CN115117336A - 一种高比能钠离子电池锰基层状正极材料、制备方法和用途 - Google Patents
一种高比能钠离子电池锰基层状正极材料、制备方法和用途 Download PDFInfo
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- 239000011572 manganese Substances 0.000 title claims abstract description 58
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 25
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 24
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- 229910052708 sodium Inorganic materials 0.000 claims description 13
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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Abstract
本发明涉及一种高比能钠离子电池锰基层状正极材料、制备方法和用途，属于钠离子电池材料技术领域。本发明在Na2/3[Li1/7Mn5/14][Mg1/ 7Mn5/14]O2中构建双蜂窝超晶格结构的策略，以同时实现晶格O氧化还原的高活性和可逆性。理论模拟和电化学实验表明，[Li1/7Mn5/14]超晶格单元能显著触发阴离子氧化还原活性，并能在层状钠离子电池正极中提供285.9mA g‑1的记录容量。核磁共振和原位x射线衍射表明[Mg1/7Mn5/14]超晶格单元有利于结构和阴离子氧化还原可逆性，Li+可逆地穿梭于Na层和过渡金属板之间，与没有[Mg1/7Mn5/14]单元的样品形成对比。我们的发现强调了多功能单元的重要性，并为先进电池材料提供了一条途径。
Description
技术领域
本发明涉及一种高比能钠离子电池锰基层状正极材料、制备方法和用途，属于钠离子电池材料技术领域。
背景技术
低成本、高性能的钠离子电池是大规模储能的关键战略。正极是决定钠离子电池输出电压和能量密度的最关键组件之一，层状氧化物由于其灵活的组成和高的理论容量而被深入研究。阴离子氧化还原有望实现超出层状正极理论极限的超高容量。然而，在层状结构中充分的氧氧化还原总是伴随着结构重排和的氧化还原不可逆性。反应活性和可逆性双高仍然是一个很大的挑战。
为了激发层状氧化物中的阴离子氧化还原活性，在TM层中引入低电负性的Li+，通过 Na-O-Li相互作用生成未杂化的氧2p态是非常必要的。Hu(非专利文献1)等人报道的Na0.72[Li0.24Mn0.76]O2在1.5-4.5V的首次放电中提供了271mAh g-1的比容量，这是迄今为止钠离子电池层状过渡金属正极中容量最大的(非专利文献2)。然而，一系列的研究结果表明， Li+可能引起多余的O活性，在充电过程中，高活性的氧离子被完全氧化为O2分子逸出材料(非专利文献3)。Na0.75[Li0.25Mn0.75]O2充电态出现空位团簇和分子O2,Li+向Na层迁移，导致结构损伤(非专利文献4)。同时，也有报道称在TM层中存在Mg2+能稳定阴离子氧化还原。与Li+相比，Mg2+与晶格O有较强的离子相互作用，在一定程度上抑制了O的损失，保持了晶格的超结构(非专利文献5)。随着Na0.67Mn1-xMgxO2中Mg2+含量的增加，循环性得到改善(非专利文献 6)。Na5/6Li1/4Mn3/4O2中Mg的掺杂提高了结构稳定性(非专利文献7)。最近值得注意的是，超晶格的调控对电化学过程中的阴离子氧化还原有很大的影响。由于锂离子与锰离子之间的价态和半径不匹配，形成了1个锂离子被6个锰离子包围的超结构(非专利文献3、8)。Bruce等人报道了Na0.6[Li0.2Mn0.8]O2材料具有带状有序的超结构，阻碍了空位团的产生。Pan等人展示了一种调节超结构基元的策略(非专利文献3)。
非专利文献1：a)S.M.Kang,D.Kim,K.S.Lee,M.S.Kim,A.Jin,J.H.Park,C.Y.Ahn,T.Y.Jeon,Y.H.Jung, S.H.Yu,J.Mun,Y.E.Sung,Adv.Sci.2020,7,2001263；b)G.H.Yoon,S.Koo,S.J.Park,J.Lee,C.Koo,S.H. Song,T.Y.Jeon,H.Kim,J.S.Bae,W.J.Moon,S.P.Cho,D.Kim,S.H.Yu,Adv.Energy Mater.2022,12, 2103384.
