CN102354617B - 一种高能镍碳超级电容器正极板浆料 - Google Patents
一种高能镍碳超级电容器正极板浆料 Download PDFInfo
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
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Abstract
本发明涉及一种高能镍碳超级电容器正极板浆料，正极板浆料由正极用粘合剂和主料构成，其中正极用粘合剂为正极粘合剂和主料所形成浆料总重量的20％-35％。本超级电容器是由氢氧化镍为主要活性物质的正极材料制成的正极板，碱金属氢氧化物水性电解液和储氢合金粉与活性碳材料为主要活性物质制成的混合负极板，以及隔膜密封在不锈钢或工程塑料外壳内构成，具有储能密度大、放电功率高等特点；该正极材料所制备的超级电容器工作电压达到1.3V，最大储能密度达到65Wh/kg，可广泛应用于电动公交车的动力电源、车辆低温启动用动力电源、军用装备的动力电源，如航空航天、歼击机、潜艇、舰艇等装备用电容器，也可应用在便携式设备用高容量动力电源，如笔记本电脑、手机、电动工具用电容器等。
Description
技术领域
本发明属于超级电容器领域，尤其是一种高能镍碳超级电容器正极板浆料。
背景技术
随着国家新能源建设的逐步推进，新能源的研究步入一个快速发展的轨道，尤其超级电容器的研究引起各国的重视。通过检索，发现如下有关超级电容器的公开专利文献：
1、一种氢氧化亚镍混和式超级电容器及其制备方法(CN200810111891.2)，该电容器包括圆柱型和方型结构，由氢氧化亚镍阳极，碱金属氢氧化物水性电解液和活性碳纤维阴极密封在不锈钢或工程塑料外壳内构成，具有储能密度大、放电功率高等特点的混和式超级电容器。氢氧化亚镍阳极采用化学反应法和电化学反应方法制备，在其中掺加适量碳纳米管及羰基镍作为添加剂，发泡镍为基体制造出阳极。活性碳阴极采用电镀镍处理过的活性碳纤维作为原材料，采用镍箔作为集流体。所组装电容器工作电压达到1.6V，最大储能密度达到20Wh/kg，峰值放电功率达到8KW/kg。在工业、交通、电子、军事等领域广泛应用。
2、一种车用启动超级电容器(CN03114837.9)，超级电容器芯子由包裹隔膜的烧结式氧化镍正极片，连续化活性碳纤维布负极和集流支撑的薄镍片构成，电容芯子通过制作、焊接电流端子后置于塑料壳体内，注入电解液，封口便得超级电容器成品。该超级电容器具有较高的功率密度和能量密度，且重量轻，成本低，寿命长，适合做各种类型车辆的启动能源，推广应用具有很好价值。
3、一种用于超级电容器的碳基多孔电极薄膜及其制备方法(CN200410009580.7)，薄膜各组分含量为：活性炭含量为72mass％～99mass％，导电碳黑或石墨含量为0.1mass％～20mass％，氧化锆纳米粉体的含量为0.1mass％～5mass％，纳米金属镍粉体含量为0.1mass％～3mass％；空隙率为45％～75％，进一步的优选空隙率为55％～65％。制备本发明薄膜首先将去离子水、有机单体和交联剂混合均匀；然后将分散剂加入溶液搅拌均匀得到预混溶液；再将原料粉体加入，球磨混合，制成浆料；将所得浆料加入除泡剂并进行真空除泡；将引发剂和催化剂加入除泡后的浆料，搅拌均匀后，在流延机上经成型、固化和脱膜后得到生坯，再经弱氧化气氛热处理，得到目标多孔电极薄膜。本发明成型工艺简单、成型时间短、易操作，薄膜厚度可控性好、中孔发达。
4、一种大倍率充放电性能超级电容器的多孔炭电极的制备方法(CN200810053475.1)，该方法包括以下过程，以微孔型沸石分子筛为模板，以气体乙炔、甲烷或乙烯为碳源，在石英管反应器中，利用高周波加热装置进行气相沉积得到富含微孔的多孔炭；多孔炭再经1000-1600℃高温热处理调节表面性质制得大比表面积多孔炭；大比表面积多孔炭与聚四氟乙烯混合分散到乙醇中，并调制为浆状，均匀地涂敷在泡沫镍片上，再经烘干压制制成多孔炭电极。本发明的优点在于：所制得的大比表面积炭具有均一的孔隙结构；多孔炭的表面亲水性低，氧含量低，所制得的多孔炭电极特别适用于大倍率充放电性能的超级电容器。
