CN107828009A - 一种含正极材料的导电树脂的制备方法 - Google Patents

一种含正极材料的导电树脂的制备方法 Download PDF

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CN107828009A
CN107828009A CN201711028778.3A CN201711028778A CN107828009A CN 107828009 A CN107828009 A CN 107828009A CN 201711028778 A CN201711028778 A CN 201711028778A CN 107828009 A CN107828009 A CN 107828009A
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positive electrode
electroconductive resin
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林炳旺
刘学
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Shandong Cisco New Material Co Ltd
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Abstract

本发明公开了一种含正极材料的导电树脂制备方法，具体来说是一种通过三相悬浮聚合方法制备含有锂电池正极材料的高分子树脂制备工艺，该树脂还具有导电的特征。本发明的树脂能够用在锂电池中作为正极材料，也能够用于电渗析装置中作为电极对锂和其它金属元素进行分离。

Description

一种含正极材料的导电树脂的制备方法
技术领域
本发明公开了一种含正极材料的导电树脂制备方法，具体来说是一种通过三相悬浮聚合方法制备含有锂电池正极材料的高分子树脂制备工艺，该树脂还具有导电的特征。
背景技术
离子交换与吸附树脂是一种功能高分子材料，广泛应用在制药、食品、环境、冶金、水处理等行业。阳离子交换树脂是其中的一种，一般在树脂的骨架结构上含有磺酸基和羧基类功能基团。采用阳离子交换树脂对水中的阳离子进行交换，存在交换选择性的问题。通常情况下，在采用阳离子交换树脂对各种金属元素进行分离时，锂离子的选择性交换能力是较差的。
为了改善树脂对锂离子交换的选择性，通常采用功能化的特种树脂，一般有两类物质对锂离子有较好的交换或吸附选择性：一类是含冠醚结构的功能基团，如树脂带有12-冠-4醚结构，利用12-冠-4的空间结构络合锂离子；另一类是树脂中带有金属氧化物结构，利用金属氧化物的晶格对锂离子有较好的空间吸附作用。但这另类产品在工业化过程中均存在问题，冠醚类树脂选择性较好，但冠醚的合成成本较高，导致树脂的成本非常高，间接影响使用；另一类带金属氧化物类的树脂在用酸碱再生或氧化还原再生时，金属氧化物流失严重，导致树脂衰减较快，使用寿命较短。
在此背景下，本发明将正极材料和导电体聚合至树脂结构中，将树脂进行功能化，得到的聚合物树脂材料具有正极材料的特征，从而即可用作锂电池正极材料，也可以用在电渗析中作为电极使用。
发明内容
针对现有树脂材料对锂的吸附选择性差、使用寿命短的、污染严重的问题，本发明提供了一种含正极材料的导电树脂制备新工艺。
为了实现上述目的，本申请采取的技术手段如下：
一种含正极材料的导电树脂制备方法，具体步骤为：
1)在单体和交联剂中，加入引发剂和交联剂，混合均匀；
2)在步骤1)制备的混合物中，加入正极材料粉末和导电体粉末，混合均匀，制成分散相；
3)将步骤2)制备的分散相加入到含有分散剂的水溶液或盐溶液连续相中，搅拌，调整粒度，在50～120℃下，聚合1～20h，进行后处理，即得含正极材料的导电树脂。
所述的引发剂用量为单体和交联剂总重量0.1～5％；致孔剂用量为单体和交联剂总重量10～200％；正极材料粉末为单体和交联剂总重量10～200％；导电体材料粉末为单体和交联剂总重量5～100％；
所述的正极材料选自磷酸铁锂类、锰酸锂、钛酸锂类中的一种或几种组合；所述的磷酸铁锂类指LixFeyMezPO4，钛酸锂类指LixMeyTizO12，Me指金属元素。
优选正极材料粉末的粒径不超过5um、堆积密度不大于2g/cm3。
所述的导电体包括能在电流下传导电子的物质。金属或非金属，固态或液态的导电物质。
优选金属粉末、石墨粉、炭黑粉、半导体粉末；
更优选的是银粉、铜粉、铝粉、铁粉、石墨粉、炭黑粉中的一种或几种组合。
所选的导电体粉末粒径不超过5um、堆积密度不大于2g/cm3。更优选的导电体粒径小于 3um，堆积密度不大于1.5g/cm3。
所述的单体选自苯乙烯、丙烯酸、丙烯酸酯、甲基丙烯酸、甲基丙烯酸酯、丙烯酰胺、二乙烯苯中的一种或几种组合；
所述的交联剂选自二乙烯苯、丁二烯、丙烯酸烯丙酯、二甲基丙烯酸乙二醇酯、衣康酸烯丙酯、N,N,-亚甲基双丙烯酰胺、三聚异氰酸烯丙酯中的一种或几种组合；
所述的致孔剂是各种有机物或无机盐。