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发明内容
本发明所要解决的技术问题是：现有的Na0.72[Li0.24Mn0.76]O2材料由于在充电态出现空位团簇和分子O2,Li+向Na层迁移，导致结构损伤的问题。本发明成功地制备出了一种具有双蜂窝超晶格的层状正极材料Na2/3[Li1/7Mn5/14][Mg1/7Mn5/14]O2的层状正极(简写为LiMn6-MgMn6)，其一方面展现出了Li+在TM层和Na层的层间迁移过程的可逆性，保持了结构完整性，另一方面增强了阴离子氧化还原的活性。
一种钠离子电池锰基层状正极材料，其化学式为Nam[LixMn0.5-x][MgyMn0.5-y]O2；0.12<x,y<0.16，0.6<m<0.7；其晶体结构为P2相，且晶体中包含两个蜂巢状结构，分别是以Li+或Mg2+为中心、周围分布6个Mn离子而构成。
所述的化学式为Na2/3[Li1/7Mn5/14][Mg1/7Mn5/14]O2。
上述的钠离子电池锰基层状正极材料的制备方法，是通过溶胶凝胶法或者固相法得到。
所述的溶胶凝胶法是按照化学计量比将钠源、锂源、锰源和镁源进行水解制备出溶胶后，转化为凝胶，再进行干燥、煅烧后得到。
所述的固相法是按照化学计量比分别将钠源、锂源、锰源、镁源的氧化物或者碳酸盐或者氢氧化物混合球磨后，再经过煅烧得到。
所述的钠源、锂、锰源、镁源分别是钠、锂、锰、镁的氧化物、碳酸盐或者氢氧化物。
所述的钠源是碳酸钠；所述的锂源是碳酸锂；所述的锰源是三氧化二锰；所述的镁源是氧化镁。
所述的碳酸钠的加入量为过量1-10％。
所述的球磨过程的转速100-500rpm，时间1-10h。
所述的煅烧过程温度750-850℃，时间12-36h。
上述的正极材料在钠离子电池中的用途。
所述的正极材料用于减小Li+在循环充放电过程中的损失。
有益效果
阴离子氧化还原是层状氧化物异常容量超过理论极限的原因之一。然而，由于结构重排和潜在的氧损失，活性和可逆性双高具有挑战性。本发明在Na2/3[Li1/7Mn5/14][Mg1/ 7Mn5/14]O2中构建双蜂窝超晶格结构的策略，以同时实现晶格O氧化还原的高活性和可逆性。Li-6Mn超晶格唤醒了阴离子氧化还原活性，从而得到了285.9mAhg-1的记录放电容量。理论模拟和电化学实验表明，[Li1/7Mn5/14]超晶格单元能显著触发阴离子氧化还原活性，并能在层状钠离子电池正极中提供285.9mA g-1的电容量。在高度脱钠的情况下，Li+将从TM层中去除，Mg-6Mn超晶格作为柱子，防止了空位团簇、氧析出和结构完整性的缺乏。核磁共振和原位x射线衍射表明[Mg1/7Mn5/14]超晶格单元有利于结构和阴离子氧化还原可逆性，Li+可逆地穿梭于Na层和过渡金属板之间，核磁共振(NMR)表明Li+在TM层中返回到原始蜂窝位置，与没有[Mg1/7Mn5/14]单元的样品形成对比，从而保持了良好的可逆性，在1C(100mA g-1)下循环50次后保持了85.5％的容量。
附图说明
图1是a)LiMn6-MgMn6的SEM图像和b)HRTEM图像。c)SEM的能量色散光谱(EDS)元素映射表明材料中钠、镁和锰元素的均匀分布。
图2是a)LiMn6和c)MgMn6的XRD图和Bragg位置。b)LiMn6和d)MgMn6的SEM图像。
图3是a)LiMn6-MgMn6的XRD谱图和Rietveld精修。注意超结构的峰值在～22°，表明蜂窝状排列。插图是SAED图像。三个正极在1.5-4.5V电压范围内，在0.1C的b)恒流首圈充电曲线；c)dQ/dV曲线。LiMn6-MgMn6的结构模型d)c轴向上，e)c轴垂直于平面向外。f)LiMn6、LiMn6-MgMn6和MgMn6的O-2p轨道的态密度(PDOS)。g)用密度泛函理论(DFT)计算的三种材料的O2p的态密度(PDOS)。
