CN112927952A - 一种锂离子混合电容器柔性钛酸锂负极及其制备方法 - Google Patents
一种锂离子混合电容器柔性钛酸锂负极及其制备方法 Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 28
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003990 capacitor Substances 0.000 title claims abstract description 12
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 42
- 239000010935 stainless steel Substances 0.000 claims abstract description 42
- 239000002243 precursor Substances 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000000151 deposition Methods 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 14
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 13
- 230000008021 deposition Effects 0.000 claims description 12
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229960004063 propylene glycol Drugs 0.000 claims description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 4
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- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims 1
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- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明提供一种锂离子混合电容器柔性钛酸锂负极及其制备方法,利用静电喷雾沉积法将钛酸锂沉积在不锈钢网上,并且引入十六烷基三甲基溴化铵(CTAB)对钛酸锂进行碳包覆改性。与传统电极制备方式不同,本次电极制备无需使用粘结剂等添加剂,同时利用不锈钢网的柔韧性配合薄活性物质层,最终获得了高倍率性能的柔性钛酸锂。
Description
技术领域
本发明属于锂离子电容器或锂离子电池中柔性电极技术领域,具体涉及一种锂离子混合电容器柔性钛酸锂负极及其制备方法。
背景技术
近年来,随着便携式设备和可穿戴电子产品的日益普及,柔性储能设备越来越受到人们的青睐。在当前储能设备中,锂离子电容器因其兼具锂电和超电的特性,成为下一代具有高能量和功率密度储能装置首选。然而,由于电化学滞后现象,负极成为限制锂离子电容器功率输出的主要原因,与多孔电极的表面控制电荷存储相比,负极常受限于块状电极的固有半无限扩散过程。尖晶石结构钛酸锂具有可忽略的体积膨胀、高的脱嵌锂平台电位和优良的循环稳定性引起广泛关注,然而其自身导电性较差,往往需要进行纳米结构设计或表面包覆等方式提升倍率性能。此外,在传统电极制备中需在浆料中添加导电剂、粘结剂等,不仅降低了电极电导率和器件整体的能量密度,还提高了制备成本。同时,传统电极上的活性物质层过厚,在电极弯折时易出现脱落失效的情况,很难满足柔性电极的需求。基于以上问题,用一种简易方法制备出具有优异电化学性能和机械性能的电极仍然是广大科研人员所追求的目标。
发明内容
为解决上述技术问题,本发明的目的是提供一种用于锂离子电容器的柔性电极。利用静电喷雾沉积法将钛酸锂沉积在不锈钢网上,并且引入十六烷基三甲基溴化铵(CTAB)对钛酸锂进行碳包覆改性。与传统电极制备方式不同,本次电极制备无需使用粘结剂等添加剂,同时利用不锈钢网的柔韧性配合薄活性物质层,最终获得了高倍率性能的柔性钛酸锂。
