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CN113943158B - 一种液流电池用石墨毡制备方法 - Google Patents

一种液流电池用石墨毡制备方法 Download PDF

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CN113943158B
CN113943158B CN202111557825.XA CN202111557825A CN113943158B CN 113943158 B CN113943158 B CN 113943158B CN 202111557825 A CN202111557825 A CN 202111557825A CN 113943158 B CN113943158 B CN 113943158B
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graphite felt
polymer
solution
honeycomb
acid
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熊仁海
王宇
陈广新
郭勇
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Hangzhou Dehai Aike Energy Technology Co ltd
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Abstract

本发明公开了一种全钒液流电池用石墨毡制备方法，包括以下步骤：S1：预处理石墨毡；S2：将聚合物溶解在溶剂中，搅拌均匀得到聚合物溶液；S3：在聚合物溶液中添加金属离子溶液，碳纳米材料，并搅拌分散均匀，得到聚合物混合溶液；S4：将所述预处理石墨毡完全浸渍在所述聚合物混合溶液中得到含有聚合物石墨毡；S5：将含有聚合物石墨毡放置在冷冻干燥机内冷冻干燥得到蜂巢状石墨毡半成品；S6：将所述蜂巢状石墨毡放入马弗炉中，升温烧结得到蜂巢状石墨毡。本发明蜂巢状石墨毡结构可大大拓展石墨毡比表面积，改善增强亲水性，有利于钒离子的传输，提升电池效率，多维度提升性能，提升幅度大。

Description

一种液流电池用石墨毡制备方法
技术领域
本发明涉及一种全钒液流电池电极材料技术领域，尤其涉及一种全钒液流电池用石墨毡制备方法。
背景技术
近年来，全钒氧化还原液流电池成为新型储能电池的焦点，电极作为液流电池的关键材料之一，其改性可大幅提升电池效率，成为研究的热点。其中，碳素类材料因具备低成本和高性能的优势，被广泛用作钒液流电池电极。
碳素类电极材料主要包括各种碳材料（玻碳、碳布、碳毡和碳纸等）和石墨材料（石墨板、石墨纤维和石墨毡等）。石墨毡表面积大、导电性好、化学稳定性和机械性能好，基本满足钒液流电池电极材料的特性要求，更进一步研究发现聚丙烯腈基石墨毡的综合性能最好，是钒液流电池电极的理想材料。
但是，目前聚丙烯腈基石墨毡电极改性主要是氧化活化、掺杂活化以及碳纳米催化剂活化等方法局限在在纤维表面修饰，未能拓展到三维立体空间，改性提升性能有限，因此需要更进一步地改善石墨毡电极表面以及内部结构，提升性能。
发明内容
本发明的目的在于提供一种全钒液流电池用石墨毡制备方法，解决了现有技术中石墨毡电极改性仅仅局限于纤维表面修饰，石墨毡内部结构和功能改性有限的问题。
