CN111395008A - 全氟磺酸树脂/聚偏氟乙烯复合电纺丝膜及其制备方法 - Google Patents

全氟磺酸树脂/聚偏氟乙烯复合电纺丝膜及其制备方法 Download PDF

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CN111395008A
CN111395008A CN202010221690.9A CN202010221690A CN111395008A CN 111395008 A CN111395008 A CN 111395008A CN 202010221690 A CN202010221690 A CN 202010221690A CN 111395008 A CN111395008 A CN 111395008A
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acid resin
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刘建国
张登华
徐泽宇
赵丽娜
严川伟
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Abstract

本发明公开了一种全氟磺酸树脂/聚偏氟乙烯复合电纺丝膜及其制备方法，属于全钒氧化还原液流电池(VRFB)电池隔膜技术领域。该方法首先采用静电纺丝制备聚偏氟乙烯树脂纺丝膜，然后将所得聚偏氟乙烯树脂纺丝膜浸泡在浓度为3～20wt.％的全氟磺酸树脂的乙醇溶液中，之后烘干成膜，重复浸泡‑烘干的过程3‑10次，即获得所述全氟磺酸树脂/聚偏氟乙烯复合电纺丝膜。本发明制备的复合电纺丝膜具有较好的阻钒性、机械性能以及较好的导电性，使VRFB具有较好的电池性能，为全钒氧化还原液流电池隔膜的发展提供新思路。