本发明提供一种上述柔性电极的制备方法,具体包括以下步骤:
(1)将十六烷基三甲基溴化铵溶解在有机溶剂中搅拌成均匀溶液,向均匀溶液中加入乙酸锂与钛酸四丁酯,再次搅拌后配制成前驱体溶液;
(2)利用静电喷雾沉积法将前驱体喷涂沉积于不锈钢网上,得到的样品经煅烧后可制备成所述柔性电极。
基于以上技术方案,优选的,所述步骤(1)中,十六烷基三甲基溴化铵用量为6-10mg/ml;
基于以上技术方案,优选的,所述步骤(1)中,乙酸锂与钛酸四丁酯的摩尔比为(4-4.5):5,所述前驱体溶液中,钛酸四丁酯的浓度为0.1mmol/ml。
基于以上技术方案,优选的,所述步骤(1)中,溶剂为乙醇、1,2-丙二醇、乙二醇、异丙醇中任一种或多种。
基于以上技术方案,优选的,所述步骤(2)中,静电喷雾沉积的条件为基底温度150-300℃,沉积速度1-5ml/h,沉积时间为1-5h,施加静电电压为5-10kV。
基于以上技术方案,优选的,所使用的不锈钢网为316L不锈钢。
基于以上技术方案,优选的,所述不锈钢网为400-700目,孔径26μm。
基于以上技术方案,优选的,煅烧条件为600-800℃下6h。
有益效果
(1)相比于传统物理喷雾方法,静电喷雾沉积法效率更高,且沉积产物形貌更加均匀,这种结构增加了材料的比表面积,有利于与电解液接触,提高了锂离子在材料晶格中的可逆嵌入或脱出,因此具有良好的电化学性能。同时,在整个制备过程中不需要使用到粘结剂等,更加经济。
(2)十六烷基三甲基溴化铵经高温煅烧后在钛酸锂颗粒外形成了氮掺杂的碳层,均匀包裹在钛酸锂颗粒外层,降低了钛酸锂电极的内阻,大大提升了电极的倍率性能。作为一种表面活性剂,十六烷基三甲基溴化铵在产物生成过程中也有效抑制了钛酸锂颗粒团聚现象。
(3)与传统铝箔、铜箔等相比,本发明使用到的不锈钢网基底具有三维立体结构,此种结构进一步提升了活性物质与电解液接触面积,提高了离子传导效率。同时依靠不锈钢网的柔韧性,将活性物质喷涂沉积于不锈钢网后使得电极整体具有良好的机械性能。
附图说明
图1为实施例1制备的复合电极实物图。
图2为实施例1制备的复合电极SEM图。
图3为实施例1制备的复合电极倍率性能图。
图4为对比例1制备的纯钛酸锂电极倍率性能图。
图5为对比例8中使用传统物理喷雾法制备的复合电极SEM图。
具体实施方式
实施例1
1、按如下步骤制备柔性氮掺杂碳包覆钛酸锂电极:
(1)将500mg十六烷基三甲基溴化铵溶解在50ml乙醇中配置成均匀溶液;
(2)向均匀溶液中加入4mmol乙酸锂与5mmol钛酸四丁酯,搅拌后配制成前驱体溶液;
(3)将15cm×10cm的不锈钢网(600目)用盐酸、丙酮、去离子水分别超声清洗3次进行预处理,然后置于仪器加热台并设置温度为300℃,将步骤(2)配制的前驱体溶液装入注射器中,设置液体流速为5ml/h,喷嘴与不锈钢网基底的距离为5cm,静电电压为7kV,喷涂沉积1小时;
(4)将步骤(3)得到的样品在转移至管式炉中,在氩气氛围下马弗炉升温速率为每分钟5℃,700℃下烧结6小时,自然冷却至室温后得到柔性氮掺杂碳包覆钛酸锂复合电极,并且将电极作为锂离子电容器负极使用。
2、按如下步骤装锂离子电池并测试:
将上述步骤所制备的电极裁成直径为14mm的圆片作为工作电极,金属锂片作为对电极组成2016型扣式电池。其中工作电极的活性物质质量为1.0mg,Celgard2325多孔膜为隔膜,1mol L-1的LiPF6+EC(碳酸乙烯酯)+DEC(碳酸二乙酯)为电解液,在充满氩气的手套箱内组装电池(Ar>99.99%,H2O<1ppm,O2<1ppm)。将组装好的电池静置10h后进行性能测试,其测试条件为:分别在0.5C/1C/3C/5C/10C/20C/30C/50C不同倍率下充放电测试5圈,测试电压区间为1-3V。
图1为柔性氮掺杂碳包覆钛酸锂复合电极的实物图,电极具有良好的柔韧性,在弯折30次后未发生活性物质脱落现象,从扫描电镜图(图2)看出沉积层形貌较为粗糙,该结构能增加活性物质与电解液的接触面积。扣式电池倍率性能测试结果于图3,在50C时仍然有约94mA h g-1的比容量,在3C倍率下循环1000后容量保持在84%,表明电极具有较好的结构稳定性和良好的倍率性能。
