CN114388732A - 电化学装置和电子装置 - Google Patents
电化学装置和电子装置 Download PDFInfo
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- CN114388732A CN114388732A CN202111581347.6A CN202111581347A CN114388732A CN 114388732 A CN114388732 A CN 114388732A CN 202111581347 A CN202111581347 A CN 202111581347A CN 114388732 A CN114388732 A CN 114388732A
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- positive electrode
- active material
- electrode active
- material layer
- electrochemical device
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- 229910052748 manganese Inorganic materials 0.000 claims abstract description 24
- 238000010828 elution Methods 0.000 claims abstract description 14
- -1 polysiloxane Polymers 0.000 claims description 33
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000011230 binding agent Substances 0.000 claims description 16
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- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
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Abstract
本申请的实施例提供了电化学装置和电子装置。电化学装置包括正极极片,正极极片包括正极活性材料层,正极活性材料层包括正极活性材料,正极活性材料包括含锰材料,含锰材料的质量与正极活性材料的质量的比率Y为0.4至1。通过控制正极活性材料层中的含锰材料的质量与正极活性材料的质量的比率Y,可以有效地控制正极活性材料层中的Mn溶出。
Description
技术领域
本申请涉及电化学储能领域,具体地涉及电化学装置和电子装置。
背景技术
伴随电化学储能技术的发展,电化学装置(例如,锂离子电池)因其高能量密度、长续航性能而备受关注,含锰材料(例如,锰酸锂)可以显著提高电化学装置的安全性能,降低材料成本,但在高温存储过程中,因为Jahn-Teller(姜泰勒)效应及电解液中HF腐蚀会发生Mn溶出,造成电化学装置的容量衰减和成本上升,削弱产品竞争力,因此抑制Mn溶出是包括含锰材料的电化学装置的性能优化的重要课题。
发明内容
本申请提供了一种电化学装置,电化学装置包括正极极片,正极极片包括正极活性材料层,正极活性材料层包括正极活性材料,正极活性材料包括含锰材料,含锰材料的质量与正极活性材料的质量的比率Y为0.4至1。