Description

全氟磺酸树脂/聚偏氟乙烯复合电纺丝膜及其制备方法
技术领域
本发明涉及全钒氧化还原液流电池(VRFB)电池隔膜技术领域，具体为一种全氟磺酸树脂/聚偏氟乙烯复合电纺丝膜及其制备方法。
背景技术
随着化石燃料消耗的迅速增加和随之而来的环境污染，迫切需要开发和有效利用风能、太阳能、生物质等可再生能源，但这些可再生能源本质上是间歇性的，导致了季节性和不稳定发电与持续稳定供电需求之间的矛盾。因此，储能包括电池在内的设备对稳定的电力供应至关重要。理想的储能技术需要低成本、环保、长寿命、高性能、高能量密度。液流氧化还原电池(RFBs)在稳定性、安全性、效率、可靠性和易用性等方面表现出优异的性能。其中，全钒氧化还原电池(VRFBs)在大型存储系统中显示出明显的优势。
VRFBs包含两个电解质容器、两个电极和一个隔膜。VRFBs的性能主要表现为库仑效率(CE)、电压效率(VE)和能量效率(EE)。隔膜是VRFBs的关键材料和核心部件之一，起到阻隔正负极混液、形成电流回路的作用。性能优异的隔膜，除具有必要机械性能和化学稳定性外，还必须满足质子导电性和离子选择性(阻钒性)之间的有效平衡，即活性离子扩散(H+、H3O+、SO42-或SO4H-)的导电能力与阻钒离子渗透能力之间的平衡。
而隔膜因自身离子传导所产生的电阻，占整个电池堆内阻的较大部分(30-50％)。因此，在保证较小的钒透过率的同时，提高隔膜电导率、降低隔膜面电阻，可有效提升电堆的工作电流密度，也是提高钒电池功率密度的有效途径之一。
发明内容
本发明的目的是提供一种全氟磺酸树脂/聚偏氟乙烯复合电纺丝膜及其制备方法，通过改变工艺参数，制备了复合电纺丝膜，在保证隔膜高离子选择透过性、高导电性同时，降低隔膜成本，提高隔膜机械强度，可适用于全钒氧化还原液流电池(VRFB)。
为实现上述目的，本发明所采用的技术方案如下：
一种全氟磺酸树脂/聚偏氟乙烯复合电纺丝膜的制备方法，包括如下步骤：
(1)将聚偏氟乙烯树脂溶于有机溶剂中，在磁力搅拌条件下溶解，配成浓度为3～25wt.％的聚偏氟乙烯树脂溶液；
(2)将步骤(1)所得的聚偏氟乙烯树脂溶液超声处理，使树脂分散均匀，并除去溶液中气泡；
(3)采用静电纺丝装置制备聚偏氟乙烯树脂纺丝膜：将经步骤(2)超声处理后的聚偏氟乙烯树脂溶液加入到静电纺丝装置的注射器中，开始静电纺丝，纺丝时间2～6h，纺丝完成后，将铝箔纸取下，铝箔纸上附有聚偏氟乙烯树脂纺丝膜，干燥条件下保存；
(4)将步骤(3)中所得的附于铝箔纸上的聚偏氟乙烯树脂纺丝膜，浸泡在浓度为3～20wt.％的全氟磺酸树脂的乙醇溶液中，之后烘干成膜，重复浸泡-烘干的过程3-10次，从而在聚偏氟乙烯树脂纺丝膜上复合一层全氟磺酸树脂，即获得所述全氟磺酸树脂/聚偏氟乙烯复合电纺丝膜。
上述步骤(1)中，有机溶剂选自二甲基亚砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮和二氯甲烷中的一种或几种。
上述步骤(2)中，超声时间为0.5～4小时。
所述静电纺丝装置包括注射器、针头、接收器和高压静电发生器，高压静电发生器的正极接到针头上，高压静电发生器的负极连接到接收器上，接收器上铺有一层铝箔纸，用于接收静电纺纤维。
上述步骤(3)中，静电纺丝过程在室温条件下进行，设置注射器针头与接收器之间距离为8～15cm，电压为10～20千伏，注射器推进速度为0.1～12.0毫升/小时。
所述室温条件为温度20℃、湿度45％。
上述步骤(3)中，所述注射器为5mL注射器，注射器针头与接收器之间距离为10cm。
上述步骤(4)中，制膜烘干温度为80～140℃，每次烘干时间为1～4h。
所述制备的全氟磺酸树脂/聚偏氟乙烯复合电纺丝膜，是由聚偏氟乙烯树脂纺丝膜和全氟磺酸树脂膜组成的两层复合结构，该复合电纺丝膜的拉伸强度大于52MPa，断裂伸长率大于108％，离子传导率大于12mS cm-1，氧化稳定性达到96.7％，钒离子渗透常数小于14×10-7cm min-1。
本发明的优点及有益效果如下：
1、本发明利用静电纺丝技术制备了隔膜的基体-聚偏氟乙烯树脂纺丝膜，再在基体上复合全氟磺酸树脂，构建了静电纺丝复合膜，降低成本的同时，降低电池内阻，提高了阻钒率，进而提高电池效率，为钒电池电极、隔膜的应用提供新的思路，对提高钒电池性能、降低储能系统成本有着非常重要的意义。
2、VRFB的性能主要表现为库仑效率(CE)、电压效率(VE)和能量效率(EE)。隔膜是VRFB的关键材料和核心部件之一，起到阻隔正负极混液、形成电流回路的作用。性能优异的隔膜，除具有必要机械性能和化学稳定性外，还必须满足质子导电性和离子选择性(阻钒性)之间的有效平衡。全钒液流电池的性能由电压效率和电流效率两方面决定，其中欧姆极化导致电池的电压损失，影响其电压效率。本发明采用静电纺丝复合膜，有效降低电池的内阻，降低电池的极化损失，提高VRFB的性能。
