CN114074956B - 一种水系钙离子电池正极活性材料及其制备方法和应用 - Google Patents
一种水系钙离子电池正极活性材料及其制备方法和应用 Download PDFInfo
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- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910001424 calcium ion Inorganic materials 0.000 title claims abstract description 55
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 16
- BQFYGYJPBUKISI-UHFFFAOYSA-N potassium;oxido(dioxo)vanadium Chemical compound [K+].[O-][V](=O)=O BQFYGYJPBUKISI-UHFFFAOYSA-N 0.000 claims abstract description 16
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 11
- 239000002070 nanowire Substances 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 239000001103 potassium chloride Substances 0.000 claims abstract description 8
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 8
- 238000004108 freeze drying Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000006183 anode active material Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- 239000004020 conductor Substances 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000006258 conductive agent Substances 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000011149 active material Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- PAJMKGZZBBTTOY-UHFFFAOYSA-N 2-[[2-hydroxy-1-(3-hydroxyoctyl)-2,3,3a,4,9,9a-hexahydro-1h-cyclopenta[g]naphthalen-5-yl]oxy]acetic acid Chemical compound C1=CC=C(OCC(O)=O)C2=C1CC1C(CCC(O)CCCCC)C(O)CC1C2 PAJMKGZZBBTTOY-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 2
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 239000002074 nanoribbon Substances 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000010405 anode material Substances 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 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
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
一种水系钙离子电池正极活性材料及其制备方法和应用。本发明属于钙离子电池领域。本发明的目的在于解决现有钙离子电池比容量低,循环性差的技术问题。正极活性材料为纳米线或纳米带状的钒酸钾;所述钒酸钾为K2V6O16·nH2O,其中0≤n≤2.7。方法:将偏钒酸铵和氯化钾溶于去离子水,然后调节pH值至2~4,再进行水热反应,产物离心洗涤、冷冻干燥后得到正极活性材料。将水系钙离子电池正极活性材料作为钙离子电池正极材料的组成物应用在钙离子电池中。本发明采用一步水热法合成了钒酸钾电极活性材料,其作为钙离子电池正极材料,电化学性能良好,表现了比较高的比容量和良好的循环性能,具有良好的综合电化学性能。
