CN118231663A - 复合补锂/补钠剂及其制备方法和应用 - Google Patents

复合补锂/补钠剂及其制备方法和应用 Download PDF

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CN118231663A
CN118231663A CN202410076709.3A CN202410076709A CN118231663A CN 118231663 A CN118231663 A CN 118231663A CN 202410076709 A CN202410076709 A CN 202410076709A CN 118231663 A CN118231663 A CN 118231663A
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lithium
sodium
supplement
supplementing
composite
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谢芳
杨雪
王琼
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Shandong Haike Innovation Research Institute Co Ltd
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Abstract

本发明提出一种复合补锂/补钠剂及其制备方法和应用，属于电池添加剂技术领域。所述复合补锂/补钠剂包括内核和包覆在内核外部的纳米包覆层；所述内核为补锂/补钠活性粒子；所述纳米包覆层为金属或金属化合物。本发明提供的复合补锂/补钠剂可有效解决锂/钠离子电池中活性锂/钠离子损失的问题，达到提升锂/钠离子电池能量密度和循环稳定性的效果。

Description

复合补锂/补钠剂及其制备方法和应用
技术领域
本发明属于电池添加剂制备技术领域，尤其涉及一种复合补锂/补钠剂及其制备方法和应用。
背景技术
无论是锂离子电池还是钠离子电池，在首次充放电过程中，均会因负极表面SEI膜的形成造成正极材料不可逆的活性锂/钠损失，从而降低电池的可用能量密度。在硬炭负极、硅碳负极中，这种不可逆消耗尤为严重。预锂化/预钠化被认为是补偿负极活性锂/锂/钠损失、提升电池能量密度的最直接有效的方法，对于提升锂离子电池性能、实现锂/钠离子电池的商业化应用具有重要意义。
按照预锂/锂/钠化处理的电极不同，可将预锂/钠化方法分为正极预锂/锂/钠化和负极预锂/钠化。相对而言，正极添加剂补锂/钠法可兼容现有锂/钠离子电池的极片制备工艺，操作简单且补锂/钠效果好，具有广阔的发展前景。目前研究较多的正极补钠添加剂有叠氮化钠、磷化钠、过氧化钠、镍酸钠、铬酸钠、碳酸钠和草酸钠等。但是这些补钠添加剂也各自存在一定的问题，如叠氮化钠、磷化钠剧毒且易爆；镍酸钠、铬酸钠容量释放效率不高，不仅不能明显提升容量提升，同时含有的重金属也对环境带来污染。碳酸钠实际补钠容量小，且O2产生会影响电池性能；过氧化钠空气稳定性差，草酸钠价格低廉、易制备更具有更高的产业化价值，但草酸钠的脱钠电压(一般＞4.2V)偏高于钠离子电池工作电压(一般＜3.95V)，一直是限制其产业化的难题。
而现有技术的复合补锂/补钠剂，通常是将补钠/补锂材料与导电炭或催化剂进行简单的混合，而这种方式使得各功能组分之间接触不充分，不利于充分发挥各组分功能，钠/锂离子扩散路径较长，分解电压较高，与现有的商业化正极材料的化成程序不能完全匹配。
发明内容
本发明提供了一种复合补锂/补钠剂及其制备方法和应用，本发明提供的复合补锂/补钠剂可有效解决锂/钠离子电池中活性锂/钠离子损失的问题，达到提升锂/钠离子电池能量密度和循环稳定性的效果。
