CN115149207A - 阴离子型多孔材料涂覆的复合隔膜及其方法与二次电池 - Google Patents
阴离子型多孔材料涂覆的复合隔膜及其方法与二次电池 Download PDFInfo
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- CN115149207A CN115149207A CN202210850980.9A CN202210850980A CN115149207A CN 115149207 A CN115149207 A CN 115149207A CN 202210850980 A CN202210850980 A CN 202210850980A CN 115149207 A CN115149207 A CN 115149207A
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Images
Classifications
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- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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Abstract
本发明公开了一种阴离子型多孔材料涂覆的复合隔膜及其方法与二次电池,属于电池隔膜技术领域。阴离子型多孔材料涂覆的复合隔膜的制备步骤如下:通过直接合成或合成后修饰获得阴离子型的多孔材料,将多孔材料与粘结剂分散于溶剂中形成均匀浆料,将浆料涂覆在隔膜表面,烘干形成复合隔膜。本发明制备的复合隔膜具有良好的机械性能、高温稳定性、浸润性,同时,多孔材料的孔道有利于离子的均匀传输,并且阴离子型的多孔材料能够抑制阴离子的迁移,提高阳离子迁移数,提升二次电池的循环稳定性。
Description
技术领域
本发明用于电池隔膜技术领域,具体涉及阴离子型多孔材料涂覆的复合隔膜及其方法与二次电池。
背景技术
随着科学技术的发展,电池能源广泛应用于电子产品、新能源汽车、间歇性可再生能源(如风能、太阳能)等领域。在所有类型的电池中,锂金属电池具有极高的能量密度。这是因为,锂金属负极具有高的质量能量密度(3860mA·h·g-1)、低的氧化还原电位(-3.040V,vs.SHE)和轻的密度(0.53g·cm-3)。但是,在锂金属电池中,有机溶剂的使用会使Li+发生溶剂化,使Li+的迁移速率小于阴离子的迁移速率,产生极化从而导致锂的不均匀沉积,产生锂枝晶。若枝晶从极板脱落,则脱落后的枝晶与极板的电接触断开,不能用于充放电反应,导致电池容量降低。并且如果枝晶逐渐生长,则可能会刺穿隔膜并与正极材料接触造成电池内部短路。所以,为了提高电池的安全性,需要解决电池的枝晶生长问题。同时也可开发能量密度有所降低,但成本更低或安全性有所提高的钠电池、锌电池、铝电池等。但是,这些电池的也存在极化带来的枝晶生长问题。因此需要调控电解液中阴阳离子的传输行为。
目前大多数电池由正极、负极和浸有电解液的隔膜组成。其中,隔膜是一个极为重要的组成部分。隔膜一方面可以作为电子绝缘的物理屏障隔离正负极,同时在浸泡了电解液之后可以作为离子传输的介质。但是,在传统商用的聚乙烯(PE)或聚丙烯(PP)隔膜中,阴离子的迁移速率高于阳离子的迁移速率,造成极化现象,导致阳离子的不均匀沉积,造成枝晶的成长。同时,商用隔膜的热稳定性差,无法在较高温度下使用。