本发明采用的技术方案如下：
一种全钒液流电池用石墨毡制备方法，包括以下步骤：
S1：石墨毡高温活化或酸活化得到预处理石墨毡；
S2：将聚合物溶解在溶剂中得到聚合物质量浓度为2-30%的聚合物溶液；
S3：在所述聚合物溶液中添加质量浓度为1%-5%的金属离子溶液，0.1%-5%的碳纳米材料，并以200-2000rpm的搅拌速度搅拌5-20min分散均匀，得到聚合物混合溶液；
S4：将所述预处理石墨毡完全浸渍在所述聚合物混合溶液中10-60min，得到含有聚合物石墨毡；
S5：将S4中含有聚合物石墨毡放置在冷冻干燥机内冷冻干燥4-24h，得到蜂巢状石墨毡半成品；
S6：将所述蜂巢状石墨毡放入马弗炉中，升温至200-800℃，烧结2-10h得到蜂巢状石墨毡。
进一步地，所述S3中聚合物溶液：金属离子溶液：碳纳米材料的质量比为98：0.5：1.5-96：2：2。
进一步地，所述S1中所述高温活化的方法为：将石墨毡放置在微波热或者空气热的环境中升温至200-600℃，维持4-24h，得到预处理石墨毡。
进一步地，所述S1中所述酸活化的方法为：将石墨毡浸泡在酸性溶液中，加热至60-120℃，维持2-10h，得到预处理石墨毡。
进一步地，所述酸性溶液为以下任意一种：6mol/L浓硝酸、18.4mol/L浓硫酸、12mol/L盐酸或1mol/L草酸。
进一步地，所述S2中所述聚合物为以下任意一种或两种以上的混合物：明胶、壳聚糖、海藻酸钠、纤维素、甲壳素、聚丙烯酸、聚丙烯酰胺、聚丙烯、聚乙烯、聚苯乙烯、聚氯乙烯、聚丙烯腈、聚二甲基硅氧烷或聚氟乙烯。
进一步地，所述S2中所述溶剂包括以下任意一种或两种以上的混合物：水、甲醇、乙醇、对二甲苯、苯、甲苯、四氢呋喃、乙酸异戊酯、二甲胺基甲酰胺、三氯甲烷或环己酮。
进一步地，所述S3中所述金属离子溶液为含Mn2+、Au4+、Pd2+、In3+、Pt4+、Te4+或Ir3+离子的任意一种或两种以上的溶液。
进一步地，所述S3中所述碳纳米材料包括以下任意一种或两种以上的混合物：氧化石墨烯、石墨烯、多壁碳纳米管、单壁碳纳米管或碳纳米纤维。
进一步地，所述S5中所述含有聚合物的石墨毡在冷冻干燥机中水平放置，保证真空干燥后孔径方向与纤维方向一致。
本发明的有益效果是：
1.本发明一种全钒液流电池用石墨毡制备方法得到的蜂巢状石墨毡结构可大大拓展石墨毡比表面积，改善增强亲水性，有利于钒离子的传输，为钒液流电池充放电反应提供更多的反应界面，提升电池效率。
2.本发明蜂巢状石墨毡复配有金属及其化合物、碳纳米材料，可提升石墨毡导电性，增加石墨毡表面功能团，为钒液流电池充放电反应提供更多的反应界面，从而降低电池内部欧姆电阻以及反应极化电阻，提高电池效率。
附图说明
图1为本发明的流程示意图；
图2为本发明的蜂巢状石墨毡示意图。
附图标记说明
1-石墨毡纤维，2-蜂巢状结构。
具体实施方式
以下对至少一个示例性实施例的描述实际上仅仅是说明性的，决不作为对本发明及其应用或使用的任何限制。基于本发明中的实施例，本领域普通技术人员在没有作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。
见图1，一种全钒液流电池用石墨毡制备方法，包括以下步骤：