所述的引发剂是偶氮类或过氧化物类，如偶氮二异丁腈、过氧化苯甲酰；如果缩聚反应，指酸和碱性物质。
所述的分散剂选自明胶、甲基羟乙基纤维素、聚乙烯醇、羧甲基纤维素；
所述的聚合温度是60～100℃。
所述的聚合时间是3～12h。
所述的球状颗粒粒径范围在50～2000um，优选的是100～800um。
所述的后处理方法蒸馏或者用低沸点溶剂淋洗或者直接用水淋洗。
正极材料和导电体微粒在树脂中均匀分散并相互接触，被树脂的网状结构紧密包裹成具有一定强度、具有微孔结构的材料，正极材料的微观结构不被破坏，其晶胞对锂离子的配位作用仍保持。在外加电路下，锂离子通过树脂的微孔扩散至树脂内部与正极材料接触，而电路中的电子通过导电体进行传递。
本发明制备的含正极材料导电树脂，使用时，在外加电路下，通过脱锂态正极材料导电树脂从含镁锂的卤水中吸附锂后转为嵌锂态，含嵌锂态正极材料导电树脂从不含锂的盐水中脱锂转为脱锂态，不断重复嵌锂和脱锂过程，实现对锂的吸附和脱附循环。
本发明所制备的树脂主要表征：比表面积20～1000m2/g、锂含量≥0.5％、粒径100～800um、导电率≤8×10-6Ω·m。
本发明首次制得了含有正极材料和导电体的高分子树脂，对高分子树脂进行了功能化，并且所制得的高分子材料保留了正极材料和导电体的特征，再将材料特征与锂电池和电渗析结合起来，解决了在电场下对锂较好的选择性嵌锂和脱锂性能。
具体实施方式
本发明通过实施例来阐明本发明，但不以任何形式限制本发明。
实施例一
制备实例：将苯乙烯50kg、含量63％的二乙烯苯80kg、过氧化苯甲酰2kg、聚乙烯醇50kg 混合均匀，再加磷酸铁锂正极材料100kg和石墨粉20公斤制成分散相。将明胶6kg、去离子水500L、氯化钠20kg制成连续相。混合均匀进行悬浮聚合。在80℃下聚合10小时后，过滤，水洗，制得含正极材料的导电树脂，锂含量1.5％，导电率6.8×10-6Ω·m，粒径在300um～600um。
实施例二
制备实例：将丙烯酸甲酯60kg、含量63％的二乙烯苯70kg、过氧化苯甲酰2kg、聚乙二醇30kg混合均匀，再加锰酸锂正极材料60kg和炭黑粉15kg制成分散相。将甲基羟乙基纤维素1kg、去离子水500L制成连续相。混合均匀进行悬浮聚合。在80℃下聚合10小时后，过滤，水洗，制得含正极材料的导电树脂，锂含量0.9％，导电率4.8×10-6Ω·m，粒径在 250um～500um。
实施例三
制备实例：将甲基丙烯酸甲酯50kg、含量63％的二乙烯苯80kg、偶氮二异丁腈2kg、聚乙二醇50kg混合均匀，再加正极材料磷酸锰铁锂90kg和铜粉20kg制成分散相。将明胶6kg、去离子水500L、氯化钠20kg制成连续相。混合均匀进行悬浮聚合。在65℃下聚合10小时后，过滤，水洗，制得含正极材料的导电树脂，锂含量1.35％，导电率4.6×10-6Ω·m。
实施例四
制备实例：将含量63％的二乙烯苯130kg、过氧化苯甲酰2.5kg、甲苯50kg混合均匀，再加钛酸锂70kg和铝粉25kg制成分散相。将明胶6kg、去离子水500L、氯化钠20kg制成连续相。混合均匀进行悬浮聚合。在76℃下聚合10小时后，水洗，蒸出致孔剂，过滤，水洗，制得含正极材料的导电树脂，锂含量1.05％，导电率5.4×10-6Ω·m，粒径在200um～500um。
实施例五：
制备实例：将含量63％的二乙烯苯100kg、丙烯酸甲酯30kg、偶氮二异丁腈2.5kg、甲基叔丁基甲酮80kg混合均匀，再加入磷酸铁锂80kg和铁粉30kg制成分散相。将甲基羟乙基纤维素1kg、去离子水500L制成连续相，混合均匀进行悬浮聚合。在66℃下聚合1h，再升温至85℃聚合10小时，水洗，蒸出致孔剂，过滤，水洗，制得含正极材料的导电树脂，锂含量1.2％，导电率6.1×10-6Ω·m，粒径在200um～400um。
对实施例一～五所得的树脂产品进行应用性能测试
应用实验方法：将约50kg含嵌锂态正极材料导电树脂装至钢树脂柱中，用去离子水冲洗后，用10％的双氧水100L缓慢淋洗，得到含脱锂态正极材料的导电树脂。
在电渗析装置中用阴离子交换膜隔成卤水室和盐水室，卤水室加入含正极材料脱锂态的导电树脂40公斤，盐水室加入含嵌锂态正极材料的导电树脂40公斤。卤水室和盐水室均各自放入导电的金属网，将金属网埋入导电树脂中。分别给金属网接入正负电。
工作时，向卤水室加入3000L卤水，盐水室加入200L质量浓度5％的氯化钠溶液。在1V 电压下，运行3h后，卤水室卤水取样检测镁和锂浓度。
分别放出卤水和盐水后，两室交换进行，原先的盐水室进3000L卤水；原先的卤水室加入200L质量浓度5％的氯化钠溶液。更换外加电流方向。在1V电压下，运行3h，分别对卤水和盐水取样检测镁和锂浓度。
计算树脂对锂的吸附量，比较卤水镁锂比和盐水中镁锂比
锂离子吸附量g/mL 镁/锂(卤水) 镁/锂(盐水)
实施例一 8.6 32/1 0.22/1
实施例二 5.2 34/1 0.22/1
实施例三 7.8 53/1 0.31/1
实施例四 6.0 45/1 0.27/1
实施例五 6.7 24/1 0.16/1
从应用实验来看，本发明的产品对锂有较好的吸附量和选择性。