为了达到上述目的，本发明提供了一种复合补锂/补钠剂，包括内核和包覆在内核外部的纳米包覆层；所述内核为补锂/补钠活性粒子；所述纳米包覆层为金属或金属化合物。
优选的，所述补锂/补钠活性粒子中补锂活性粒子为草酸锂、氟化锂、硫化锂、氧化锂和氯化锂中的一种或多种；补钠活性粒子为草酸钠和/或氟化钠。
优选的，所述补锂/补钠活性粒子的粒径为30nm～500nm，比表面积为20～300m2/g。
优选的，所述金属为Ti、Cr、Mn、Fe、Co、Ni、Cu、Zn、Mo、Sn、Au、Ag、Pd、Pd、Ta、Sn、Rh中的一种或多种；所述金属化合物为金属氧化物或金属氮化物。
优选的，按重量百分比计，所述复合补锂/补钠剂中补锂/补钠活性粒子占比为90～99.99％，纳米包覆层占比为0.01％～10％。
本发明提供了上述任意一项所述的复合补锂/补钠剂的制备方法，包括如下步骤：
1)将补锂/补钠活性粒子置入流化床-原子层沉积设备内进行流化；
2)在流化床-原子层沉积设备内通入反应气和气化的包覆层原料进行原子层沉积，得到复合补锂/补钠剂。
优选的，步骤2)中当包覆层为金属氧化物时，反应气为水蒸气、氧气和臭氧中的至少一种；当包覆层金属氮化物时，反应气为氮气、氨气或氨气与水蒸气的混合物的至少一种。
优选的，步骤2)中所述包覆层用原料包括金属，金属的氯化物、氟化物、碘化物、酯化物，烷基金属有机化合物或烷基金属氧化物。
优选的，步骤2)中所述反应气的通入量为0.05～1L/min，气化的包覆层原料的通入量为0.1～5L/min；沉积时间为5～300min。
本发明提供了上述任意一项所述的复合补锂/补钠剂在锂/钠离子电池正极中的应用。
与现有技术相比，本发明的优点和积极效果在于：
(1)本发明提供的复合补锂/补钠剂，以补锂/补钠活性粒子为内核，外部包覆纳米级别的金属成分，该纳米包覆层具有催化补锂/补钠活性粒子分解的作用，可以降低补锂/钠活性粒子的电荷转移能垒，降低脱锂/钠电位，提高脱锂/钠效率，且小粒径的金属成分比表面积大，从而增大与活性粒子的接触面积，脱锂/钠更加充分，循环产气量少，补锂/钠效果优异。
(2)本发明提供的复合补锂/补钠剂的包覆层为原子级包覆层，几乎不占据活性物质质量，补锂容量可得到充分利用；
(3)制备得到的复合补锂/补钠剂的粒径小，有利于锂/钠离子扩散，提高补锂/补钠效果。
(4)本发明提供的复合补锂/补钠剂，补锂/补钠活性粒子价格低廉、空气稳定性好、补锂容量适中。
(5)本发明提供的复合补锂/补钠剂分解产物为气体，化成时可排出，对电池后续循环无影响；
(6)本发明制备过程绿色环保无污染，操作简单，易工业化，合成工艺简单高效、能耗小。
附图说明
图1为实施例1和7制备得到的产品的SEM图；
图2为实施例1和7制备得到的产品的HRTEM图；
图3为实施例1和7制备得到的产品的半电池充电曲线图；
图4为实施例1和7制备得到的产品的全电池首圈充放电曲线。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、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。
本发明提供了一种复合补锂/补钠剂，包括内核和包覆在内核外部的纳米包覆层；所述内核为补锂/补钠活性粒子；所述纳米包覆层为金属或金属化合物。
在本发明中，所述补锂/补钠活性粒子中补锂活性粒子优选为草酸锂、氟化锂、硫化锂、氧化锂和氯化锂中的一种或多种；补钠活性粒子优选为草酸钠和/或氟化钠。在本发明中，所述补锂/补钠活性粒子的粒径优选为30nm～500nm，比表面积为20～300m2/g。在本发明中，采用上述材料作为补锂/补钠活性粒子，不仅价格低廉，空气稳定性好，且补锂容量适中。