为了解决传统隔膜热稳定性差以及迁移数低的问题,可以在隔膜表面涂覆纳米颗粒,比如氧化铝、氧化硅等。涂覆了纳米颗粒的隔膜热稳定性有所提高,并且,纳米颗粒通过Lewis酸碱相互作用抑制阴离子的迁移,减少极化现象。但是,致密的纳米颗粒会阻塞离子传输的通路,因此,可以通过使用多孔纳米颗粒增加离子传输的通路,比如多孔氧化铝、多孔二氧化硅、金属有机框架(MOF)、共价-有机框架(COF)等。但是,这些纳米多孔颗粒通过孔径或Lewis酸碱相互作用束缚阴离子,其与阴离子的相互作用能力较弱,因此阳离子迁移数的提高比较有限。
为了进一步抑制阴离子的迁移,本发明使用阴离子型多孔材料作为复合隔膜的涂层材料。由于阴离子被共价连接在多孔材料骨架上,因此阴离子的迁移能力大大减弱,有利于阳离子迁移数的提高,减少极化现象。
发明内容
本发明的目的在于解决目前隔膜涂覆技术中存在的抑制阴离子迁移的能力有限的问题,提供了一种阴离子型多孔材料涂覆的复合隔膜及其方法与二次电池。本发明通过在复合隔膜上涂覆阴离子型多孔材料,利用阴离子基团与多孔材料骨架强的共价键相互作用,更有效地抑制阴离子的运动,减少极化。
本发明所采用的具体技术方案如下:
第一方面,本发明提供了一种阴离子型多孔材料涂覆的复合隔膜的制备方法,具体如下:
S1:将阴离子型多孔材料与有机粘结剂按质量比(98-30):(2-70)混合,加入溶剂形成均匀浆料;
S2:将浆料涂覆在基底隔膜的单面或双面,干燥后获得阴离子型多孔材料涂覆的复合隔膜。
作为优选,阴离子型多孔材料为具有共价连接配位的阴离子基团的多孔材料。
作为优选,阴离子型多孔材料包括金属-有机框架材料(MOF)或介孔二氧化硅。
进一步的,金属-有机框架是以钛、锆、铪、铬、铁、钴、镍、铜、铝为金属中心中的一种或多种。
进一步的,介孔二氧化硅为MCM-41、SBA-3、SBA-15、MCM-48、MCM-50、SBA-16、SBA-1、SBA-6、SBA-2、SBA-12、FDU-1、HMS、MSU、KIT-1中的一种或多种。
作为优选,阴离子型多孔材料中的阴离子基团包括-R-COOX、-R-SO3X、-R-NXSO2CF3、-R-SO2NXSO2CF3中的一种或几种;其中,X为H、Li、Na、K、Zn、Mg、Ca和Al中的一种或多种,R代表有机链段。
作为优选,基底隔膜为多孔膜,包括聚乙烯膜、聚丙烯膜、玻璃纤维膜、无纺布和氧化铝涂覆的聚烯烃膜的一种。
进一步的,基底隔膜厚度为2~500μm。
作为优选,有机粘结剂为聚偏氟乙烯(PVDF)、聚甲基丙烯酸甲酯(PMMA)、聚四氟乙烯(PTFE)、聚偏氟乙烯-六氟丙烯(PVDF-HFP)、聚丙烯腈(PAN)、聚酰亚胺(PI)、聚乙二醇(PEG)、聚环氧乙烯(PEO)、聚多巴胺(PDA)、羧甲基纤维素钠/丁苯橡胶(CMC/SBR)、聚乙烯醇(PVA)、聚丙烯酸(PAA)、聚丙烯酸锂(LiPAA)、聚乙烯吡咯烷酮(PVP)、聚乳酸(PLA)、海藻酸钠(SA)、聚对苯乙烯磺酸(PSS)、聚苯并咪唑(PBI)、聚对苯乙烯磺酸锂(LiPSS)和明胶中的一种或多种。
作为优选,所涂覆的阴离子型多孔材料涂层厚度为0.5~100μm。
作为优选,所用溶剂为水、N-甲基吡咯烷酮(NMP)、丙酮、乙腈、甲醇、乙醇、碳酸二甲酯、碳酸甲乙酯、碳酸二乙酯、四氢呋喃、N,N-二甲基甲酰胺、二甲醚、二甲基硫醚、1,3-二氧环戊烷、1,4-二氧环噁烷、1,2-二甲氧乙烷、乙二醇二甲醚、双-三氟乙基醚、六氟异丙基甲醚、六氟异丙基乙醚、全氟丁基甲醚、全氟丁基乙醚、四氟乙基四氟丙基醚、四氟乙基八氟戊基醚中的一种或多种。
第二方面,本发明提供了一种根据第一方面任一所述制备方法得到的阴离子型多孔材料涂覆的复合隔膜。
第三方面,本发明提供了一种采用第二方面所述阴离子型多孔材料涂覆的复合隔膜的二次电池,具体如下:
将阴离子型多孔材料涂覆的复合隔膜设置于二次电池正极和负极之间。
作为优选,二次电池以锂离子、钠离子、钾离子、锌离子、铝离子、镁离子或钙离子作为传输离子类型。
作为优选,二次电池包括但不限于锌-卤素(Zn-Cl2,Zn-Br2)、金属空气基(Li-Air,Na-Air,Al-Air,Zn-Air)、锂离子、钠离子、锂金属、钠金属电池。
本发明相对于现有技术而言,具有以下有益效果:
(1)本发明采用的多孔材料,孔隙率高,比表面积大,能够改善复合隔膜对电解液的浸润性。
(2)阴离子型多孔材料涂层能够增加复合隔膜的热稳定性,并且其较高的杨氏模量能够抑制锂枝晶的生长。
(3)使用多孔隔膜作为基底(即基底隔膜),能够增加复合隔膜的拉伸性能和柔性。
(4)阴离子基团通过共价键连接到多孔材料的骨架上,抑制了阴离子的移动,增加了阳离子迁移数,减弱电池的极化现象。
附图说明
图1是实施例1所制备的UiO-66-COOLi@PBI/PE复合隔膜的扫描电镜图。
图2是实施例1所制备UiO-66-COOLi@PBI/PE复合隔膜(b)和对照PE隔膜(a)的EIS图。
图3是实施例1所制备Thick Li||electrolyte||25μm Li对称电池的循环性能对比图。
图4是实施例1所制备的Thick Li||electrolyte||Cu库伦效率对比图。
图5是实施例1、实施例2、实施例3所制备的复合隔膜和对照PE隔膜对电解液的浸润性测试。
图6是实施例1、实施例2、实施例3所制备的复合隔膜和对照PE隔膜在120℃下的热稳定性测试。
具体实施方式
本发明制备了一种阴离子型多孔材料涂覆的复合隔膜及其方法与二次电池。以下实施例进一步说明本发明的内容,但不应理解为对本发明的限制。
实施例1
(1)将1.275g 1,2,3,5-均苯四甲酸(H4BTC)和1.219g氯化锆(ZrCl4)溶于30mL去离子水和20mL乙酸混合溶液中,在100℃下冷凝回流24h。冷却至室温后,离心,并用乙醇洗涤干燥,获得羧基接枝的UiO-66,记为UiO-66-COOH。
(2)将步骤(1)中的UiO-66-COOH用1M LiTFSI(双三氟甲磺酰亚胺锂)的乙腈溶液进行离子交换3次,将羧基的质子置换为锂离子,然后用乙腈洗涤并在120℃下干燥3h,获得UiO-66-COOLi。
(3)将1g PBI溶于20mL NMP中,配置PBI浆料。
(4)将100mg步骤(2)中获得的UiO-66-COOLi与125μL PBI浆料混合,然后加入1mLNMP溶剂进行研磨,得到混合浆料。
(5)将步骤(4)中的混合浆料均匀涂覆在20μm的PE隔膜上,然后在80℃下进行真空干燥,获得UiO-66-COOLi@PBI/PE复合隔膜。
(6)使用UiO-66-COOLi@PBI/PE复合隔膜进行thick Li||electrolyte||25μmLi扣式电池测试。使用的电解液为1M的含LiPF6的FEC/DMC溶液,其中LiPF6和FEC/DMC体积比为4:6。
复合隔膜的扫描电镜如图1所示。UiO-66-COOLi@PBI均匀涂覆在PE表面,所涂覆的UiO-66-COOLi@PBI涂层没有明显裂缝。图2为所制备UiO-66-COOLi@PBI/PE复合隔膜和未经处理的PE隔膜(记为对照PE)的EIS图。实验结果表明,所制备的UiO-66-COOLi@PBI/PE复合隔膜具有更高的离子电导率,0.88mS cm-1.图3为对称电池循环性能,在进行0.5mA cm-2充放电0.5mAh cm-2时,电池能够稳定循环200h,具有良好的循环性能。图4是不同隔膜装备的Thick Li||electrolyte||Cu库伦效率对比图,使用UiO-66-COOLi@PBI/PE复合隔膜电池具有更高的库伦效率(98.5%)。