3、本发明制备的膜电极具有良好的阻钒性能、机械性能以及良好导电性，提高单个VRB电池性能，可应用于全钒氧化还原液流电池领域。
具体实施方式
为了进一步理解本发明，以下结合实例对本发明进行描述，但实例仅为对本发明的特点和优点做进一步阐述，而不是对本发明权利要求的限制。
以下实施例中所用静电纺丝装置包括注射器、针头、接收器(板)和高压静电发生器，高压静电发生器的正极接到针头上，高压静电发生器的负极连接到接收器上，接收器上铺有一层铝箔纸，用于接收静电纺纤维。静电纺丝过程在室温条件(温度20℃、湿度45％)下进行。
实施例1
本实施例述静电纺丝膜的制备方法，包括如下步骤：
(1)将2g聚偏氟乙烯树脂溶于N,N-二甲基乙酰胺中，在磁力搅拌条件下溶解，配成质量百分数为15％的聚偏氟乙烯树脂溶液；
(2)将步骤(1)中所得的聚偏氟乙烯树脂溶液超声处理1h，使树脂分散均匀，除去气泡；
(3)将以步骤(2)处理后的聚偏氟乙烯树脂溶液加入到注射器中，在室温条件下设置针头与接收器之间距离为10cm，电压为15千伏，注射器推进速度为0.5毫升/小时；
(4)然后将高压静电发生器的正极接到针头上，负极连接到接收器上，接收器上铺有一层铝箔纸，用于接收静电纺纤维，开始静电纺丝，纺丝5h，纺丝完成后，将铝箔纸取下，干燥条件下保存；
(5)将步骤(4)中所得的聚偏氟乙烯纺丝膜，浸泡在浓度为10wt.％的全氟磺酸树脂中，之后烘干成膜，重复浸泡－烘干的过程3次，获得全氟磺酸树脂/聚偏氟乙烯复合电纺丝膜。
所述全氟磺酸树脂/聚偏氟乙烯复合电纺丝膜是由聚偏氟乙烯树脂纺丝膜和全氟磺酸树脂膜组成的两层复合结构，所获得的隔膜光滑，分布均匀，无分层现象。
实施例2
与实施例1不同之处在于：
1、步骤(1)将2g聚偏氟乙烯树脂溶于N,N-二甲基乙酰胺中，在磁力搅拌器中溶解，配成质量百分数为10％的聚偏氟乙烯树脂溶液；
2、其余步骤与实施例1相同。本实施例中，所获得的隔膜光滑，分布均匀，无分层现象。
实施例3
与实施例1不同之处在于：
1、步骤(5)将步骤(4)中所得的聚偏氟乙烯纺丝膜，浸泡在浓度为10wt.％的全氟磺酸树脂中，之后烘干成膜，浸泡5次。
2、其余步骤与实施例1相同。本实施例中，所获得的隔膜光滑，分布均匀，无分层现象。
对上述实施例1-3所制备的钒电池用隔膜以及对比例所得的钒电池用离子交换膜进行相关性能测试，测试结果如表1所示，测试方法如下，
拉伸强度测试：按照GB/T 1040-2006《塑料拉伸性能试验方法》进行测试。
离子传导率：制备的隔膜的阻抗，是采用两电极交流阻抗法在电化学工作站上测得的，测试频率为1Hz～0.1MHz。将样品浸入3M H2SO4中12h，用3M H2SO4溶液填充两个电解质容器，并控制温度在25℃下。离子传导率根据下列公式计算：
Figure BDA0002426323530000051
其中，σ为离子传导率(S cm-1)，L为两电极之间的距离(cm)，R为所测样品的交流阻抗，A为膜的横截面面积。
氧化稳定性：将膜在60℃下干燥5h，迅速并且准确称取其质量，然后，将隔膜浸泡在40℃的0.1M L-1VO2++3.0M L-1H2SO4溶液中20小时后取出，洗涤、干燥、测定隔膜的重量保留率。计算公式为：
保留率＝(浸泡后膜重量-浸泡前膜重量)/浸泡前膜重量×100％
钒离子渗透常数：用自制装置测试了膜的VO2+渗透性，左右容器分别在3.0H2SO4溶液中填充200毫升1.65M VOSO4，在3.0M H2SO4中分别填充200毫升1.65M MgSO4。膜夹在两个容器之间，随着时间的推移，用紫外-可见光谱仪测量了MgSO4侧的钒离子浓度。根据文献法计算VO2渗透系数。
从表1可以看出，本发明实施例公开的钒电池用隔膜拉伸强度均大于52MPa，断裂伸长率均大于108％，离子传导率均大于12mS cm-1，氧化稳定性均达到96.7％，钒离子渗透常数均小于14×10-7cm min-1。可见，本发明实施例公开的钒电池用隔膜具有更加优异的拉伸性能和化学稳定性，且其具有更高的离子传导率和更低的钒离子渗透，符合钒电池用隔膜使用要求。
表1
项目 拉伸强度 断裂伸长率 离子传导率 氧化稳定性 钒离子渗透常数
单位 MPa ％ mS cm<sup>-1</sup> ％ ×10<sup>-7</sup>cm/min
实施例1 52.32 108.32 12.78 96.7 15.63
实施例2 54.65 109.12 13.09 98.3 14.96
实施例3 55.42 112.15 13.48 99.3 14.57
实验结果表明：本发明采用静电纺丝法，制备了全氟磺酸树脂/聚偏氟乙烯复合电纺丝膜。本发明制备的全氟磺酸树脂/聚偏氟乙烯复合电纺丝膜具有较好的阻钒性能、导电性能、以及良好电池性能等优点，降低电池内阻，提高隔膜机械性能，满足钒电池使用要求，可广泛地应用于全钒氧化还原液流电池领域。