在本发明中，所述纳米包覆层为金属或金属化合物。所述金属优选为Ti、Cr、Mn、Fe、Co、Ni、Cu、Zn、Mo、Sn、Au、Ag、Pd、Pt、Ta、Sn、Rh中的一种或多种；所述金属化合物优选为金属氧化物或金属氮化物，更优选为氧化锌或二氧化钛。
金属氧化物、氮化物，尤其是过渡金属氧化物、氮化物如Co3O4、MnO2、TiO2、ZnO、Cu3N、TiN等具有较高的催化活性，可以降低锂盐和钠盐的分解能垒，进一步降低脱锂/脱钠电位。而贵金属如Au、Ag、Pd、Pd、Rh等，不仅具有较高的催化活性，而且还具有优异的导电性，不仅可以催化锂盐和钠盐的分解能垒，还可以提供优异的电子导电性，降低脱锂/钠极化。从性价比来看，金属氧化物为最优选。
在本发明中，按重量百分比计，所述复合补锂/补钠剂中补锂/补钠活性粒子占比优选为90～99.99％，纳米包覆层占比优选为0.01％～10％。在本发明中，将补锂/补钠活性粒子和纳米包覆层的用量限定在上述范围内，既可以充分将补锂/补钠活性粒子进行包覆，同时包覆层几乎不占据活性物质质量，补锂/补钠容量可得到充分利用。
本发明提供的复合补锂/补钠剂，以金属或金属化合物作为纳米包覆层，该纳米包覆层具有催化补锂/钠活性粒子分解的作用，可以降低补锂/钠活性粒子的电荷转移能垒，降低脱锂/钠电位，提高脱锂/钠效率。同时该复合补锂/补钠剂分解产物为气体，化成时可排出，对后续电池循无影响。
本发明提供了上述任意一项所述的复合补锂/补钠剂的制备方法，包括如下步骤：
1)将补锂/补钠活性粒子置入流化床-原子层沉积设备内进行流化；
2)在流化床-原子层沉积设备内通入反应气和气化的包覆层原料进行原子层沉积，得到复合补锂/补钠剂。
本发明将补锂/补钠活性粒子置入流化床-原子层沉积设备内进行流化。在本发明中，补锂/补钠活性粒子在进行流化前优选先进行研磨和喷雾干燥。目前市场售卖的草酸锂、氟化锂、硫化锂、氧化锂和氯化锂的粒径一般在数十微米，粒径相对较大。在本发明中，通过研磨和喷雾干燥可以减少粒径，使粒径控制在几十到几百纳米，从而利于锂/钠离子扩散，提高补锂/补钠效果。
在本发明中，当包覆层为金属氧化物时，反应气优选为水蒸气、氧气和臭氧中的至少一种；当包覆层金属氮化物时，反应气优选为氮气、氨气或氨气与水蒸气的混合物的至少一种。在本发明中，所述包覆层所用原料优选包括金属的氯化物、氟化物、碘化物、酯化物、烷基金属有机化合物或烷基金属氧化物，更优选为ZnCl2、ZnMe2、ZnEt2、Zn(OAc)2、TiCl4、TiI4、TiBr4、Ti(OMe)4、Ti(OEt)4和Ti(OBu)4中的一种或多种。在本发明中，通过在流化床-原子层沉积设备中同时通入反应气和气化的包覆层原料，从而在设备内进行反应，得到纳米包覆层，并包覆在补锂/补钠活性粒子上。
在本发明中，流化床可以保证颗粒在原子沉积设备的腔体内始终保持流化状态，保证表面可以均匀沉积；原子层沉积法可以精准地控制包覆层的原子层数量和包覆层厚度，从而得到最佳的包覆效果。本发明通过流化床-原子层沉积对补锂/补钠活性粒子进行包覆，使包覆层物料为原子级别，粒径小，比表面积大，从而大大增加与补锂/补钠活性离子的接触面积，提高对补锂/补钠活性粒子的催化分解作用。而且包覆层为原子级包覆层，最终的厚度仅为数纳米，几乎不占据活性物质质量，补锂容量可得到充分利用。
在本发明中，通过控制调控反应气和气化的包覆层原料的通入量，以及沉积时间来控制包覆层的厚度。在本发明中，所述反应气的通入量优选为0.05～1L/min，气化的包覆层原料的通入量为0.1～5L/min；沉积时间为5～300min。在本发明中，通过将通入量及沉积时间控制在上述参数范围内，可以使得纳米包覆层的厚度在1～50个原子层。