在一些实施例中,含锰材料包括锰酸锂。在一些实施例中,锰酸锂包括立方晶系锰酸锂。在一些实施例中,正极活性材料层的面密度为X mg/cm2,18≤X≤52。在一些实施例中,正极极片的Mn溶出量为Z ppm,Z=(-52.99X+3215.5)*10Y/9,且160≤Z≤2500。在一些实施例中,含锰材料的质量与正极活性材料层的质量的比率为0.38至0.95。在一些实施例中,正极极片还包括正极集流体,正极活性材料层设置在正极集流体的一侧或两侧的表面。在一些实施例中,正极活性材料层还包括导电剂和粘结剂。在一些实施例中,导电剂包括导电炭黑、科琴黑、片层石墨、石墨烯、碳纳米管或碳纤维中的至少一种,粘结剂包括羧甲基纤维素、聚偏氟乙烯、聚丙烯酸、聚乙烯基吡咯烷酮、聚苯胺、聚酰亚胺、聚酰胺酰亚胺、聚硅氧烷、丁苯橡胶、环氧树脂、聚酯树脂、聚氨酯树脂或聚芴中的至少一种,正极活性材料层中的正极活性材料、导电剂和粘结剂的质量比为(80-99):(0.1-10):(0.1-10)。
本申请的实施例还提供了一种电子装置,包括上述的电化学装置。
本申请通过控制正极活性材料层中的含锰材料的质量与正极活性材料的质量的比率Y,可以有效地控制正极活性材料层中的Mn溶出。
具体实施方式
下面的实施例可以使本领域技术人员更全面地理解本申请,但不以任何方式限制本申请。
本申请的一些实施例提供了一种电化学装置,电化学装置包括正极极片。在一些实施例中,正极极片包括正极活性材料层。在一些实施例中,正极活性材料层包括正极活性材料。在一些实施例中,正极活性材料包括含锰材料,其中,含锰材料的质量与正极活性材料的质量的比率Y为0.4至1。通过将含锰材料的质量与正极活性材料的质量的比率Y控制为0.4至1,可以将正极活性材料层中的Mn溶出控制在较低水平,进而改善电化学装置的存储容量损失。另外,当含锰材料的质量与正极活性材料的质量的比率Y低于0.4时,正极活性材料中的Mn溶出对容量造成的损失不占主导作用,并且Mn溶出不符合下述关系式,不利于Mn溶出的控制。
在一些实施例中,含锰材料包括锰酸锂。锰酸锂的成本较低,稳定性较好,有利于提升电化学装置的安全性能。在一些实施例中,锰酸锂包括立方晶系锰酸锂。在一些实施例中,立方晶系锰酸锂的极化效应较低,可以缓解电化学装置的容量衰减。在一些实施例中,在高温存储过程中,锰酸锂材料容易发生J-T效应。J-T效应是由于Mn的平均价态低于+3.5时,发生晶体结构扭曲,由立方晶系向四方晶系发生转变,导致晶格畸变,使电极极化效应增强,从而引起容量衰减的现象。
在一些实施例中,正极活性材料层的面密度为X mg/cm2,18≤X≤52。正极活性材料层的面密度指的是单位面积的正极活性材料层的重量。在该高面密度下,电解液在正极极片径向(垂直于正极活性材料层表面)的迁移能力降低,正极活性材料层中的远离电解液的那一侧的颗粒受到HF腐蚀作用减弱,因此Mn溶出显著降低。在一些实施例中,如果正极活性材料层的面密度过大,正极活性材料层出现干燥不良,正极活性材料层的表面开裂,这增大了正极极片的孔隙率,有利于电解液浸润,但是会恶化Mn溶出;另外,如果正极活性材料层的面密度偏小,极片曲折度/孔隙率未明显减小,无法有效抑制远离电解液的正极活性材料层的Mn溶出。
在一些实施例中,正极极片的Mn溶出量为Z ppm,Z=(-52.99X+3215.5)*10Y/9,且160≤Z≤2500。在60℃存储28天检测指标下建立了Mn溶出(Z/ppm)、面密度X:mg/cm2)和正极活性材料锰酸锂的质量比例(Y)关系式。基于该关系式,可以优化含锰材料体系开发,提高含锰材料体系电化学装置的竞争力。
在一些实施例中,含锰材料的质量与正极活性材料层的质量的比率为0.38至0.95。基于正极活性材料层中的正极活性材料的含量以及含锰材料的质量与正极活性材料的质量的比率Y,可以得到含锰材料的质量与正极活性材料层的质量的比率。