图4是a)LiMn6、MgMn6和LiMn6-MgMn6首次充电态(蚀刻20nm后)的O 2p XPS光谱和拟合结果。b)对应的(O2)n-组分中，LiMn6-MgMn6所占比例最高。c)首圈放电曲线。d)在初始两次循环中收集的LiMn6-MgMn6的原位XRD图谱。e)用总电子产额(TEY)模式收集各态下OK-edge sXAS数据。f)电化学曲线(数值表示采集sXAS时的状态)和阴影区综合强度变化(e)。
图5是LiMn6-MgMn6的第一次充电期间的原位差分电化学质谱。
图6是a)0.1C时LiMn6-MgMn6前3次充放电曲线。b)1C条件下(同时反映库仑效率)50次循环性能。c)统计钠离子电池阴离子氧化还原正极的首圈放电容量、平均电压和能量密度。报道的LiMn6-MgMn6材料用星标记。d)不同电流密度下的倍率性能测试。
图7是a)LiMn6和c)LiMn6-MgMn6在第一个循环不同阶段的7Li NMR谱。b)LiMn6和d)LiMn6-MgMn6在不同状态下的结构示意图。
具体实施方式
材料制备
对于以下三种材料：
Na0.78Li0.26Mn0.74O2(LiMn6)；
Na0.67Mg0.28Mn0.72O2(MgMn6)；
Na2/3[Li1/7Mn5/14][Mg1/7Mn5/14]O2(LiMn6-MgMn6)；
材料采用传统的固相反应制备。
原料为Na2CO3、Li2CO3、MgO和Mn2O3。材料是根据指定的化学计量比例称重。因为Na2CO3很容易挥发，所以Na2CO3过量5％。将原料粉末在ZrO2球磨罐中以300rpm的转速研磨5h，混合均匀后压成直径为16mm的圆片，然后在氧化铝坩埚中马弗炉800℃保温24h，自然冷却至室内温度。冷却后的颗粒被研磨成粉末，并妥善储存以备将来的实验。
材料元素组成表征
采用电感耦合等离子体光学发射光谱法(ICP-OES)分析金属离子元素的摩尔比，结果与设计的组份一致。如表1所示：
表1
SEM和XRD表征
用扫描电子显微镜(SEM)对其形貌进行了表征，均为片状颗粒。
LiMn6-MgMn6的高分辨率透射电镜(HRTEM)图像，如图1所示。通过XRD对三种样品的晶体结构进行了分析，均为P2相特征(图3的a和图2)。利用GSAS+EXPGUI套组软件对 LiMn6-MgMn6晶体结构进行精修，如图3的a所示，详细晶格参数列于表2.在TM层中可见一个超结构峰，表明以Li+/Mg2+为中心的6个Mn离子呈蜂巢状排列，这与图3的a中所示的选区电子衍射(SAED)图像一致。大亮点是典型的p2相结构衍射。SAED中亮点被超晶格的有序排列的暗点包围，表明原始材料中存在超结构。结构模型如图3的d,e所示，Li-6Mn、Mg-6Mn 超晶格单元交替排列。通过比较各种构成结构形成能，通过DFT计算确定合适的超晶格结构，这里描述的构型在能量上要低得多。
表2
电化学测试方法
采用CR2032扣式电池进行电化学试验，该电池由正极和钠金属负极组成。以活性物质、乙炔黑和聚偏氟乙烯(PVDF)的质量比为75:20:5制备正极电极。将半电池的正极涂在铝箔上，然后在120℃左右的真空下干燥5h，然后组装电池。电极中活性物质的负载量为0.7～2.0mg，正极直径为12mm。电池被组装在一个充满高纯氩气(99.999％)的手套箱中。电解液为1mol L-1 NaClO4溶于碳酸丙烯酯，以5vol％氟化碳酸乙烯为电解液添加剂。每个电池使用100μL 的电解液。玻璃纤维作为每个钠半电池的隔膜。使用Land BT2001A电池测试系统，在1.5-4.5 V电压窗口下静置8小时后，在室温下对半电池进行恒流充放电测试，所有电化学测试1C 对应于100mA g-1。
在钠半电池中通过恒电流测试评价了其电化学性能。图3的b为第一次充电过程中，在电压范围为1.5～4.5V，电流密度为0.1C时，三个电极的电化学曲线。三种正极的曲线结构都表现为先呈现陡坡，然后是长的平台。～4.2V处的平台对应于O的氧化还原。值得注意的是，曲线中观察到斜坡与平台之间有一个转折点，这个转折点可以定义为O氧化起始电位。正如我们所预料的那样，Li+对LiMn6中O氧化还原的活化作用较强，因此O参与时间最早。 MgMn6的O氧化还原参与时间最晚，MgMn6-MgMn6的O氧化还原位于中间位置。通过观察对应的dQ/dV曲线(图3的c)更加明显，当dQ/dV约为0.1时，三条曲线的斜率都在加速。图4的f显示了三个正极的O氧化起始电位。图3的g和部分放大的插图显示了用密度泛函理论(DFT)计算的三种材料的O 2p的态密度(PDOS)。费米能级(0ev)附近的O 2p电子布居分布决定了O提供电荷补偿的难度，说明O的活性顺序为LiMn6、LiMn6-MgMn6和MgMn6。理论计算结果与实验结果吻合较好。