S1：石墨毡高温活化或酸活化得到预处理石墨毡；所述高温活化的方法为：将石墨毡放置在微波热或者空气热的环境中升温至200-600℃，维持4-24h，得到预处理石墨毡；所述酸活化的方法为：将石墨毡浸泡在酸性溶液中，加热至60-120℃，维持2-10h，得到预处理石墨毡；所述酸性溶液为以下任意一种：6mol/L浓硝酸、18.4mol/L浓硫酸、12mol/L盐酸或1mol/L草酸。
S2：将聚合物溶解在溶剂中，在温度为25-50℃搅拌2-8h得到聚合物质量浓度为2-30%的聚合物溶液；所述聚合物为以下任意一种或两种以上的混合物：明胶、壳聚糖、海藻酸钠、纤维素、甲壳素、聚丙烯酸、聚丙烯酰胺、聚丙烯、聚乙烯、聚苯乙烯、聚氯乙烯、聚丙烯腈、聚二甲基硅氧烷或聚氟乙烯；所述溶剂包括以下任意一种或两种以上的混合物：水、甲醇、乙醇、对二甲苯、苯、甲苯、四氢呋喃、乙酸异戊酯、二甲胺基甲酰胺、三氯甲烷或环己酮；
S3：在所述聚合物溶液中添加质量浓度为1%-5%的金属离子溶液，0.1%-5%的碳纳米材料，并以200-2000rpm的搅拌速度搅拌5-20min分散均匀，得到聚合物混合溶液；所述聚合物溶液：金属离子溶液：碳纳米材料的质量比为98：0.5：1.5-96：2：2；所述金属离子溶液为含Mn2+、Au4+、Pd2+、In3+、Pt4+、Te4+或Ir3+离子的任意一种或两种以上的溶液；所述碳纳米材料包括以下任意一种或两种以上的混合物：氧化石墨烯、石墨烯、多壁碳纳米管、单壁碳纳米管或碳纳米纤维；
S4：将所述预处理石墨毡完全浸渍在所述聚合物混合溶液中10-60min，得到含有聚合物石墨毡；
S5：将S4中含有聚合物石墨毡放置在冷冻干燥机内冷冻干燥4-24h，得到蜂巢状石墨毡半成品；所述含有聚合物的石墨毡在冷冻干燥机中水平放置，保证真空干燥后孔径方向与纤维方向一致；
S6：将所述蜂巢状石墨毡放入马弗炉中，升温至200-800℃，烧结2-10h得到蜂巢状石墨毡。
见图2，一种蜂巢状石墨毡的结构为石墨毡纤维1与蜂巢状结构2合为一体构成蜂巢状石墨毡。
实施例1
一种蜂巢状石墨毡制备方法包括以下步骤：
S1：石墨毡浸泡在18.4mol/L浓硫酸中，加热至100℃，维持6h，得到预处理石墨毡；
S2：将明胶缓慢加入水中，40℃搅拌4h得到质量浓度为2%的明胶溶液；
S3：在98g所述明胶溶液中添加0.5g质量浓度为2%的Pd2+离子溶液，1.5g浓度为0.1%的单壁碳纳米管，并以1000rpm的搅拌速度搅拌10min分散均匀，得到明胶混合溶液；
S4：将所述预处理石墨毡完全浸渍在所述明胶混合溶液中30min，得到含有明胶石墨毡；
S5：将S4中含有明胶石墨毡放置在冷冻干燥机内水平放置冷冻干燥12h，保证真空干燥后孔径方向与纤维方向一致，得到蜂巢状石墨毡半成品；
S6：将所述蜂巢状石墨毡放入马弗炉中，升温至600℃，烧结8h得到蜂巢状石墨毡。
实施例2
一种蜂巢状石墨毡制备方法包括以下步骤：
S1：石墨毡放置空气热的环境中升温至500℃，维持6h，使得石墨毡纤维带上-OH官能团，得到预处理石墨毡；
S2：将壳聚糖缓慢加入水中，50℃搅拌3h得到质量浓度为8%的壳聚糖溶液；
S3：在97g所述壳聚糖溶液中添加1g质量浓度为1%的Au4+离子溶液和2g质量浓度为1.0%的氧化石墨烯，并以200rpm的搅拌速度搅拌5min分散均匀，得到壳聚糖混合溶液；
S4：将所述预处理石墨毡完全浸渍在所述壳聚糖混合溶液中10min，得到含有壳聚糖石墨毡；
S5：将S4中含有壳聚糖石墨毡放置在冷冻干燥机内水平放置冷冻干燥18h，保证真空干燥后孔径方向与纤维方向一致，得到蜂巢状石墨毡半成品；