为了提高锂盐/钠盐与包覆层间的结合力，可以将气相沉积后的产品进行低温热处理(＜300℃)，温度高则锂盐/钠盐分解，温度低则键合效果不佳。
本发明提供了上述任意一项所述的复合补锂/补钠剂在锂/钠离子电池正极中的应用。
在本发明中，所述复合补锂/补钠剂的添加量为正极活性物质质量的0.5％～5％。在本发明中，当为锂电池时，所述正极活性物质优选为磷酸锂铁、三元镍钴锰、磷酸锰铁锂、钴酸锂中的至少一种，更优选为磷酸铁锂；当为钠电池时，所述正极活性物质优选包括磷酸钒钠、氟磷酸钒钠、磷酸铁钠、焦磷酸铁纳、磷酸钒锰钠、钴酸钠、锰酸钠、镍酸钠、铬酸钠、镍锰酸钠中的一种，更优选为焦磷酸铁纳。在本发明中，所述锂离子电池的负极优选为人造石墨或天然石墨，更优选为人造石墨。在本发明中，所述钠离子电池的负极优选为软碳或硬炭，更优选为硬碳。
为了进一步说明本发明，下面结合实施例对本发明提供的技术方案进行详细地描述，但不能将它们理解为对本发明保护范围的限定。
实施例1
将草酸锂进行砂磨2h、闭式喷雾干燥得纳米草酸锂，测试草酸锂的粒径分布D10-D90范围为：30～200nm；取30g上述纳米草酸锂置于流化床-ALD设备中，保持进气口温度为120℃，先后通入水蒸气(通入量为0.1L/min)进行草酸锂衬底饱和吸附、通入氩气吹扫多余水蒸气、通入TiCl4气体(通入量为2L/min)进行原子沉积反应、通入氩气吹扫多余TiCl4气体和副产物，如此反复循环反应30min后，降温收料得Li2C2O4@TiO2复合补锂剂。制备得到的复合补锂剂的SEM图如图1所述，HRTEM图如图2所示。由图1～2可以看出复合补锂剂表层具有约1～5nm的均匀包覆层。
实施例2
将草酸锂进行砂磨5h、闭式喷雾干燥得纳米草酸锂，测试草酸锂的粒径分布D10-D90范围为：100nm～400nm；取30g纳米草酸锂置于流化床-ALD设备中，保持进气口温度为150℃，先后通入水蒸气(通入量为1L/min)进行草酸锂衬底饱和吸附、通入氮气吹扫多余水蒸气、通入ZnEt2气体(通入量为5L/min)进行原子沉积反应、通入氩气吹扫多余TiCl4气体和副产物，如此反复循环反应120min后，通过氮气气体吹扫尾气及副产物，降温收料得Li2C2O4@ZnO复合补锂剂。
实施例3
将氟化锂进行砂磨4h、闭式喷雾干燥得纳米氟化锂，测试氟化锂的粒径分布D10-D90范围为：50nm～300nm；取30g上述纳米氟化锂置于流化床-ALD设备中，保持进气口温度为150℃，先后通入氧气(通入量为0.05L/min)进行氟化锂衬底饱和吸附、通入氮气吹扫多余氧气、通入SnI4气体(通入量为2L/min)进行原子沉积反应、通入氮气吹扫多余TiCl4气体和副产物，如此反复循环反应40min后，通过氮气气体吹扫尾气及副产物，降温收料得LiF@SnO复合补锂剂。
实施例4
将氟化锂进行砂磨、闭式喷雾干燥得纳米氟化锂，测试氟化锂的粒径分布D10-D90范围为：40nm-200nm；取20g上述纳米氟化锂置于流化床-ALD设备中，保持进气口温度为180℃，先后通入氨气(通入量为0.08L/min)进行氟化锂衬底饱和吸附、通入氮气吹扫多余氨气、通入Cu(BuAMD)气体(通入量为4L/min)进行原子沉积反应、通入氮气吹扫多余TiCl4气体和副产物，如此反复循环反应180min后，通过氮气吹扫尾气及副产物，降温收料得LiF@Cu3N复合补锂剂。
实施例5
将草酸锂进行砂磨2h、闭式喷雾干燥得纳米草酸锂，测试草酸锂的粒径分布D10-D90范围为：30～300nm；取20g上述纳米草酸锂置于流化床-ALD设备中，保持进气口温度为150℃，先后通入氢气(通入量为0.05L/min)进行草酸锂衬底饱和吸附、通入氮气吹扫多余氢气、通入Pd(thd)2气体(通入量为4L/min)进行原子沉积反应、通入氮气吹扫多余Pd(thd)2气体和副产物，如此反复循环20min后，通过氮气气体吹扫尾气及副产物，降温收料得Li2C2O4@Pd复合补锂剂。