在一些实施例中,正极极片还可以包括正极集流体。在一些实施例中,正极集流体可以采用铝箔,当然,也可以采用本领域常用的其他正极集流体。在一些实施例中,正极活性材料层可以设置在正极集流体的一侧或两侧的表面。在一些实施例中,正极集流体的厚度可以为1μm至50μm。在一些实施例中,正极活性材料层可以仅涂覆在正极的集流体的部分区域上。
在一些实施例中,正极活性材料层还可以包括其他正极活性材料、导电剂和粘结剂。在一些实施例中,正极极片的导电剂可以包括导电炭黑、片层石墨、石墨烯或碳纳米管中的至少一种。在一些实施例中,正极极片中的粘结剂可以包括聚偏氟乙烯、偏氟乙烯-六氟丙烯的共聚物、苯乙烯-丙烯酸酯共聚物、苯乙烯-丁二烯共聚物、聚酰胺、聚丙烯腈、聚丙烯酸酯、聚丙烯酸、聚丙烯酸盐、羧甲基纤维素纳、聚醋酸乙烯酯、聚乙烯呲咯烷酮、聚乙烯醚、聚甲基丙烯酸甲酯、聚四氟乙烯或聚六氟丙烯中的至少一种。在一些实施例中,其他正极活性材料包括但不限于钴酸锂、镍酸锂、镍锰酸锂、镍钴酸锂、磷酸铁锂、镍钴铝酸锂或镍钴锰酸锂中的至少一种。在一些实施例中,正极活性材料层中的正极活性材料、导电剂和粘结剂的质量比为(80-99):(0.1-10):(0.1-10),但是这仅是示例,可以采用任何其他合适的质量比。
在一些实施例中,负极极片包括负极集流体和负极活性材料层。在一些实施例中,负极活性材料层可以位于负极集流体的一侧或两侧上。在一些实施例中,负极活性材料层中还可以包括负极活性材料、导电剂和粘结剂。在一些实施例,负极活性材料可以包括石墨、硅基材料中的至少一种。在一些实施例中,硅基材料包括硅、硅氧材料、硅碳材料或硅氧碳材料中的至少一种。在一些实施例中,负极活性材料层中的导电剂可以包括导电炭黑、科琴黑、片层石墨、石墨烯、碳纳米管或碳纤维中的至少一种。在一些实施例中,负极活性材料层中的粘结剂可以包括羧甲基纤维素、聚偏氟乙烯、聚丙烯酸、聚乙烯基吡咯烷酮、聚苯胺、聚酰亚胺、聚酰胺酰亚胺、聚硅氧烷、丁苯橡胶、环氧树脂、聚酯树脂、聚氨酯树脂或聚芴中的至少一种。在一些实施例中,负极活性材料层中的负极活性材料、导电剂和粘结剂的质量比可以为(78至98.5):(0.1至10):(0.1至10)。应该理解,以上所述仅是示例,可以采用任何其他合适的材料和质量比。在一些实施例中,负极集流体可以采用铜箔、镍箔或碳基集流体中的至少一种。
在一些实施例中,隔离膜包括聚乙烯、聚丙烯、聚偏氟乙烯、聚对苯二甲酸乙二醇酯、聚酰亚胺或芳纶中的至少一种。例如,聚乙烯包括选自高密度聚乙烯、低密度聚乙烯或超高分子量聚乙烯中的至少一种。尤其是聚乙烯和聚丙烯,它们对防止短路具有良好的作用,并可以通过关断效应改善电池的稳定性。在一些实施例中,隔离膜的厚度在约3μm至20μm的范围内。
在一些实施例中,隔离膜表面还可以包括多孔层,多孔层设置在隔离膜的至少一个表面上,多孔层包括无机颗粒和粘结剂,无机颗粒选自氧化铝(Al2O3)、氧化硅(SiO2)、氧化镁(MgO)、氧化钛(TiO2)、二氧化铪(HfO2)、氧化锡(SnO2)、二氧化铈(CeO2)、氧化镍(NiO)、氧化锌(ZnO)、氧化钙(CaO)、氧化锆(ZrO2)、氧化钇(Y2O3)、碳化硅(SiC)、勃姆石、氢氧化铝、氢氧化镁、氢氧化钙或硫酸钡中的至少一种。在一些实施例中,隔离膜的孔具有在约0.01μm至1μm的范围的直径。多孔层的粘结剂选自聚偏氟乙烯、偏氟乙烯-六氟丙烯的共聚物、聚酰胺、聚丙烯腈、聚丙烯酸酯、聚丙烯酸、聚丙烯酸盐、羧甲基纤维素钠、聚乙烯呲咯烷酮、聚乙烯醚、聚甲基丙烯酸甲酯、聚四氟乙烯或聚六氟丙烯中的至少一种。隔离膜表面的多孔层可以提升隔离膜的耐热性能、抗氧化性能和电解质浸润性能,增强隔离膜与极片之间的粘结性。