S6：将所述蜂巢状石墨毡放入马弗炉中，升温至200℃，烧结10h得到蜂巢状石墨毡。
实施例3
一种蜂巢状石墨毡制备方法包括以下步骤：
S1：石墨毡放置空气热的环境中升温至600℃，维持4h，使得石墨毡纤维带上-OH官能团，得到预处理石墨毡；
S2：将海藻酸钠和甲壳素缓慢加入水中，30℃搅拌8h得到质量浓度为5%的聚合物溶液；
S3：在96g所述聚合物溶液中添加2g质量浓度为3%的Pt4+离子溶液和2g质量浓度为2.0%的氧化石墨烯，并以1500rpm的搅拌速度搅拌15min分散均匀，得到聚合物混合溶液；
S4：将所述预处理石墨毡完全浸渍在所述聚合物混合溶液中60min，得到含有聚合物的石墨毡；
S5：将S4中含有聚合物的石墨毡放置在冷冻干燥机内水平放置冷冻干燥4h，保证真空干燥后孔径方向与纤维方向一致，得到蜂巢状石墨毡半成品；
S6：将所述蜂巢状石墨毡放入马弗炉中，升温至800℃，烧结2h得到蜂巢状石墨毡。
实施例4
一种蜂巢状石墨毡制备方法包括以下步骤：
S1：石墨毡浸泡在18.4mol/L浓硫酸中，加热至80℃，维持5h，得到预处理石墨毡；
S2：将聚丙烯酸缓慢加入水中，25℃搅拌4h得到质量浓度为30%的聚丙烯酸溶液；
S3：在97g所述聚丙烯酸溶液中添加1.5g质量浓度为5%的Au4+离子溶液和1.5g质量浓度为2.5%碳纳米纤维，并以2000rpm的搅拌速度搅拌20min分散均匀，得到聚丙烯酸混合溶液；
S4：将所述预处理石墨毡完全浸渍在所述聚丙烯酸混合溶液中50min，得到含有聚丙烯酸石墨毡；
S5：将S4中含有聚丙烯酸石墨毡放置在冷冻干燥机内水平放置冷冻干燥24h，保证真空干燥后孔径方向与纤维方向一致，得到蜂巢状石墨毡半成品；
S6：将所述蜂巢状石墨毡放入马弗炉中，升温至800℃，烧结5h得到蜂巢状石墨毡。
实施例5
一种蜂巢状石墨毡制备方法包括以下步骤：
S1：石墨毡浸泡在18.4mol/L浓硫酸中，加热至80℃，维持6h，得到预处理石墨毡；
S2：将聚丙稀酰胺缓慢加入水中，25℃搅拌2h得到质量浓度为25%的聚丙稀酰胺溶液；
S3：在96g所述聚丙稀酰胺溶液中添加2g质量浓度为3%的Mn2+离子溶液和2g质量浓度为5%的氧化石墨烯，并以2000rpm的搅拌速度搅拌20min分散均匀，得到聚丙稀酰胺混合溶液；
S4：将所述预处理石墨毡完全浸渍在所述聚丙稀酰胺混合溶液中40min，得到含有聚丙稀酰胺石墨毡；
S5：将S4中含有聚丙稀酰胺石墨毡放置在冷冻干燥机内水平放置冷冻干燥19h，保证真空干燥后孔径方向与纤维方向一致，得到蜂巢状石墨毡半成品；
S6：将所述蜂巢状石墨毡放入马弗炉中，升温至800℃，烧结5h得到蜂巢状石墨毡。
实施例6
一种蜂巢状石墨毡制备方法包括以下步骤：
S1：石墨毡放置微波热的环境中升温至200℃，维持24h，使得石墨毡纤维带上-OH官能团，得到预处理石墨毡；
S2：将纤维素和聚丙烯酸（质量比纤维素：聚丙烯酸=2：3）缓慢加入水和甲醇（质量比水：甲醇=5：1）的溶液中，30℃搅拌8h得到质量浓度为4%的聚合物溶液；
S3：在98g所述聚合物溶液中添加0.5g质量浓度为3%的Pt4+离子溶液和1.5g质量浓度为2%的氧化石墨烯，并以1500rpm的搅拌速度搅拌15min分散均匀，得到聚合物混合溶液；
S4：将所述预处理石墨毡完全浸渍在所述聚合物混合溶液中60min，得到含有聚合物石墨毡；
S5：将S4中含有聚合物石墨毡放置在冷冻干燥机内水平放置冷冻干燥4h，保证真空干燥后孔径方向与纤维方向一致，得到蜂巢状石墨毡半成品；
