矿正极材料的制备方法,其特征在于,在步骤(1)中,偏钒酸钠溶液的浓度为0.05~0.15mol/L。
3.根据权利要求1所述镁离子电池层状水钒铜矿正极材料的制备方法,其特征在于,所述步骤(1)中,通过加入盐酸将偏钒酸钠溶液的pH值调整至5~6。
4.根据权利要求1所述镁离子电池层状水钒铜矿正极材料的制备方法,其特征在于,所述步骤(2)中,二水氯化铜的浓度为0.02~0.06mol/L。
5.根据权利要求1所述镁离子电池层状水钒铜矿正极材料的制备方法,其特征在于,所述步骤(3)中,苯甲酸溶液的浓度为0.03~0.15mol/L。
6.根据权利要求1所述镁离子电池层状水钒铜矿正极材料的制备方法,其特征在于,所述步骤(4)中,混合溶液通过磁力搅拌30~60min使前驱体溶液混合均匀。
7.根据权利要求1所述镁离子电池层状水钒铜矿正极材料的制备方法,其特征在于,所述步骤(5)中,溶剂热反应温度为80~120℃,反应时间为10~24h。
8.根据权利要求1所述镁离子电池层状水钒铜矿正极材料的制备方法,其特征在于,所述步骤(5)中得到的反应产物分别用DMF和无水乙醇洗涤多次。
9.根据权利要求1所述镁离子电池层状水钒铜矿正极材料的制备方法,其特征在于,所述步骤(5)中产物置于100~150℃真空干燥箱中,干燥时间12h。
10.一种镁离子电池层状水钒铜矿正极材料的应用,其特征在于,采用权利要求1~9任一所述方法制备得到镁离子电池层状水钒铜矿正极材料,所述镁离子电池层状水钒铜矿正极材料应用于镁离子电池、锂离子电池、锌离子电池和钠离子电池的制备。
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4668594A (en) * | 1984-04-06 | 1987-05-26 | Matsushita Electric Industrial Co., Ltd. | Rechargeable electrochemical apparatus and positive electrode thereof |
CN105895894A (zh) * | 2016-04-20 | 2016-08-24 | 淮阴工学院 | 一种钒酸铜材料及其制备方法与电化学性能 |
CN108117098A (zh) * | 2017-12-14 | 2018-06-05 | 陕西科技大学 | 一种珊瑚状α-Cu2V2O7粉体的制备方法 |
CN109534401A (zh) * | 2018-11-12 | 2019-03-29 | 青岛科技大学 | 一种钒酸铜的制备方法,该方法制备得到的钒酸铜及其在锂离子电池中的应用 |
KR20200009549A (ko) * | 2018-07-19 | 2020-01-30 | 한국과학기술연구원 | 질소산화물 환원용 촉매 및 이의 제조방법 |
CN112670494A (zh) * | 2021-01-20 | 2021-04-16 | 广东工业大学 | 一种钒酸盐电极材料及其制备方法和应用 |
CN112791730A (zh) * | 2021-01-11 | 2021-05-14 | 中南大学 | 一种z型纳米钒酸铜基复合光催化剂及其制备方法和应用 |
CN115043429A (zh) * | 2022-06-24 | 2022-09-13 | 重庆镁储新材料科技有限公司 | 一种层状羟基焦钒酸铜正极材料的制备方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7045249B2 (en) * | 2003-07-02 | 2006-05-16 | The Gillette Company | Lithium cell with improved cathode |
-
2021
- 2021-11-15 CN CN202111349034.8A patent/CN114031115B/zh active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4668594A (en) * | 1984-04-06 | 1987-05-26 | Matsushita Electric Industrial Co., Ltd. | Rechargeable electrochemical apparatus and positive electrode thereof |
CN105895894A (zh) * | 2016-04-20 | 2016-08-24 | 淮阴工学院 | 一种钒酸铜材料及其制备方法与电化学性能 |
CN108117098A (zh) * | 2017-12-14 | 2018-06-05 | 陕西科技大学 | 一种珊瑚状α-Cu2V2O7粉体的制备方法 |
KR20200009549A (ko) * | 2018-07-19 | 2020-01-30 | 한국과학기술연구원 | 질소산화물 환원용 촉매 및 이의 제조방법 |
CN109534401A (zh) * | 2018-11-12 | 2019-03-29 | 青岛科技大学 | 一种钒酸铜的制备方法,该方法制备得到的钒酸铜及其在锂离子电池中的应用 |
CN112791730A (zh) * | 2021-01-11 | 2021-05-14 | 中南大学 | 一种z型纳米钒酸铜基复合光催化剂及其制备方法和应用 |
CN112670494A (zh) * | 2021-01-20 | 2021-04-16 | 广东工业大学 | 一种钒酸盐电极材料及其制备方法和应用 |
CN115043429A (zh) * | 2022-06-24 | 2022-09-13 | 重庆镁储新材料科技有限公司 | 一种层状羟基焦钒酸铜正极材料的制备方法 |
Non-Patent Citations (1)
Title |
---|
Switchable and Strain-Releasable Mg-Ion Diffusion Nanohighway Enables High-Capacity and Long-Life Pyrovanadate Cathode;Xiu-Fen Ma et al.,;《Small》;第18卷;2202250 (1-9) * |
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