实施例2
1、按如下步骤制备柔性氮掺杂碳包覆钛酸锂电极:
(1)将500mg十六烷基三甲基溴化铵溶解在50ml乙醇中配置成均匀溶液;
(2)向均匀溶液中加入4.5mmol乙酸锂与5mmol钛酸四丁酯,搅拌后配制成前驱体溶液;
(3)将15cm×10cm的不锈钢网(600目)用盐酸、丙酮、去离子水分别超声清洗3次进行预处理,然后置于仪器加热台并设置温度为300℃,将步骤(2)配制的前驱体溶液装入注射器中,设置液体流速为5ml/h,喷嘴与不锈钢网基底的距离为5cm,静电电压为7kV,喷涂沉积1小时;
(4)将步骤(3)得到的样品在转移至管式炉中,在氩气氛围下马弗炉升温速率为每分钟5℃,700℃下烧结6小时,自然冷却至室温后得到复合电极,并且将电极作为锂离子电容器负极使用。
按实施例1中扣式电池组装方式及测试条件进行性能测试,在50C时比容量约91mAh g-1,电池在3C倍率循环1000圈后,容量保持在初始值的89%。
实施例3
(1)将500mg十六烷基三甲基溴化铵溶解在50ml乙醇中配置成均匀溶液;
(2)向均匀溶液中加入4mmol乙酸锂与5mmol钛酸四丁酯,搅拌后配制成前驱体溶液;
(3)将15cm×10cm的不锈钢网(600目)用盐酸、丙酮、去离子水分别超声清洗3次进行预处理,然后置于仪器加热台并设置温度为150℃,将步骤(2)配制的前驱体溶液装入注射器中,设置液体流速为5ml/h,喷嘴与不锈钢网基底的距离为5cm,静电电压为7kV,喷涂沉积1小时;
(4)将步骤(3)得到的样品在转移至管式炉中,在氩气氛围下马弗炉升温速率为每分钟5℃,700℃下烧结6小时。
按实施例1中扣式电池组装方式及测试条件进行性能测试,在50C时比容量约82mAh g-1,电池在3C倍率循环1000圈后,容量保持在初始值的86%。
实施例4
(1)将500mg十六烷基三甲基溴化铵溶解在50ml乙二醇中配置成均匀溶液;
(2)向均匀溶液中加入4mmol乙酸锂与5mmol钛酸四丁酯,搅拌后配制成前驱体溶液;
(3)将15cm×10cm的不锈钢网(600目)用盐酸、丙酮、去离子水分别超声清洗3次进行预处理,然后置于仪器加热台并设置温度为300℃,将步骤(2)配制的前驱体溶液装入注射器中,设置液体流速为1ml/h,喷嘴与不锈钢网基底的距离为5cm,静电电压为7kV,喷涂沉积5小时;
(4)将步骤(3)得到的样品在转移至管式炉中,在氩气氛围下马弗炉升温速率为每分钟5℃,700℃下烧结6小时。
按实施例1中扣式电池组装方式及测试条件进行性能测试,在50C时比容量约87mAh g-1,电池在3C倍率循环1000圈后,容量保持在初始值的86%。
实施例5
(1)将500mg十六烷基三甲基溴化铵溶解在50ml乙二醇中配置成均匀溶液;
(2)向均匀溶液中加入4mmol乙酸锂与5mmol钛酸四丁酯,搅拌后配制成前驱体溶液;
(3)将15cm×10cm的不锈钢网(600目)用盐酸、丙酮、去离子水分别超声清洗3次进行预处理,然后置于仪器加热台并设置温度为300℃,将步骤(2)配制的前驱体溶液装入注射器中,设置液体流速为5ml/h,喷嘴与不锈钢网基底的距离为5cm,静电电压为7kV,喷涂沉积1小时;
(4)将步骤(3)得到的样品在转移至管式炉中,在氩气氛围下马弗炉升温速率为每分钟5℃,700℃下烧结6小时。
按实施例1中扣式电池组装方式及测试条件进行性能测试,在50C时比容量约80mAh g-1,电池在3C倍率循环1000圈后,容量保持在初始值的89%。
实施例6
(1)将500mg十六烷基三甲基溴化铵溶解在50ml乙醇中配置成均匀溶液;
(2)向均匀溶液中加入4mmol乙酸锂与5mmol钛酸四丁酯,搅拌后配制成前驱体溶液;
(3)将15cm×10cm的不锈钢网(400目)用盐酸、丙酮、去离子水分别超声清洗3次进行预处理,然后置于仪器加热台并设置温度为300℃,将步骤(2)配制的前驱体溶液装入注射器中,设置液体流速为5ml/h,喷嘴与不锈钢网基底的距离为5cm,静电电压为7kV,喷涂沉积1小时;
(4)将步骤(3)得到的样品在转移至管式炉中,在氩气氛围下马弗炉升温速率为每分钟5℃,700℃下烧结6小时。