S6：将所述蜂巢状石墨毡放入马弗炉中，升温至800℃，烧结2h得到蜂巢状石墨毡。
实施例7
一种蜂巢状石墨毡制备方法包括以下步骤：
S1：石墨毡浸泡在6mol/L浓硝酸中，加热至120℃，维持10h，得到预处理石墨毡；
S2：将聚丙烯酰胺和聚丙烯酸（质量比聚丙烯酰胺：聚丙烯酸=4：1）缓慢加入水和甲醇（质量比水：甲醇=5：1）的溶液中，30℃搅拌6h得到质量浓度为20%的聚合物溶液；
S3：在97g所述聚合物溶液中添加1g质量浓度为2%的Pt4+和1%的Au4+离子的混合溶液以及2g质量浓度为2%的氧化石墨烯，并以1500rpm的搅拌速度搅拌15min分散均匀，得到聚合物混合溶液；
S4：将所述预处理石墨毡完全浸渍在所述聚合物混合溶液中60min，得到含有聚合物石墨毡；
S5：将S4中含有聚合物石墨毡放置在冷冻干燥机内水平放置冷冻干燥4h，保证真空干燥后孔径方向与纤维方向一致，得到蜂巢状石墨毡半成品；
S6：将所述蜂巢状石墨毡放入马弗炉中，升温至800℃，烧结2h得到蜂巢状石墨毡。
实施例8
一种蜂巢状石墨毡制备方法包括以下步骤：
S1：石墨毡浸泡在12mol/L盐酸中，加热至60℃，维持9h，得到预处理石墨毡；
S2：将聚丙烯缓慢加入乙酸异戊酯中，45℃搅拌3h得到质量浓度为6%的聚丙烯溶液；
S3：在96g所述聚丙烯溶液中添加2g质量浓度为1%的Mn2+离子和1%的In3+离子的混合溶液以及2g质量浓度为1.5%的多壁碳纳米管，并以200rpm的搅拌速度搅拌5min分散均匀，得到聚丙烯混合溶液；
S4：将所述预处理石墨毡完全浸渍在所述聚丙烯混合溶液中10min，得到含有聚丙烯石墨毡；
S5：将S4中含有聚丙烯石墨毡放置在冷冻干燥机内水平放置冷冻干燥8h，保证真空干燥后孔径方向与纤维方向一致，得到蜂巢状石墨毡半成品；
S6：将所述蜂巢状石墨毡放入马弗炉中，升温至200℃，烧结10h得到蜂巢状石墨毡。
实施例9
一种蜂巢状石墨毡制备方法包括以下步骤：
S1：石墨毡浸泡在1mol/L草酸中，加热至100℃，维持10h，得到预处理石墨毡；
S2：将聚乙烯缓慢加入对二甲苯中，50℃搅拌5h得到质量浓度为8%的聚乙烯溶液；
S3：在97g所述聚乙烯溶液中添加1.5g质量浓度为1%的Pd2+离子和1%的Pt4+离子的混合溶液以及1.5g质量浓度为0.1%的单壁碳纳米管，并以500rpm的搅拌速度搅拌10min分散均匀，得到聚乙烯混合溶液；
S4：将所述预处理石墨毡完全浸渍在所述聚乙烯混合溶液中20min，得到含有聚乙烯石墨毡；
S5：将S4中含有聚乙烯石墨毡放置在冷冻干燥机内水平放置冷冻干燥12h，保证真空干燥后孔径方向与纤维方向一致，得到蜂巢状石墨毡半成品；
S6：将所述蜂巢状石墨毡放入马弗炉中，升温至600℃，烧结4h得到蜂巢状石墨毡。
实施例10
一种蜂巢状石墨毡制备方法包括以下步骤：
S1：石墨毡浸泡在18.4mol/L浓硫酸中，加热至90℃，维持2h，得到预处理石墨毡；
S2：将聚苯乙烯缓慢加入苯和甲苯的混合溶液中，35℃搅拌7h得到质量浓度为9%的聚苯乙烯溶液；
S3：在96g所述聚苯乙烯溶液中添加2g质量浓度为1%的Te4+离子溶液和2g质量浓度为0.3%的单壁碳纳米管，并以800rpm的搅拌速度搅拌15min分散均匀，得到聚苯乙烯混合溶液；
S4：将所述预处理石墨毡完全浸渍在所述聚苯乙烯混合溶液中30min，得到含有聚苯乙烯石墨毡；