实施例6
将草酸锂进行砂磨2h、闭式喷雾干燥得纳米草酸锂，测试草酸锂的粒径分布D10-D90范围为：50～500nm；取20g上述纳米草酸锂置于流化床-ALD设备中，保持进气口温度为150℃，先后通入氧气(通入量为0.1L/min)进行草酸锂衬底饱和吸附、通入氮气吹扫多余氧气、通入Rh(acac)3气体(通入量为3L/min)进行原子沉积反应、通入氮气吹扫多余Rh(acac)3气体和副产物，如此反复循环反应90min后，通过氮气气体吹扫尾气及副产物，降温收料得Li2C2O4@Rh复合补锂剂。
实施例7
与实施例1的区别仅在于，将草酸锂更换为草酸钠，测试草酸钠的粒径分布D10-D90范围为：50nm～300m，其他与实施例1相同，制备得到Na2C2O4@TiO2复合补钠剂。制备得到的复合补锂剂的SEM图如图1所述，HRTEM图如图2所示。由图1～2可以看出复合补钠剂表层具有约1～5nm的均匀包覆层。
实施例8
与实施例2的区别仅在于，将草酸锂更换为草酸钠，测试草酸钠的粒径分布D10-D90范围为：50nm～300m，其他与实施例2相同，制备得到Na2C2O4@ZnO复合补钠剂。
实施例9
与实施例3的区别仅在于，将氟化锂更换为氟化钠，测试氟化钠的粒径分布D10-D90范围为：40nm～200nm，其他与实施例3相同，制备得到NaF@SnO复合补钠剂。
实施例10
与实施例4的区别仅在于，将氟化锂更换为氟化钠，测试氟化钠的粒径分布D10-D90范围为：40nm～200nm，其他与实施例4相同，制备得到NaF@Cu3N复合补钠剂。
实施例11
与实施例5的区别仅在于，将草酸锂更换为草酸钠，其他与实施例5相同，制备得到Na2C2O4@Pd复合补钠剂。
实施例12
与实施例6的区别仅在于，将草酸锂更换为草酸钠，其他与实施例6相同，制备得到Na2C2O4@Rh复合补钠剂。
对比例1
将草酸锂进行砂磨2h、闭式喷雾干燥得纳米草酸锂，测试草酸锂的粒径分布D10-D90范围为：30～200nm，不进行ALD包覆。
对比例2
将氟化锂进行砂磨4h、闭式喷雾干燥得纳米氟化锂，测试氟化锂的粒径分布D10-D90范围为：50nm～300nm，不进行ALD包覆。
对比例3
将草酸钠进行砂磨2h、闭式喷雾干燥得纳米草酸钠，测试草酸钠的粒径分布D10-D90范围为：50nm～300m，不进行ALD包覆。
对比例4
将商业氟化钠进行砂磨2h、闭式喷雾干燥得纳米氟化钠，测试氟化钠的粒径分布D10-D90范围为：40nm～200nm，不进行ALD包覆。
对比例5
将草酸锂与TiO2(草酸锂与TiO2的质量比为100:1)混合，进行砂磨2h、闭式喷雾干燥，得复合补锂剂Li2C2O4/TiO2，测试复合补锂剂的粒径分布D10-D90范围为30～200nm。
性能测试
分别对实施例及对比例制备得到的补锂/补钠剂的性能进行测试，其中：
将90wt％的磷酸铁锂、2wt％复合补锂、4％SuperP和4％PVDF混合均匀后，通过匀浆、涂覆、烘干、滚压，获得正极极片；采用人造石墨作为负极活性物质，制备负极极片；组装正负极极片获得锂离子全电池，组装正极片和锂片获得锂离子半电池。0.1C化成后，分别测试锂离子电池的首次充放电克容量以及100周循环后容量保持率。具体结果如表1所示。
表1全电池性能
将90wt％的焦磷酸铁纳、2wt％复合补钠添加剂、4％SuperP和4％PVDF混合均匀后，通过匀浆、涂覆、烘干、滚压，获得正极极片；采用硬碳作为负极活性物质，制备负极极片；组装正负极极片获得钠离子全电池，组装正极片和钠片获得钠离子半电池。0.1C化成后，分别测试锂/钠离子电池的首次充放电克容量以及100周循环后容量保持率。具体结果如表2所示。其中添加实施例1和7所制备的复合补锂/补钠剂的电池的半电池充电曲线图如图2所示。添加实施例1和实施例7所制备的复合补锂/补钠剂的电池的全电首放性能图如图3所示。