在一些实施例中,电化学装置包括锂离子电池,但是本申请不限于此。在一些实施例中,电化学装置还包括电解液,电解液包括氟醚、氟代碳酸乙烯酯或醚腈中至少一种。在一些实施例中,电解液还包括锂盐,锂盐包括双(氟磺酰基)酰亚胺锂和六氟磷酸锂,锂盐的浓度为1mol/L至2mol/L,且双(氟磺酰基)酰亚胺锂和六氟磷酸锂的质量比为0.06至5。在一些实施例中,电解液还可以包括非水溶剂。非水溶剂可为碳酸酯化合物、羧酸酯化合物、醚化合物、其它有机溶剂或它们的组合。
碳酸酯化合物可为链状碳酸酯化合物、环状碳酸酯化合物、氟代碳酸酯化合物或其组合。
链状碳酸酯化合物的实例为碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸二丙酯(DPC)、碳酸甲丙酯(MPC)、碳酸乙丙酯(EPC)、碳酸甲乙酯(MEC)及其组合。所述环状碳酸酯化合物的实例为碳酸亚乙酯(EC)、碳酸亚丙酯(PC)、碳酸亚丁酯(BC)、碳酸乙烯基亚乙酯(VEC)或者其组合。所述氟代碳酸酯化合物的实例为碳酸氟代亚乙酯(FEC)、碳酸1,2-二氟亚乙酯、碳酸1,1-二氟亚乙酯、碳酸1,1,2-三氟亚乙酯、碳酸1,1,2,2-四氟亚乙酯、碳酸1-氟-2-甲基亚乙酯、碳酸1-氟-1-甲基亚乙酯、碳酸1,2-二氟-1-甲基亚乙酯、碳酸1,1,2-三氟-2-甲基亚乙酯、碳酸三氟甲基亚乙酯或者其组合。
羧酸酯化合物的实例为乙酸甲酯、乙酸乙酯、乙酸正丙酯、乙酸叔丁酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、γ-丁内酯、癸内酯、戊内酯、甲瓦龙酸内酯、己内酯、甲酸甲酯或者其组合。
醚化合物的实例为二丁醚、四甘醇二甲醚、二甘醇二甲醚、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷、乙氧基甲氧基乙烷、2-甲基四氢呋喃、四氢呋喃或者其组合。
其它有机溶剂的实例为二甲亚砜、1,2-二氧戊环、环丁砜、甲基环丁砜、1,3-二甲基-2-咪唑烷酮、N-甲基-2-吡咯烷酮、甲酰胺、二甲基甲酰胺、乙腈、磷酸三甲酯、磷酸三乙酯、磷酸三辛酯、和磷酸酯或者其组合。
本申请的实施例还提供了包括上述电化学装置的电子装置。本申请实施例的电子装置没有特别限定,其可以是用于现有技术中已知的任何电子装置。在一些实施例中,电子装置可以包括,但不限于,笔记本电脑、笔输入型计算机、移动电脑、电子书播放器、便携式电话、便携式传真机、便携式复印机、便携式打印机、头戴式立体声耳机、录像机、液晶电视、手提式清洁器、便携CD机、迷你光盘、收发机、电子记事本、计算器、存储卡、便携式录音机、收音机、备用电源、电机、汽车、摩托车、助力自行车、自行车、无人机、照明器具、玩具、游戏机、钟表、电动工具、闪光灯、照相机、家庭用大型蓄电池和锂离子电容器等。
下面列举了一些具体实施例和对比例以更好地对本申请进行说明,其中,采用锂离子电池作为示例。
实施例1
负极极片的制备:集流体采用铜箔,负极活性材料采用人造石墨,粘结剂采用丁苯橡胶和羧甲基纤维素。将负极活性材料、丁苯橡胶、乙炔黑和羧甲基纤维素钠按质量百分含量比96:1.7:1.0:1.3混合后分散于去离子水中形成浆料,搅拌均匀后涂布于铜箔上,干燥,形成负极活性材料层,负极活性材料层的厚度为140μm,冷压、分条后得到负极极片。
正极极片制备:将锰酸锂与磷酸铁锂组成的正极活性材料(正极活性材料中的锰酸锂的质量比为40%)、导电炭黑、粘结剂聚偏氟乙烯(PVDF)按质量百分含量比94.8:2.4:2.8在N-甲基吡咯烷酮溶剂体系中充分搅拌混合均匀后,涂覆于铝箔上,面密度18mg/cm2,得到正极活性材料层,正极活性材料层的厚度为200μm。再经烘干、冷压,得到正极极片。
隔离膜的制备:将聚丙烯酸酯拌形成均匀浆料,将浆料涂布到多孔基材(聚乙烯)的两侧表面上,烘干后形成隔离膜。