Claims (10)

1.一种含正极材料的导电树脂制备方法，其特征在于：具体步骤为：
1)在单体和交联剂中，加入引发剂、致孔剂和交联剂，混合均匀；
2)在步骤1)制备的混合物中，加入正极材料粉末和导电体粉末，混合均匀，制成分散相；
3)将步骤2)制备的分散相加入到含有分散剂的水溶液或盐溶液连续相中，搅拌，调整粒径为50～2000um，在50～120℃下，聚合1～20h，进行后处理，即得含正极材料的导电树脂。
2.如权利要求1所述的含正极材料的导电树脂制备方法，其特征在于：所述的引发剂用量为单体和交联剂总重量0.1～5％；致孔剂用量为单体和交联剂总重量10～200％；正极材料粉末为单体和交联剂总重量10～200％；导电体材料粉末为单体和交联剂总重量5～100％。
3.如权利要求1所述的含正极材料的导电树脂制备方法，其特征在于：所述的正极材料选自磷酸铁锂类、锰酸锂、钛酸锂类中的一种或几种组合。
4.如权利要求3所述的含正极材料的导电树脂制备方法，其特征在于：所述的磷酸铁锂类指LixFeyMezPO4，钛酸锂类指LixMeyTizO12，Me指金属元素。
5.如权利要求1所述的含正极材料的导电树脂制备方法，其特征在于：所述的后处理方法蒸馏或者用低沸点溶剂淋洗或者直接用水淋洗。
6.如权利要求1所述的含正极材料的导电树脂制备方法，其特征在于：所述的导电体选自金属粉末、半导体粉末、石墨粉或碳粉中的一种或几种组合。
7.如权利要求6所述的含正极材料的导电树脂制备方法，其特征在于：所述的金属粉选自银粉、铜粉、铝粉中的一种或几种组合。
8.如权利要求1所述的含正极材料的导电树脂制备方法，其特征在于：所述的单体选自苯乙烯、丙烯酸、丙烯酸酯、甲基丙烯酸、甲基丙烯酸酯、丙烯酰胺、二乙烯苯中的一种或几种组合；所述的交联剂选自二乙烯苯、丁二烯、丙烯酸烯丙酯、二甲基丙烯酸乙二醇酯、衣康酸烯丙酯、N,N’-亚甲基双丙烯酰胺、三聚异氰酸烯丙酯一种或几种组合；所述的致孔剂是各种有机物或无机盐；所述的引发剂是偶氮类或过氧化物类；所述的分散剂选自明胶、甲基羟乙基纤维素、聚乙烯醇、羧甲基纤维素。
9.如权利要求8所述的含正极材料的导电树脂制备方法，其特征在于：所述的所述的偶氮类选自偶氮二异丁腈、过氧化物类选自过氧化苯甲酰。
10.如权利要求1所述的含正极材料的导电树脂制备方法，其特征在于：所述的聚合温度是60～100℃；所述的聚合时间是3～12h；所述的粒径为100～800um。
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