实施例2
(1)将浓硫酸与30%过氧化氢溶液通过体积比7:3混合配置食人鱼溶液。
(2)将2g MCM-41与100mL食人鱼溶液混合,在70℃下加热30min。然后用去离子水和乙醇进行洗涤并在120℃下干燥3h获得MCM-41-OH。
(3)取1g步骤(2)中获得的MCM-41-OH和2g 3-巯丙基三甲氧基硅烷(MPTMS)于50mL甲苯中,在氮气气氛下冷凝回流24h。将获得的产物用乙醇洗涤并干燥,获得接枝磺酸根的MCM-41-R-SO3H。
(4)将(3)中获得的MCM-41-R-SO3H用1M LiCl水溶液进行离子交换,并用乙醇进行洗涤,然后在120℃下干燥3h,获得MCM-41-R-SO3Li。
(5)将1g PVDF-HFP溶于20mL NMP中,配置PVDF-HFP浆料。
(6)将100mg步骤(4)中获得的MCM-41-R-SO3Li与125μL PVDF-HFP浆料混合,然后加入1mL NMP溶剂进行研磨,得到混合浆料。
(7)将步骤(6)中的混合浆料均匀涂覆在PE隔膜上,然后在80℃下进行真空干燥,获得MCM-41-R-SO3Li@PVDF-HFP/PE复合隔膜。
实施例3
(1)将浓硫酸与30%过氧化氢溶液通过体积比7:3混合配置食人鱼溶液。
(2)将2g MCM-41与100mL食人鱼溶液混合,在70℃下加热30min。然后用去离子水和乙醇进行洗涤并在120℃下干燥3h获得MCM-41-OH。
(3)取1g步骤(2)中获得的MCM-41-OH和2g 3-氨基丙基三甲氧基硅烷于50mL甲苯中,在氮气气氛下冷凝回流24h。将获得的产物用乙醇洗涤并干燥,获得接枝磺酸根的MCM-41-R-NH2。
(4)取0.3g步骤(3)获得的MCM-41-R-NH2、0.1518g三乙胺和20mL二氯甲烷混合并冷却至0℃。加入0.3385g三氟甲磺酸酐,然后逐滴加入0.0791g吡啶,0℃下搅拌30min。然后在室温下搅拌72h。反应完成后,先后用甲苯和乙醇洗涤,并干燥,获得MCM-41-R-NHSO2CF3。
(5)将(3)中获得的MCM-41-R-NHSO2CF3用1M LiTFSI乙腈溶液进行离子交换,并用乙腈进行洗涤,然后在120℃下干燥3h,获得MCM-41-R-NLiSO2CF3。
(6)将1g PVDF-HFP溶于20mL NMP中,配置PVDF-HFP浆料。
(7)将100mg步骤(4)中获得的MCM-41-R-NLiSO2CF3与125μLPVDF-HFP浆料混合,然后加入1mL NMP溶剂进行研磨,得到混合浆料。
(8)将步骤(6)中的混合浆料均匀涂覆在PE隔膜上,然后在80℃下进行真空干燥,获得MCM-41-R-NLiSO2CF3@PVDF-HFP/PE复合隔膜。
图5为制备的不同的复合隔膜与对照PE隔膜的接触角的对比图,阴离子多孔材料涂覆的复合隔膜具有更小的接触角,说明其对电解液的浸润性好。图6为制备的复合隔膜和对照PE隔膜在120℃处理之后的图片,实验发现阴离子型多孔材料涂覆的复合隔膜收缩程度更小,说明其热稳定性高。
实施例4
(1)将1g ZrOCl2·8H2O和0.83g 2-磺酸对苯二甲酸单钠盐溶于11.7mL甲酸和30mLN’N-二甲基乙酰胺(DMA)中,在150℃下反应24h。冷却至室温后,离心,用DMA和甲醇对产物进行洗涤,干燥得到UiO-66-SO3Na。
(2)将步骤(1)中获得的UiO-66-SO3Na用1M LiTFSI乙腈溶液进行离子交换,然后用乙腈洗涤并干燥,获得UiO-66-SO3Li。
(3)将1g PVDF溶于20mL NMP中,配置PVDF浆料。