5、一种氢氧化亚镍混和式超级电容器及其制备方法(CN200810111891.2)，该电容器包括圆柱型和方型结构，由氢氧化亚镍阳极，碱金属氢氧化物水性电解液和活性碳纤维阴极密封在不锈钢或工程塑料外壳内构成具有储能密度大、放电功率高等特点的混和式超级电容器。氢氧化亚镍阳极采用化学反应法和电化学反应方法制备，在其中掺加适量碳纳米管及羰基镍作为添加剂，发泡镍为基体制造出阳极。活性碳阴极采用电镀镍处理过的活性碳纤维作为原材料，采用镍箔作为集流体。所组装电容器工作电压达到1.6V，最大储能密度达到20Wh/kg，峰值放电功率达到8KW/kg。在工业、交通、电子、军事等领域广泛应用。
6、一种混合型超级电容器及其制备方法(CN200910079669.3)，混合型超级电容器的负极活性材料为纳米TiO2或TiO2的同质异像体TiO2-B中的一种或几种，正极活性材料为碳纳米管、碳纳米纤维、石墨、导电炭黑、氢氧化镍、氢氧化锰或氢氧化钼中的一种或几种。混合型超级电容器以正负极活性材料、粘结剂和导电剂为原料制成电极，在手套箱中装配成模拟电池制成超级电容器。本发明提供的制备方法具有可调控，制备流程简单，操作容易，组装的混合超级电容器模型具有比容量高、电位低、性能稳定、可大电流充放电、循环寿命长、成本低廉、机械化大规模生产容易实现等特点。
7、一种超级电容器的制备方法(CN200910063288.6)，它包括如下步骤：1)将泡沫镍基板放入化学气相沉积反应炉中，通入氩气10-60分钟，排尽炉内空气，然后，加热升温至450-750℃，在氩气氛围中以25-40ml/min的流量通入烃类气体，450-750℃下反应30秒至50分钟，反应完成后，得到生长有碳纳米管的泡沫镍；2)除去表面疏松层产物后，直接以生长有碳纳米管的泡沫镍基体直接用作超级电容器电极；3)将步骤2所得的两片厚度、大小相同的电极干燥，用电解液充分浸泡1-36小时，再用同样浸满电解液的隔膜隔开，组装得到超级电容器；所述烃类气体是乙炔、甲烷、乙烯、或丙烯。本发明碳纳米管是直接生长在泡沫镍基板上，无需使用粘合剂；泡沫镍为基板，电极物质体积密度更高，孔分布合理。
经过对比，上述各项专利技术所涉及的正极材料与本专利申请有较大不同。
发明内容
本发明的目的在于克服现有技术的不足之处，提供一种储能密度大、放电功率高的高能镍碳超级电容器的正极板浆料。
为解决上述技术问题，本发明采用下列技术方案：
一种高能镍碳超级电容器正极板浆料，由正极用粘合剂和主料构成，其中正极用粘合剂为正极粘合剂和主料所形成的总重量的20％-35％；其中：
正极用粘合剂的原料构成及其重量配比范围分别为：
羧甲基纤维素钠 2％～4％
去离子水 96％～98％；
主料的原料构成及其重量百分比范围分别为：
而且，所述正极用粘合剂的配制方法为：
(2)按重量配比，分别称好羧甲基纤维素钠及去离子水的重量；
(2)将称好的去离子水加热到80℃，将水倒入配料桶中，慢慢加入羧甲基纤维素钠，边加入边搅拌，搅拌均匀即可，然后放置24小时，至常温。
而且，所述高温添加剂为氧化锆、氧化锌、氧化釔的其中至少一种。
本发明的优点及积极效果是：
1、本超级电容器是由氢氧化镍为主要活性物质的正极材料制成正极板，碱金属氢氧化物水性电解液和储氢合金粉与活性碳材料为主要活性物质组成的混合负极板，以及隔膜密封在不锈钢或工程塑料外壳内构成，具有储能密度大、放电功率高等特点。
2、本发明所发明的正极材料所制备的超级电容器工作电压达到1.3V，最大储能密度达到65Wh/kg。可广泛应用于电动公交车的动力电源、车辆低温启动用动力电源、军用装备的动力电源，如航空航天、歼击机、潜艇、舰艇等装备用电容器，也可应用在便携式设备用高容量动力电源，如笔记本电脑、手机、电动工具用电容器等。应用领域涉及到车辆、交通、工业、航空、军事、消费电子、绿色能源等，具有非常广泛的应用前景。