氧化还原可逆性的对比
1.XPS表征
在蚀刻20nm后，对三个样品在4.5V充电态下进行XPS实验检测氧的种类(图4的a)。530.5eV处的峰属于氧化态晶格氧(O2)n-(0<n<4)。LiMn6-MgMn6的(O2)n-比例占主导，与其他两种样品形成鲜明对比(图4的b)，说明晶格氧在LiMn6-MgMn6中具有良好的氧化还原可逆性。
2.DEMS表征
通过原位微分电化学质谱(DEMS)表征，在LiMn6-MgMn6的第一次充电过程中，氧化的氧仍然局限在晶格中，不产生O2(图5)。因此，对于后续的放电过程(图4的c)，由于其突出的结构可逆性，LiMn6-MgMn6正极表现出285.9mAh g-1放电比容量，达到了较高水平。由于O2的形成和随后从正极逸出，LiMn6的容量在三个样品中最低。通过原位XRD观察了LiMn6-MgMn6正极的晶格参数变化和相变过程。从最初两次循环的原位XRD谱图(图4的d)可以看出，虽然峰的位置发生了变化，但并没有发生相变，这进一步验证了该结构的可逆。
在LiMn6-MgMn6充放电过程中，在不同状态下进行了非原位O K-edge XAS测量，在图2f 中以不同标记。图4的e中总电子产额(TEY)模式在较低能量(<532eV)下，～529eV和～531eV 的两个峰收集的光谱为从O1s到空Mn 3d轨道与O 2p轨道耦合的电子跃迁。阴影区域的积分强度反映了空态密度的变化，计算并显示在图4的f中。积分强度在充放电过程中呈现出规律性的变化，这与氧的电子失去以及由此产生的O 2p轨道空穴不可避免地有关。
3.电化学性能的表征
在1.5-4.5V的0.1C倍率下测试的LiMn6-MgMn6的前3圈充放电循环曲线如图6的a所示。首次放电时，LiMn6-MgMn6正极具有超高的比容量285.9mAh g-1，这是迄今为止报道的钠离子电池层状过渡金属氧化物正极的最高容量。图6的c的散点图进一步显示了具有阴离子氧化还原的部分层状正极材料首圈放电容量、平均电压和能量密度，精确地显示出LiMn6-MgMn6最高的比容量和最高的能量密度。此外，在循环表现较差的阴离子氧化还原材料中，监测到的LiMn6-MgMn6的循环性能大致令人满意，在1C倍率下循环50圈后达到了85.5％的容量保持率。进一步研究了倍率性能(图6的d)，并表现良好。
4.NMR表征
核磁共振对锂离子局域环境敏感，因此核磁共振是研究锂离子在不同充放电状态下层内和层间运动的理想技术。因此，通过该技术可以合理推断出LiMn6和LiMn6-MgMn6正极充放电态的超结构转变(非磁性Mg2+为无核磁信号)。在LiMn6和LiMn6-MgMn6不同状态下采集的实验 7Li NMR谱如图7所示。原始LiMn6和LiMn6-MgMn6粉末样品呈现明显的两组峰。在2000和 1500ppm左右分离的两个峰(LiTM1和LiTM2)很可能源于Li位置的差异，而它们都位于TM 层，呈蜂窝状排列。2000ppm(LiTM1)左右的共振为由6个最接近的Mn离子包围的Li离子， 1500ppm(LiTM2)左右的共振为由小于6个最接近的Mn离子包围的Li离子，这可能是由于不完全完美晶格排列造成的。TM层中的锂离子位点标记为蓝紫色阴影。峰值集中在750ppm 左右(LiAM1和LiAM2在循环状态)，归因于锂离子位于Na层，并被标记为浅绿色阴影。LiMn6 和LiMn6-MgMn6材料的LiAM1峰在Na+嵌入/脱出过程中几乎不动，通过合理推测可能以局部缺陷或杂质的形式存在。在充电态，两种材料在750ppm(LiAM1)峰的右侧出现了新的宽共振(LiAM2)，这表明Li+从TM层向Na层的层外迁移。同时，迁移结果显示在图4中的示意图中。放电时，迁移到Na层(LiAM2)的Li+在LiMn6中几乎不会返回到TM层，而LiMn6-MgMn6中的Li+能够返回到TM层的LiTM1位点，说明Li+在LiMn6-MgMn6中迁移是可逆的。放电后LiMn6-MgMn6上的锂离子分布证明了TM层中蜂窝结构的部分可逆性和保持性。此外，循环样品中出现的0ppm处的峰值可以归因于电解质分解在表面形成的抗磁性含锂杂质(如Li2CO3和LiF)。