S5：将S4中含有聚苯乙烯石墨毡放置在冷冻干燥机内水平放置冷冻干燥16h，保证真空干燥后孔径方向与纤维方向一致，得到蜂巢状石墨毡半成品；
S6：将所述蜂巢状石墨毡放入马弗炉中，升温至400℃，烧结6h得到蜂巢状石墨毡。
实施例11
一种蜂巢状石墨毡制备方法包括以下步骤：
S1：石墨毡浸泡在6mol/L浓硝酸中，加热至100℃，维持4h，得到预处理石墨毡；
S2：将聚氯乙烯缓慢加入四氢呋喃中，30℃搅拌8h得到质量浓度为12%的聚氯乙烯溶液；
S3：在98g所述聚氯乙烯溶液中添加0.5g质量浓度为2%的Ir3+离子溶液和1.5g质量浓度为2%的碳纳米纤维，并以1000rpm的搅拌速度搅拌20min分散均匀，得到聚氯乙烯混合溶液；
S4：将所述预处理石墨毡完全浸渍在所述聚氯乙烯混合溶液中50min，得到含有聚氯乙烯石墨毡；
S5：将S4中含有聚氯乙烯石墨毡放置在冷冻干燥机内水平放置冷冻干燥20h，保证真空干燥后孔径方向与纤维方向一致，得到蜂巢状石墨毡半成品；
S6：将所述蜂巢状石墨毡放入马弗炉中，升温至800℃，烧结3h得到蜂巢状石墨毡。
实施例12
一种蜂巢状石墨毡制备方法包括以下步骤：
S1：石墨毡放置微波热的环境中升温至400℃，维持12h，使得石墨毡纤维带上-OH官能团，得到预处理石墨毡；
S2：将聚丙烯腈缓慢加入二甲胺基甲酰胺中，25℃搅拌6h得到质量浓度为15%的聚丙烯腈溶液；
S3：在96g所述聚丙烯腈溶液中添加2g质量浓度为4%的In3+离子溶液和2g质量浓度为3%的石墨烯，并以1300rpm的搅拌速度搅拌18min分散均匀，得到聚丙烯腈混合溶液；
S4：将所述预处理石墨毡完全浸渍在所述聚丙烯腈混合溶液中25min，得到含有聚丙烯腈石墨毡；
S5：将S4中含有聚丙烯腈石墨毡放置在冷冻干燥机内水平放置冷冻干燥24h，保证真空干燥后孔径方向与纤维方向一致，得到蜂巢状石墨毡半成品；
S6：将所述蜂巢状石墨毡放入马弗炉中，升温至500℃，烧结5h得到蜂巢状石墨毡。
实施例13
一种蜂巢状石墨毡制备方法包括以下步骤：
S1：石墨毡放置空气热的环境中升温至500℃，维持8h，使得石墨毡纤维带上-OH官能团，得到预处理石墨毡；
S2：将聚二甲基硅氧烷缓慢加入三氯甲烷中，40℃搅拌4h得到质量浓度为20%的聚二甲基硅氧烷溶液；
S3：在97g所述聚二甲基硅氧烷溶液中添加1.5g质量浓度为2%的In3+离子和2%的Ir3+离子的混合溶液以及1.5g质量浓度为4%的多壁碳纳米管，并以300rpm的搅拌速度搅拌16min分散均匀，得到聚二甲基硅氧烷混合溶液；
S4：将所述预处理石墨毡完全浸渍在所述聚二甲基硅氧烷混合溶液中15min，得到含有聚二甲基硅氧烷石墨毡；
S5：将S4中含有聚二甲基硅氧烷石墨毡放置在冷冻干燥机内水平放置冷冻干燥18h，保证真空干燥后孔径方向与纤维方向一致，得到蜂巢状石墨毡半成品；
S6：将所述蜂巢状石墨毡放入马弗炉中，升温至300℃，烧结7h得到蜂巢状石墨毡。
实施例14
一种蜂巢状石墨毡制备方法包括以下步骤：
S1：石墨毡放置空气热的环境中升温至300℃，维持20h，使得石墨毡纤维带上-OH官能团，得到预处理石墨毡；
S2：将聚氟乙烯缓慢加入环己酮中，45℃搅拌5h得到质量浓度为7%的聚氟乙烯溶液；
S3：在96g所述聚氟乙烯溶液中添加2g质量浓度为1%的Ir3+离子溶液和2g质量浓度为5%的多壁碳纳米管，并以1800rpm的搅拌速度搅拌11min分散均匀，得到聚氟乙烯混合溶液；
S4：将所述预处理石墨毡完全浸渍在所述聚氟乙烯混合溶液中35min，得到含有聚氟乙烯石墨毡；