Description
技术领域
本发明属于钙离子电池领域;具体涉及一种水系钙离子电池正极活性材料及其制备方法和应用。
背景技术
随着化石燃料的枯竭以及所带来的环境污染,导致各种可再生能源和清洁能源兴起。然而,这些可再生能源通常具有间歇性等特点。目前,锂离子电池是目前使用最广泛的二次电池,其具有高的能量密度等优点,但因锂元素地球含量相对较少,使得未来使用锂电池进行大规模储能的愿望破灭。所以,多价金属离子电池技术以低成本,更安全,高的理论比容量引起了人们的关注。其中,钙离子电池以低成本(钙元素地球储量丰富),极化低、标准电极电势与锂接近(标准还原电位仅比锂电池高170mV),钙离子为+2价是单价离子电荷载体的两倍等优势受到关注。因此,钙离子电池在未来有很大的发展潜能和应用前景。
然而,目前钙离子电池开发出来的正极材料种类很少,仅有普鲁士蓝及其类似物、V2O5、WO3、NH4V4O10、α-MoO3、CaCo2O4、Mg0.25V2O5·H2O、K0.31MnO2·0.25H2O等十种左右材料可以实现钙离子的嵌脱,然而这些材料大部分都具有比容量低,循环性能差等缺点,导致钙离子电池综合电化学性能较差。
发明内容
本发明的目的在于解决现有钙离子电池比容量低,循环性差的技术问题,而提供了一种水系钙离子电池正极活性材料及其制备方法和应用。
本发明的一种水系钙离子电池正极活性材料为纳米线或纳米带状的钒酸钾;所述钒酸钾为K2V6O16·nH2O,其中0≤n≤2.7。
进一步限定,所述纳米线或纳米带的长度为0.5μm~1.5μm,宽度为70nm~100nm。
本发明的一种水系钙离子电池正极活性材料的制备方法按以下步骤进行:
一、将偏钒酸铵加入到去离子水中,搅拌至其完全溶解,得到淡黄色溶液,然后加入氯化钾,继续搅拌至其完全溶解,得到混合溶液;
二、调节步骤一得到的混合溶液的pH值至2~4,然后转移至反应釜中进行水热反应,反应结束后自然冷却至室温,得到褐绿色产物;
三、将步骤二得到的褐绿色产物进行离心洗涤,然后冷冻干燥,得到纳米线或纳米带状的钒酸钾。
进一步限定,步骤一中所述偏钒酸铵与氯化钾的摩尔比为(2~4):1。
进一步限定,步骤一中所述偏钒酸铵与氯化钾的摩尔比为3:1。
进一步限定,步骤一中所述偏钒酸铵的质量与去离子水的体积的比为(0.25~0.45)g:30mL。
进一步限定,步骤一中所述偏钒酸铵的质量与去离子水的体积的比为0.35g:30mL。
进一步限定,步骤一中所述搅拌溶解过程在60~80℃下进行。
进一步限定,步骤二中用盐酸调节pH值。
进一步限定,步骤二中所述水热反应参数为:温度为170~190℃,时间为20h~24h。
进一步限定,步骤二中所述水热反应参数为:温度为180℃,时间为24h。
进一步限定,步骤三中用去离子水离心洗涤1次以上。
进一步限定,步骤三中所述冷冻干燥参数为:温度为-40~-60℃,时间为20h~24h。
进一步限定,步骤三中所述冷冻干燥参数为:温度为-50℃,时间为24h。
本发明的一种水系钙离子电池正极活性材料的应用在于将水系钙离子电池正极活性材料作为钙离子电池正极材料的组成物应用在钙离子电池中。
进一步限定,所述钙离子电池正极材料由集流体材料和涂覆于集流体材料表面的复合导电材料构成;所述复合导电材料按质量分数由70%~90%的水系钙离子电池正极活性材料、5%~15%的导电剂和5%~15%的粘结剂混合而成。
进一步限定,所述集流体材料为铜、铝、泡沫镍或碳纸。
进一步限定,所述导电剂为导电炭黑、乙炔黑、碳纳米管、石墨烯或活性炭。
进一步限定,所述粘结剂为聚四氟乙烯、聚偏氟乙烯、聚乙烯醇、羟甲基纤维素钠或丁苯橡胶。
本发明与现有技术相比具有的显著效果如下:
本发明采用一步水热法合成了钒酸钾电极活性材料,其作为钙离子电池正极材料,电化学性能良好,表现了比较高的比容量和良好的循环性能,具有良好的综合电化学性能。此外,本发明的合成工艺简单,成本低,利于未来商业化使用。与目前其它钙离子电池正极材料的区别在于主要的活性物质材料不同,该发明的活性材料同时兼具较高比容量和好的循环性能的优势。
附图说明
图1为具体实施方式一的水系钙离子电池正极活性材料的SEM照片;
图2为具体实施方式一的水系钙离子电池正极活性材料的TEM照片;
图3为具体实施方式三的水系钙离子电池正极材料在电流密度20mAg-1下和电位区间0-1V下得到的充放电曲线;
图4为具体实施方式三的水系钙离子电池正极材料在电流密度50mAg-1下和电位区间0-1V下得到的循环容量及其库伦效率曲线图;
图5为具体实施方式三的水系钙离子电池正极材料在电流密度100mAg-1下和电位区间0-1V下得到的循环容量及其库伦效率曲线图。