按实施例1中扣式电池组装方式及测试条件进行性能测试,在50C时比容量约83mAh g-1,电池在3C倍率循环1000圈后,容量保持在初始值的88%。
对比例1
1、按如下步骤制备纯钛酸锂电极:
(1)将4mmol乙酸锂与5mmol钛酸四丁酯加到50ml乙醇,搅拌后配制成前驱体溶液;
(2)将15cm×10cm的不锈钢网(600目)用盐酸、丙酮、去离子水分别超声清洗3次进行预处理,然后置于仪器加热台并设置温度为300℃,将步骤(2)配制的前驱体溶液装入注射器中,设置液体流速为5ml/h,喷嘴与不锈钢网基底的距离为5cm,静电电压为7kV,喷涂沉积1小时;
(3)将步骤(2)得到的样品在转移至管式炉中,在氩气氛围下马弗炉升温速率为每分钟5℃,700℃下烧结6小时,自然冷却至室温后得到复合电极,并且将电极作为锂离子电容器负极使用。
按实施例1中扣式电池组装方式及测试条件进行性能测试,测试结果见图4。
对比例2
按实施例1中条件,将不锈钢网600目更换成200目,进行对比实验。
对比例3
按实施例1中条件,将不锈钢网基底更换成泡沫镍基底制备电极,进行对比实验。
对比例4
按实施例1中条件,将基底温度由300℃改为100℃,进行对比实验。
对比例5
按实施例1中条件,将静电电压由7kV改为3kV,进行对比实验。
对比例6
按实施例1中条件,将煅烧温度由700℃改为300℃,进行对比实验。
表1是实施例1与对比例2-6的性能对比,比较不同制备条件的性能差异。
表1
注明:在对比例3中,与不锈钢网基底相比,泡沫镍基底的样品明显不具备柔性,在弯折5次后断裂。以对比例6中煅烧温度合成钛酸锂样品中有二氧化钛杂相,物相不纯。
对比例7
在150-250℃温度下,水热反应合成钛酸锂,配制浆料涂覆于不锈钢网上进行对比实验。实验结果涂覆层很难控制厚度,并且在弯折时出现活性物质脱落的现象,性能急剧下降。另外水热过程繁琐复杂、时间长,不符合高效率制备柔性电极这一目标。
对比例8
按实施例1中条件,采用传统物理喷雾的方式,使用气喷枪将前驱体溶液喷涂于不锈钢网基底,煅烧后制备复合电极。实验结果活性物质脱落严重,扫描电镜图片(图5)观察到钛酸锂颗粒较大,不利于提升材料倍率性能。经测试50C时比容量仅为47mAh/g。
Claims (9)
1.一种柔性电极的制备方法,其特征在于,包括以下步骤:
(1)将十六烷基三甲基溴化铵溶解在有机溶剂中,搅拌得到溶液A,向溶液A中加入乙酸锂与钛酸四丁酯,搅拌后,得到前驱体溶液;
(2)利用静电喷雾沉积法将所述前驱体溶液喷涂沉积于不锈钢网上,煅烧,得到所述柔性电极。
2.根据权利要求1所述的制备方法,其特征在在于,所述溶液A中,十六烷基三甲基溴化铵的浓度为6-10mg/ml。
3.根据权利要去1所述的制备方法,其特征在于,乙酸锂与钛酸四丁酯的摩尔比为4-4.5:5;所述前驱体溶液中,钛酸四丁酯的浓度为0.1mmol/ml。
4.根据权利要求1所述的制备方法,其特征在于,所述溶剂为乙醇、1,2-丙二醇、乙二醇、异丙醇中的至少一种。
5.根据权利要求1所述的制备方法,其特征在于,所述静电喷雾沉积法的条件为:不锈钢网温度150-300℃,沉积速度1-5ml/h,沉积时间为1-5h,施加静电电压为5-10kV。
6.根据权利要求1所述的制备方法,其特征在于,所述不锈钢网的材质为316L不锈钢;所述不锈钢网为400-700目,孔径20-50μm。
7.根据权利要求1所述的制备方法,其特征在于,所述煅烧条件为600-800℃下6-8h。
8.一种权利要求1-7任意一项所述制备方法制备的柔性电极,其特征在于,所述的柔性电极包括不锈钢网和沉积层;所述沉积层为碳包覆层包覆的钛酸锂,所述沉积层厚度为1-2.5μm;钛酸锂粒径大为50-90nm;碳包覆层的厚度为2-5nm,所述碳包覆层为氮掺杂的碳包覆层;氮以吡啶氮、石墨氮、吡咯氮三种形式掺杂于碳中,所述氮掺杂的碳包覆层中,掺杂量占碳含量的1-6wt%。
9.一种权利要求8所述的柔性电极的应用,其特征在于,所述柔性电极在锂离子电容器或锂离子电池中作为负极。
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