具体实施方式
下面将结合具体实施方式对本发明进行进一步阐述，但本发明要求保护的范围并不局限于下列实施方式。
本发明所涉及的高能镍碳超级电容器正极板浆料其配制方法分两步，首先是配制正极用粘合剂，需提前一天时间配制，配好正极用粘合剂后再配制与主料混合制备正极材料。
实施例1：
一种高能镍碳超级电容器正极板浆料，制备方法为：
一、配制正极用粘合剂，其原料的重量配比分别为：
羧甲基纤维素钠 2％
去离子水 98％。
配制方法的步骤是：
1、分别称好羧甲基纤维素钠及去离子水的重量；
2、将称好的去离子水加热到80℃左右，将水倒入配料桶中，慢慢加入羧甲基纤维素钠，边加入边搅拌，搅拌3-5分钟后均匀即可，然后放置24小时，至常温，备用。
二、主料的原料构成及重量百分比如下：
本正极板浆料制备方法的具体步骤如下(以100公斤为例)：
1、将已经配好的正极用粘合剂放在搅拌机上搅拌均匀后放入配料桶内，其重量为30公斤。
2、将氧化亚钴5.6公斤、亚氧化钛1.4公斤用去离子水溶解，注意去离子水要多次、少量慢慢加入，边加入边搅拌，以免粉料结块，形成混合浆液。
3、将去离子水与氧化亚钴、亚氧化钛形成的混合浆液加到配料桶里，搅拌均匀。
4、向配料桶中添加高温添加剂氧化锆1.4公斤。
5、然后加入球形氢氧化镍59.5公斤，先少量加入约12公斤，搅拌均匀后继续分4批加入氢氧化镍，放到搅拌机内搅拌。
6、加完后再均匀搅拌半小时。
7、之后加入PTFE(聚四氟乙烯)乳液2.1公斤，所加入的PTFE乳液为常用的浓度，浓度为60％，将溶液搅拌均匀，即可形成正极浆料。
实施例2：
一种高能镍碳超级电容器正极板浆料，制备方法为：
一、配制正极用粘合剂，其原料的重量配比分别为：
羧甲基纤维素钠 4％
去离子水 96％。
配制方法的步骤是：
1、分别称好羧甲基纤维素钠及去离子水的重量；
2、将称好的去离子水加热到80℃左右，将水倒入配料桶中，慢慢加入羧甲基纤维素钠，边加入边搅拌，搅拌几分钟后均匀即可，然后放置24小时，至常温，备用。
二、主料的原料构成及重量百分比如下：
本正极板浆料制备方法的具体步骤如下(以100公斤为例)：
1、准备好已经配好的正极用粘合剂，放在搅拌机上搅拌均匀后放入配料桶内，其重量为25公斤。
2、将氧化亚钴3公斤、亚氧化钛2.25公斤用去离子水溶解，注意去离子水要多次、少量慢慢加入，边加入边搅拌，以免粉料结块，形成混合溶液。
3、将去离子水与氧化亚钴、亚氧化钛形成的混合溶液加到配料桶里，搅拌均匀。
4、向配料桶中添加氧化锌0.75公斤。
5、然后加入球形氢氧化镍67.5公斤，先少量加入13.5公斤，搅拌均匀后继续分5批加入氢氧化镍，放到搅拌机内搅拌。
6、加完后再均匀搅拌半小时。
7、之后加入PTFE(聚四氟乙烯)乳液1.5公斤，所加入的PTFE乳液为常用的浓度，浓度为60％，将溶液搅拌均匀，即可形成正极浆料。
采用上述正极板浆料所制成的超级电容器的高温、低温特性检测结果见下表：
检测单位：信息产业部化学物理电源产品质量监督检验中心
Claims (2)
1.一种高能镍碳超级电容器正极板浆料，其特征在于：由正极用粘合剂和主料构成，其中正极用粘合剂为正极粘合剂和主料所形成的总重量的20%-35%；其中：
正极用粘合剂的原料构成及其重量配比范围分别为：
羧甲基纤维素钠 2%～4%
去离子水 96%～98%；
主料的原料构成及其重量百分比范围分别为：
所述高温添加剂为氧化锆、氧化锌、氧化钇的其中至少一种。
2.根据权利要求1所述的高能镍碳超级电容器正极板浆料，其特征在于：所述正极用粘合剂的配制方法为：
⑴按重量配比，分别称好羧甲基纤维素钠及去离子水的重量；
⑵将称好的去离子水加热到80℃，将水倒入配料桶中，慢慢加入羧甲基纤维素钠，边加入边搅拌，搅拌均匀即可，然后放置24小时，至常温。
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