Claims (9)

1.一种全氟磺酸树脂/聚偏氟乙烯复合电纺丝膜的制备方法，其特征在于：该方法包括如下步骤：
(1)将聚偏氟乙烯树脂溶于有机溶剂中，在磁力搅拌条件下溶解，配成浓度为3～25wt.％的聚偏氟乙烯树脂溶液；
(2)将步骤(1)所得的聚偏氟乙烯树脂溶液超声处理，使树脂分散均匀，并除去溶液中气泡；
(3)采用静电纺丝装置制备聚偏氟乙烯树脂纺丝膜：将经步骤(2)超声处理后的聚偏氟乙烯树脂溶液加入到静电纺丝装置的注射器中，开始静电纺丝，纺丝时间2～6h，纺丝完成后，将铝箔纸取下，铝箔纸上附有聚偏氟乙烯树脂纺丝膜，干燥条件下保存；
(4)将步骤(3)中所得的附于铝箔纸上的聚偏氟乙烯树脂纺丝膜，浸泡在浓度为3～20wt.％的全氟磺酸树脂的乙醇溶液中，之后烘干成膜，重复浸泡-烘干的过程3-10次，从而在聚偏氟乙烯树脂纺丝膜上复合一层全氟磺酸树脂，即获得所述全氟磺酸树脂/聚偏氟乙烯复合电纺丝膜。
2.按照权利要求1所述的全氟磺酸树脂/聚偏氟乙烯复合电纺丝膜的制备方法，其特征在于：步骤(1)中，有机溶剂选自二甲基亚砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮和二氯甲烷中的一种或几种。
3.按照权利要求1所述的全氟磺酸树脂/聚偏氟乙烯复合电纺丝膜的制备方法，其特征在于：步骤(2)中，超声时间为0.5～4小时。
4.按照权利要求1所述的全氟磺酸树脂/聚偏氟乙烯复合电纺丝膜的制备方法，其特征在于：所述静电纺丝装置包括注射器、针头、接收器和高压静电发生器，高压静电发生器的正极接到针头上，高压静电发生器的负极连接到接收器上，接收器上铺有一层铝箔纸，用于接收静电纺纤维。
5.按照权利要求4所述的全氟磺酸树脂/聚偏氟乙烯复合电纺丝膜的制备方法，其特征在于：步骤(3)中，静电纺丝过程在室温条件下进行，设置注射器针头与接收器之间距离为8～15cm，电压为10～20千伏，注射器推进速度为0.1～12.0毫升/小时。
6.按照权利要求5所述的全氟磺酸树脂/聚偏氟乙烯复合电纺丝膜的制备方法，其特征在于：所述室温条件为温度20℃、湿度45％。
7.按照权利要求5所述的全氟磺酸树脂/聚偏氟乙烯复合电纺丝膜的制备方法，其特征在于：步骤(3)中，所述注射器为5mL注射器，注射器针头与接收器之间距离为10cm。
8.按照权利要求1所述的全氟磺酸树脂/聚偏氟乙烯复合电纺丝膜的制备方法，其特征在于：步骤(4)中，制膜烘干温度为80～140℃，每次烘干时间为1～4h。
9.一种利用权利要求1-8任一所述方法制备的全氟磺酸树脂/聚偏氟乙烯复合电纺丝膜，其特征在于：该复合电纺丝膜是由聚偏氟乙烯树脂纺丝膜和全氟磺酸树脂膜组成的两层复合结构，该复合电纺丝膜的拉伸强度大于52MPa，断裂伸长率大于108％，离子传导率大于12mS cm-1，氧化稳定性达到96.7％，钒离子渗透常数小于14×10-7cm min-1。
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