具体实施方式
具体实施方式一:本实施方式的一种水系钙离子电池正极活性材料为纳米线状的钒酸钾;所述钒酸钾为K2V6O16·2.7H2O;所述纳米线的长度为0.5μm~1.5μm,宽度为70nm~100nm。
图1为具体实施方式一的钒酸钾K2V6O16·2.7H2O的扫描电镜图片,表明所得产物为纳米线,其长度0.5μm~1.5μm,宽度70nm~100nm。
图2为具体实施方式一的钒酸钾K2V6O16·2.7H2O的透射电镜图片,进一步表明其为纳米线结构。
具体实施方式二:制备具体实施方式一所述的一种水系钙离子电池正极活性材料的方法按以下步骤进行:
一、将0.349g的NH4VO3加入到30mL去离子水中,于70℃下搅拌至其完全溶解,得到淡黄色溶液,然后加入0.895g的KCl,继续于70℃下搅拌至其完全溶解,得到混合溶液;
二、采用盐酸调节步骤一得到的混合溶液的pH值至3,然后转移至聚四氟乙烯内衬的反应釜中,将反应釜置于鼓风干燥箱中,于180℃下水热反应24h,反应结束后自然冷却至室温,得到褐绿色产物;
三、将步骤二得到的褐绿色产物用去离子水进行离心洗涤3次,然后于-50℃下冷冻干燥24h,得到长度为0.5μm~1.5μm,宽度为70nm~100nm的纳米线状的K2V6O16·2.7H2O。
具体实施方式三:将具体实施方式一所述的一种水系钙离子电池正极活性材料作为钙离子电池正极材料的组成物应用在钙离子电池中;所述钙离子电池正极材料由碳纸和涂覆于碳纸表面的复合导电材料构成;所述复合导电材料按质量分数由80%的水系钙离子电池正极活性材料、10%的乙炔黑和10%的聚偏氟乙烯混合而成。
为验证本发明的水系钙离子电池正极活性材料作为钙离子电池正极材料的性能,进行下述试验:
将具体实施方式三的正极材料作为工作电极在三电极体系下进行测试,对电极为铂片电极,参比电极为银/氯化银电极,电解液为浓度为5mol/L的硝酸钙的水溶液。
图3为具体实施方式三的正极材料在电流密度20mAg-1下得到了113.9mAhg-1的放电比容量。
图4为具体实施方式三的正极材料在电流密度50mAg-1得到了94.0mAhg-1的放电比容量,其在100个循环后依然保持了78.3%的容量。
图5为具体实施方式三的正极材料在电流密度为100mAg-1的循环性能,仍然可以达到高达60mAhg-1的放电比容量,在200个循环后容量依然可以保持66.5%,而且其库伦效率超过99%。
综上所述,本发明所述正极活性物质应用于钙离子电池时,在0-1V较低的工作电压,就可以实现高的比容量和好的循环性能,未来可以通过进一步提高电压进一步提高比容量和其电化学综合性能,拥有良好的应用前景。
Claims (6)
1.一种水系钙离子电池正极活性材料的应用,其特征在于,该正极活性材料为纳米线或纳米带状的钒酸钾;所述钒酸钾为K2V6O16·2.7H2O,所述纳米线或纳米带的长度为0.5μm~1.5μm,宽度为70nm~100nm;
制备方法按以下步骤进行:
一、将偏钒酸铵加入到去离子水中,搅拌至其完全溶解,得到淡黄色溶液,然后加入氯化钾,继续搅拌至其完全溶解,得到混合溶液;
二、调节步骤一得到的混合溶液的pH值至2~4,然后转移至反应釜中进行水热反应,反应结束后自然冷却至室温,得到褐绿色产物;
三、将步骤二得到的褐绿色产物进行离心洗涤,然后在- 40~ - 60℃下冷冻干燥20h~24h,得到纳米线或纳米带状的钒酸钾;
将水系钙离子电池正极活性材料作为钙离子电池正极材料的组成物应用在钙离子电池中。
2.根据权利要求1所述的一种水系钙离子电池正极活性材料的应用,其特征在于,步骤一中所述偏钒酸铵与氯化钾的摩尔比为(2~4):1;步骤一中所述偏钒酸铵的质量与去离子水的体积的比为(0.25~0.45)g:30mL。
3.根据权利要求1所述的一种水系钙离子电池正极活性材料的应用,其特征在于,步骤一中搅拌溶解过程在60~80℃下进行。
4.根据权利要求1所述的一种水系钙离子电池正极活性材料的应用,其特征在于,步骤二中所述水热反应参数为:温度为170~190℃,时间为20h~24h。
5.根据权利要求1所述的一种水系钙离子电池正极活性材料的应用,其特征在于,所述钙离子电池正极材料由集流体材料和涂覆于集流体材料表面的复合导电材料构成;所述复合导电材料按质量分数由70%~90%的水系钙离子电池正极活性材料、5%~15%的导电剂和5%~15%的粘结剂混合而成。
6.根据权利要求5所述的一种水系钙离子电池正极活性材料的应用,其特征在于,所述集流体材料为铜、铝、泡沫镍或碳纸;所述导电剂为导电炭黑、乙炔黑、碳纳米管、石墨烯或活性炭;所述粘结剂为聚四氟乙烯、聚偏氟乙烯、聚乙烯醇、羟甲基纤维素钠或丁苯橡胶。
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