电解液的制备:在含水量小于10ppm的环境下,将六氟磷酸锂与非水有机溶剂(碳酸乙烯酯(EC):碳酸二乙酯(DEC):碳酸亚丙酯(PC):丙酸丙酯(PP):碳酸亚乙烯酯(VC)=20:30:20:28:2,质量百分含量比)按质量百分含量比8:92配制以形成锂盐浓度为1mol/L的电解液。
锂离子电池的制备:将正极极片、隔离膜、负极极片按顺序依次叠好,使隔离膜处于正极极片和负极极片中间起到隔离的作用,并卷绕得到电极组件。将电极组件置于外包装铝塑膜中,在105℃下脱去水分后,注入上述电解液并封装,经过化成,脱气,整形等工艺流程得到锂离子电池。
在其他实施例与对比例中,负极极片、隔离膜、电解液和锂离子电池制备均与实施例1相同,仅正极极片的制备有些不同,参数的差异示出于相应的表格中。
另外,在本申请中,采用如下方法测量相应的参数。
1.Mn溶出测试:
1)存储前:利用无极化曲线(25℃ 0.01C放电曲线),查找锂离子电池的荷电状态(State of Charge,以下简称SOC)为30%时对应的电压点,误差不超过±5mV;
2)存储中:60℃ 30%SOC存储28天,每7天做容量恢复,
容量恢复流程如下(假设30%SOC对应3.24V):
①温度设定为25℃ ②静置10min,③0.2C恒流充电至4.2V,恒压充电至0.05C ④静置10min ⑤0.2C恒流放电至2.8V,⑥静置10min ⑦第2步到第6步循环3次,⑧0.2C恒流充电至3.24V,恒压充电至0.05C,⑨静置10min;
3)存储后:拆解锂离子电池,取负极极片几何中心的12个小圆片(半径:7mm),利用电感耦合等离子(ICP)设备测量Mn溶出数值,最终测量值取它们的平均值,鉴于设备差异及电解液等因素干扰,规定:Mn溶出测量值与公式计算值误差小于20%,可视作一致,即:|测量值-计算值|/计算值≤20%。
2.容量恢复率测试:
存储前容量测试流程:
1)测试温度为25℃
2)静置10min
3)0.2C恒流充电至4.2V,恒压充电至0.05C
4)静置10min
5)0.5C恒流放电至2.8V
6)静置10min
7)第3步到第6步循环3次,记录第三次容量作为初始容量A0
8)0.2C恒流充电至3.24V,恒压充电至0.05C(将锂离子电池调整到30%荷电状态(SOC)
9)静置10min,开始存储:
60℃存储28天后容量测试,其中每7天容量恢复,流程如下:
(1)测试温度为25℃
(2)静置2h
(3)0.5C恒流放电至2.8V(记录为残余容量)
(4)静置10min
(5)0.2C恒流充电至4.2V,恒压充电至0.05C
(6)静置10min
(7)0.5C恒流放电至2.8V
(8)静置10min
(9)0.2C恒流充电至4.2V,恒压充电至0.05C
(10)静置10min
(11)第(2)步到第(7)步循环3次(分别记录3次恢复容量,即第一次恢复容量1、第二次恢复容量2、第三次恢复容量3),第三次恢复容量3作为存储后的容量A1
(12)0.2C恒流充电至3.24V,恒压充电至0.05C(存储调电压至指定荷电状态(SOC))
(13)静置10min。
计算容量恢复率:|A0-A1|/A0*100%。
表1示出了实施例1至35和对比例1至5的各项参数和评估结果。其中,实施例2至35和对比例1至5的锂离子电池的制备方法同实施例1,除了正极活性材料层的面密度和/或正极活性材料中锰酸锂的质量比不同之外,具体差异见下表1。
表1
通过比较实施例1至7可知,在正极活性材料层的面密度相同的条件下,随着锰酸锂占正极活性材料的质量比(Y)增加,Mn溶出总体呈现正相关上升的趋势。这主要是锰酸锂颗粒与电解液的接触面积增大,同时叠加姜泰勒(J-T)效应,导致Mn溶出量显著上升。通过比较实施例8至12、或者比较实施例16至21、或者比较实施例23至28、或者比较实施例30至35也能够得到同样的结论。