表2全电池性能
由表1和2可知，本发明提供的复合补锂/补钠添加剂在充放电过程中可以有效补充活性锂/钠离子，提升锂/钠离子电池的整体性能。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (10)

1.一种复合补锂/补钠剂，其特征在于，包括内核和包覆在内核外部的纳米包覆层；所述内核为补锂/补钠活性粒子；所述纳米包覆层为金属或金属化合物。
2.根据权利要求1所述的复合补锂/补钠剂，其特征在于，所述补锂/补钠活性粒子中补锂活性粒子为草酸锂、氟化锂、硫化锂、氧化锂和氯化锂中的一种或多种；补钠活性粒子为草酸钠和/或氟化钠。
3.根据权利要求1所述的复合补锂/补钠剂，其特征在于，所述补锂/补钠活性粒子的粒径为30nm～500nm，比表面积为20～300m2/g。
4.根据权利要求1所述的复合补锂/补钠剂，其特征在于，所述金属为Ti、Cr、Mn、Fe、Co、Ni、Cu、Zn、Mo、Sn、Au、Ag、Pd、Pd、Ta、Sn、Rh中的一种或多种；所述金属化合物为金属氧化物或金属氮化物。
5.根据权利要求1所述的复合补锂/补钠剂，其特征在于，按重量百分比计，所述复合补锂/补钠剂中补锂/补钠活性粒子占比为90～99.99％，纳米包覆层占比为0.01％～10％。
6.权利要求1～5任意一项所述的复合补锂/补钠剂的制备方法，其特征在于，包括如下步骤：
1)将补锂/补钠活性粒子置入流化床-原子层沉积设备内进行流化；
2)在流化床-原子层沉积设备内通入反应气和气化的包覆层原料进行原子层沉积，得到复合补锂/补钠剂。
7.根据权利要求6所述的制备方法，其特征在于，步骤2)中当包覆层为金属氧化物时，反应气为水蒸气、氧气和臭氧中的至少一种；当包覆层金属氮化物时，反应气为氮气、氨气或氨气与水蒸气的混合物的至少一种。
8.根据权利要求6所述的制备方法，其特征在于，步骤2)中所述包覆层所用原料包括金属单质，金属的氯化物、氟化物、碘化物、酯化物，烷基金属有机化合物或烷基金属氧化物。
9.根据权利要求6所述的制备方法，其特征在于，步骤2)中所述反应气的通入量为0.05～1L/min，气化的包覆层原料的通入量为0.1～5L/min；沉积时间为5～300min。
10.权利要求1～5任意一项所述的复合补锂/补钠剂在锂/钠离子电池正极中的应用。
CN202410076709.3A 2024-01-18 2024-01-18 复合补锂/补钠剂及其制备方法和应用 Pending CN118231663A (zh)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118867246A (zh) * 2024-07-09 2024-10-29 厦门海辰储能科技股份有限公司 补钠材料及其制备方法、正极极片、钠离子电池
CN119361710A (zh) * 2024-11-22 2025-01-24 浙江锂威能源科技有限公司 一种复合补锂材料、补锂正极及锂离子电池

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118867246A (zh) * 2024-07-09 2024-10-29 厦门海辰储能科技股份有限公司 补钠材料及其制备方法、正极极片、钠离子电池
CN119361710A (zh) * 2024-11-22 2025-01-24 浙江锂威能源科技有限公司 一种复合补锂材料、补锂正极及锂离子电池

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