S5：将S4中含有聚氟乙烯石墨毡放置在冷冻干燥机内水平放置冷冻干燥13h，保证真空干燥后孔径方向与纤维方向一致，得到蜂巢状石墨毡半成品；
S6：将所述蜂巢状石墨毡放入马弗炉中，升温至700℃，烧结4h得到蜂巢状石墨毡。
对比例
采用未处理的石墨毡作为对比。
将制作的石墨毡电极组装在电堆上进行测试，在相同测试条件下测试并记录库伦效率、电压效率及能量效率。测试结果表1所示：
表1：采用一体化电机组装电堆的电池性能测试表
Figure 697186DEST_PATH_IMAGE001
由此可见，本发明具有更高的电压效率和能量效率。通过电池效率可以反馈出本发明蜂巢状石墨毡结构可大大提高石墨毡比表面积，改善增强亲水性，增加石墨毡的导电性和增加表面功能团有利于提高钒液流电池的效率。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (5)

1.一种全钒液流电池用石墨毡制备方法，其特征在于，包括以下步骤：
S1：石墨毡高温活化或酸活化得到预处理石墨毡；
S2：将聚合物溶解在溶剂中得到聚合物质量浓度为2-30%的聚合物溶液；所述聚合物为以下任意一种或两种以上的混合物：明胶、壳聚糖、海藻酸钠、纤维素、甲壳素、聚丙烯酸、聚丙烯酰胺；
S3：在所述聚合物溶液中添加质量浓度为1%-5%的金属离子溶液，0.1%-5%的碳纳米材料，并搅拌分散均匀，搅拌的速度为200-2000rpm，时间为5-20min；得到聚合物混合溶液；所述聚合物溶液：金属离子溶液：碳纳米材料的质量比为98：0.5：1.5-96：2：2；所述金属离子溶液为含Mn2+、Au4+、Pd2+、In3+、Pt4+、Te4+或Ir3+离子的任意一种或两种以上的溶液；
S4：将所述预处理石墨毡完全浸渍在所述聚合物混合溶液中，浸渍的时间为10-60min，得到含有聚合物石墨毡；
S5：将S4中含有聚合物石墨毡放置在冷冻干燥机内冷冻干燥，冷冻干燥的时间为4-24h，得到蜂巢状石墨毡半成品；所述含有聚合物的石墨毡在冷冻干燥机中水平放置，保证真空干燥后孔径方向与纤维方向一致；
S6：将所述蜂巢状石墨毡放入马弗炉中进行烧结得到蜂巢状石墨毡，马弗炉中的温度为200-800℃，烧结时间为2-10h。
2.如权利要求1所述的一种全钒液流电池用石墨毡制备方法，其特征在于，所述S1中所述高温活化的方法为：将石墨毡放置在微波热或者空气热的环境中升温至200-600℃，维持4-24h，得到预处理石墨毡；所述S1中所述酸活化的方法为：将石墨毡浸泡在酸性溶液中，加热至60-120℃，维持2-10h，得到预处理石墨毡。
3.如权利要求2所述的一种全钒液流电池用石墨毡制备方法，其特征在于，所述酸性溶液为以下任意一种：6mol/L硝酸、18.4mol/L浓硫酸、12mol/L盐酸或1mol/L草酸。
4.如权利要求1所述的一种全钒液流电池用石墨毡制备方法，其特征在于，所述S2中所述溶剂包括以下任意一种或两种以上的混合物：水、甲醇、乙醇、对二甲苯、苯、甲苯、四氢呋喃、乙酸异戊酯、二甲胺基甲酰胺、三氯甲烷或环己酮。
5.如权利要求1所述的一种全钒液流电池用石墨毡制备方法，其特征在于，所述S3中所述碳纳米材料包括以下任意一种或两种以上的混合物：氧化石墨烯、石墨烯、多壁碳纳米管、单壁碳纳米管或碳纳米纤维。
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