5.ICP表征
ICP检测循环后电解液中溶解的金属离子含量，验证了Li+在LiMn6正极中的溶解，结果如表3和表4所示。表3显示的是LiMn6和LiMn6-MgMn6在放电1.5V状态下电解液中离子含量的ICP-OES结果，是通过电解液经过ICP测试显示的离子浓度，单位为mg/L，表4显示的是从LiMn6和LiMn6-MgMn6在放电1.5V状态下的ICP-OES结果计算出的相对Li损失。
表3
表4
综上所述，经过电化学循环后，LiMn6中的蜂窝有序结构无法恢复，导致Li+从正极脱出。相反，LiMn6-MgMn6中保留了蜂窝状排列，表现出良好的可逆性和超高的放电容量。
Claims (10)
1.一种钠离子电池锰基层状正极材料，其特征在于，其化学式为Nam[LixMn0.5-x][MgyMn0.5-y]O2；0.12<x,y<0.16，0.6<m<0.7；其晶体结构为P2相，且晶体中包含两个蜂巢状结构，分别是以Li+或Mg2+为中心、周围分布6个Mn离子而构成。
2.根据权利要求1所述的钠离子电池锰基层状正极材料，其特征在于，所述的化学式为Na2/3[Li1/7Mn5/14][Mg1/7Mn5/14]O2。
3.权利要求1所述的钠离子电池锰基层状正极材料的制备方法，其特征在于，是通过溶胶凝胶法或者固相法得到。
4.权利要求3所述的钠离子电池锰基层状正极材料的制备方法，其特征在于，所述的溶胶凝胶法包括如下步骤：按照化学计量比将钠源、锂源、锰源和镁源进行水解制备出溶胶后，转化为凝胶，再进行干燥、煅烧后得到。
5.权利要求3所述的钠离子电池锰基层状正极材料的制备方法，其特征在于，所述的固相法是按照化学计量比分别将钠源、锂源、锰源、镁源的氧化物或者碳酸盐或者氢氧化物混合球磨后，再经过煅烧得到。
6.权利要求5所述的钠离子电池锰基层状正极材料的制备方法，其特征在于，所述的钠源、锂、锰源、镁源分别是钠、锂、锰、镁的氧化物、碳酸盐或者氢氧化物。
7.权利要求6所述的钠离子电池锰基层状正极材料的制备方法，其特征在于，所述的钠源是碳酸钠；所述的锂源是碳酸锂；所述的锰源是三氧化二锰；所述的镁源是氧化镁。
8.权利要求7所述的钠离子电池锰基层状正极材料的制备方法，其特征在于，所述的碳酸钠的加入量为过量1-10％。
9.权利要求5所述的钠离子电池锰基层状正极材料的制备方法，其特征在于，球磨过程的转速100-500rpm，时间1-10h；煅烧过程温度750-850℃，时间12-36h。
10.权利要求1所述的正极材料在钠离子电池中的用途。
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| JP2006335596A (ja) * | 2005-06-01 | 2006-12-14 | Tohoku Univ | 規則性のある大表面積ミクロポーラス炭素の簡便な合成方法 |
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| CN113782714A (zh) * | 2021-08-02 | 2021-12-10 | 南京大学 | 高比能钠离子电池锰基层状正极材料及其制备方法 |
| CN114229923A (zh) * | 2021-11-24 | 2022-03-25 | 北京大学深圳研究生院 | 一种锰基氧化物及其电极与电池 |
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