(4)将100mg步骤(2)中获得的UiO-66-SO3Li与125μL PVDF浆料混合,然后加入1mLNMP溶剂进行研磨,得到混合浆料。
(5)将步骤(4)中的混合浆料均匀涂覆在氧化铝涂覆的PE膜上,然后在80℃下进行真空干燥,获得UiO-66-SO3Li@PVDF/PE复合隔膜。
本发明制备的复合隔膜具有良好的机械性能、高温稳定性、浸润性,同时,多孔材料的孔道有利于离子的均匀传输,并且阴离子型的多孔材料能够抑制阴离子的迁移,提高阳离子迁移数,提升二次电池的循环稳定性。
以上所述的实施例只是本发明的一种较佳的方案,然其并非用以限制本发明。有关技术领域的普通技术人员,在不脱离本发明的精神和范围的情况下,还可以做出各种变化和变型。因此凡采取等同替换或等效变换的方式所获得的技术方案,均落在本发明的保护范围内。
Claims (10)
1.一种阴离子型多孔材料涂覆的复合隔膜的制备方法,其特征在于,制备方法如下:
将阴离子型多孔材料与有机粘结剂按质量比(98-30):(2-70)混合,加入溶剂形成均匀浆料;所述阴离子型多孔材料为具有共价连接配位的阴离子基团的多孔材料;将所述的浆料涂覆在基底隔膜的单面或双面,干燥后获得阴离子型多孔材料涂覆的复合隔膜。
2.根据权利要求1所述的阴离子型多孔材料涂覆的复合隔膜的制备方法,其特征在于,所述的多孔材料为金属-有机框架材料或介孔二氧化硅。
3.根据权利要求2所述的阴离子型多孔材料涂覆的复合隔膜的制备方法,其特征在于,所述的金属-有机框架材料是以钛、锆、铪、铬、铁、钴、镍、铜、铝为金属中心中的一种或多种;所述的介孔二氧化硅为MCM-41、SBA-3、SBA-15、MCM-48、MCM-50、SBA-16、SBA-1、SBA-6、SBA-2、SBA-12、FDU-1、HMS、MSU、KIT-1中的一种或多种。
5.根据权利要求1所述的离子型多孔材料涂覆的复合隔膜的制备方法,其特征在于,所述基底隔膜为多孔膜,包括聚乙烯膜、聚丙烯膜、玻璃纤维膜、无纺布和氧化铝涂覆的聚烯烃膜的一种;所述的基底隔膜厚度为2~500μm。
6.根据权利要求1所述的阴离子型多孔材料涂覆的复合隔膜的制备方法,其特征在于,所述的有机粘结剂为聚偏氟乙烯、聚甲基丙烯酸甲酯、聚四氟乙烯、聚偏氟乙烯-六氟丙烯、聚丙烯腈、聚酰亚胺、聚乙二醇、聚环氧乙烯、聚多巴胺、羧甲基纤维素钠/丁苯橡胶、聚乙烯醇、聚丙烯酸、聚丙烯酸锂、聚乙烯吡咯烷酮、聚乳酸、海藻酸钠、聚对苯乙烯磺酸、聚苯并咪唑、聚对苯乙烯磺酸锂和明胶中的一种或多种。
7.根据权利要求1所述的阴离子型多孔材料涂覆的复合隔膜的制备方法,其特征在于,所述基底隔膜上涂覆的阴离子型多孔材料的厚度为0.5~100μm。
8.根据权利要求1所述的阴离子型多孔材料涂覆的复合隔膜的制备方法,其特征在于,所用溶剂为水、N-甲基吡咯烷酮、丙酮、乙腈、甲醇、乙醇、碳酸二甲酯、碳酸甲乙酯、碳酸二乙酯、四氢呋喃、N,N-二甲基甲酰胺、二甲醚、二甲基硫醚、1,3-二氧环戊烷、1,4-二氧环噁烷、1,2-二甲氧乙烷、乙二醇二甲醚、双-三氟乙基醚、六氟异丙基甲醚、六氟异丙基乙醚、全氟丁基甲醚、全氟丁基乙醚、四氟乙基四氟丙基醚、四氟乙基八氟戊基醚中的一种或多种。
9.一种根据权利要求1~8任一所述制备方法得到的阴离子型多孔材料涂覆的复合隔膜。
10.一种二次电池,其特征在于,包括设置于正极和负极之间的如权利要求9所述的阴离子型多孔材料涂覆的复合隔膜,该二次电池的传输离子类型为锂离子、钠离子、钾离子、锌离子、铝离子、镁离子或钙离子中的一种。
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