通过比较实施例1、8、16、23、30可知,在锰酸锂比例一定的条件下,Mn溶出含量随面密度增加而显著降低;在正极活性材料层的高面密度下,电解液在正极极片的径向的迁移能力降低,靠近正极集流体的正极活性材料颗粒受到HF腐蚀作用减弱,因此Mn溶出含量显著降低。通过比较实施例7、15、22和29可以得到同样的结论。
通过比较对比例4、5可知,低面密度下叠加低锰酸锂材料比例,Mn溶出会显著降低,这符合Mn溶出降低基本原理,但二者叠加交互,会明显降低Mn溶出,超过公式预测范围,但同时也失去低成本优势,不利于工业化降成本生产。另外,锂离子电池的容量损失(或容量恢复率)与Mn溶出总体呈现正相关性,例如,参见实施例8至12,面密度28mg/cm2,随着Mn溶出含量增加,存储容量恢复率逐渐降低,此时容量损失机理是Mn溶出破坏负极固相电解质界面膜(SEI膜),导致容量损失。然而,其他实施例中吻合度降低,这表明存储容量损失和Mn溶出不是一一对应,容量损失也可能来源于负极副反应等。
以上描述仅为本申请的较佳实施例以及对所运用技术原理的说明。本领域技术人员应当理解,本申请中所涉及的公开范围,并不限于上述技术特征的特定组合而成的技术方案,同时也应涵盖由上述技术特征或其等同特征进行任意组合而形成的其它技术方案。例如上述特征与本申请中公开的具有类似功能的技术特征进行互相替换而形成的技术方案。
Claims (10)
1.一种电化学装置,其包括:
正极极片,所述正极极片包括正极活性材料层,所述正极活性材料层包括正极活性材料,所述正极活性材料包括含锰材料,所述含锰材料的质量与所述正极活性材料的质量的比率Y为0.4至1。
2.根据权利要求1所述的电化学装置,其中,所述含锰材料包括锰酸锂。
3.根据权利要求2所述的电化学装置,其中,所述锰酸锂包括立方晶系锰酸锂。
4.根据权利要求1所述的电化学装置,其中,所述正极活性材料层的面密度为X mg/cm2,18≤X≤52。
5.根据权利要求4所述的电化学装置,其中,
所述正极极片的Mn溶出量为Z ppm,Z=(-52.99X+3215.5)*10Y/9,且160≤Z≤2500。
6.根据权利要求1所述的电化学装置,其中,所述含锰材料的质量与所述正极活性材料层的质量的比率为0.38至0.95。
7.根据权利要求1所述的电化学装置,其中,所述正极极片还包括正极集流体,所述正极活性材料层设置在所述正极集流体的一侧或两侧的表面。
8.根据权利要求1所述的电化学装置,其中,所述正极活性材料层还包括导电剂和粘结剂。
9.根据权利要求8所述的电化学装置,其中,所述导电剂包括导电炭黑、科琴黑、片层石墨、石墨烯、碳纳米管或碳纤维中的至少一种,所述粘结剂包括羧甲基纤维素、聚偏氟乙烯、聚丙烯酸、聚乙烯基吡咯烷酮、聚苯胺、聚酰亚胺、聚酰胺酰亚胺、聚硅氧烷、丁苯橡胶、环氧树脂、聚酯树脂、聚氨酯树脂或聚芴中的至少一种,所述正极活性材料层中的所述正极活性材料、所述导电剂和所述粘结剂的质量比为(80-99):(0.1-10):(0.1-10)。
10.一种电子装置,包括根据权利要求1至9中任一项所述的电化学装置。
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CN115295768A (zh) * | 2022-09-29 | 2022-11-04 | 比亚迪股份有限公司 | 一种正极片及锂离子电池 |
CN116565293A (zh) * | 2023-07-06 | 2023-08-08 | 宁德新能源科技有限公司 | 一种电化学装置及电子装置 |
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