CN1293653C - 全固态锂微电池正极薄膜制备方法 - Google Patents

全固态锂微电池正极薄膜制备方法 Download PDF

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CN1293653C
CN1293653C CNB2005100183573A CN200510018357A CN1293653C CN 1293653 C CN1293653 C CN 1293653C CN B2005100183573 A CNB2005100183573 A CN B2005100183573A CN 200510018357 A CN200510018357 A CN 200510018357A CN 1293653 C CN1293653 C CN 1293653C
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刘韩星
朱先军
甘小燕
胡晨
曹明贺
罗大兵
欧阳世翕
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Wuhan University of Technology WUT
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

本发明公开了一种全固态锂微电池LiNi1-xCoxO2正极薄膜的制备方法，它是以乙酰丙酮锂，乙酰丙酮镍，醋酸钴为原料，按所制备的LiNi1-xCoxO2，0≤x＜1.0中Li、Ni、Co的摩尔比为Li/(Ni+Co)＝1.00～1.05∶1.00准确称量各原料，溶于醋酸和醇类混合溶剂中制成溶胶。采用匀胶的方法，在具有Pt或Au表面的基体上制得凝胶薄膜，经过350～400℃预热分解，再在氧气氛中650～750℃退火，制得LiNi1-xCoxO2正极薄膜。本发明提供的薄膜制备方法，工艺、设备简单，易于制作较大面积的正极薄膜。

Description

全固态锂微电池正极薄膜制备方法
技术领域
本发明公开了一种全固态锂微电池用LiNi1-xCoxO2正极薄膜的制备方法。它属于电化学和电子产品应用技术领域。
背景技术
全固态锂微电池是近几年发展起来的新型微电池，其原因在于随看微电子器件、动态随机储存器、微传感器、微电机械系统、植入体内的医用器件等系统朝着超微型化方向发展，对电源的要求不再以追求功率和电流为主，迫切要求有体积小、重量轻、比容量高的微型电源与之相匹配。全固态薄膜锂微电池具有机械强度高，不含易燃和易挥发成分，不存在漏液等安全问题，而且这类电池具有超长的储存寿命，适合做各类微电子产品的支撑电源。全固态薄膜锂微电池性能受正极薄膜材料性能的影响较大，正极薄膜材料通常为过渡金属氧化物，而获得价廉，高性能的复合氧化物正极材料薄膜是发展全固态薄膜锂微电池的关键。目前，正极材料薄膜的制备方法主要有射频磁控溅射法，脉冲激光沉积法、化学气相沉积(CVD)法等。这些制膜手段中，涉及昂贵的仪器设备，制膜成本高，或者制膜工艺复杂，制得薄膜性能不佳等。
发明内容
本发明的目的在于将LiNi1-xCoxO2材料用于全固态薄膜锂微电池用正极薄膜，并提供一种制备全固态薄膜锂微电池用LiNi1-xCoxO2正极薄膜的方法。该方法避免了目前有关专利文献中正极薄膜制备成本高，工艺复杂，制得薄膜的性能不佳等缺点，使正极薄膜制备工艺大大简化；制备的正极薄膜致密，且具有较好的电化学性能；可制得较大面积的薄膜。
本发明的目的是这样实现的：
本发明的全固态薄膜锂微电池用正极薄膜材料为LiNi1-xCoxO2，x的值为0≤x＜1.0。
所说的全固态薄膜锂微电池用正极薄膜的制备方法：以乙酰丙酮锂，乙酰丙酮镍，醋酸钴为原料，按所制备的LiNi1-xCoxO2，0≤x＜1.0中Li、Ni、Co的摩尔比为Li/(Ni+Co)＝1.00～1.05∶1.00准确称量各原料，溶于醋酸与醇类的摩尔比为1∶1的混合溶剂中制成溶胶；将溶胶涂敷在具有Pt或Au表面的基体上制得凝胶薄膜，所得凝胶薄膜在350～400℃的平板电炉上蒸发溶剂并将Li、Ni和Co的有机盐分解，制成氧化物薄膜。将氧化物薄膜置于高温烧结炉中，在氧气氛下，650～750℃退火10～60min，即得具有α-NaFeO2层状结构的LiNi1-xCoxO2薄膜。根据需要制得薄膜厚度，可将“匀胶→加热→退火”过程重复多次，直到要求的膜厚度为止。
所说的溶胶涂敷采用的方法为匀胶法(spin coating)。。
所说的醇类包括：甲醇、乙醇、丙醇、丁醇、2-甲氧基乙二醇，及所述醇的两种和两种以上的混合醇。
经测试，制得的LiNi1-xCoxO2薄膜致密性好、均匀、且具有较好的电化学性能。相对于锂参比电极的放电电位在4.15～3.50V之间，可用于全固态锂微电池正极薄膜。
与已有技术相比，本发明制备的LiNi1-xCoxO2正极薄膜具有以下几个显著特点：
1  制备的LiNi1-xCoxO2薄膜致密、均匀，具有α-NaFeO2层状结构
2  薄膜的比容量高、循环性能好
3  可制得较厚、较大面积的薄膜
4  工艺、设备简单，易于掌握，成本低
下面结合实例对本发明作进一步说明：
具体实施方式
实施例1：
LiNi0.80Co0.20O2薄膜制备：准确称取Li(CH3COCH2COCH2)0.5817g，Ni(CH3COCH2COCH2)2·4H2O 1.2722g，Co(CH3COO)2·4H2O 0.2705g，溶入10ml叔丁醇和6.1ml醋酸的混合溶剂中，完全溶解后制成溶胶。采用匀胶的方法将所制得的溶胶涂敷在经过打磨、抛光的Pt基体上，制得凝胶薄膜。匀胶转速为3000转/分，匀胶时间为30秒。将所得凝胶薄膜在平板电炉上于400℃温度加热5min，使溶剂蒸发，并将Li、Ni、Co的有机盐分解成氧化物薄膜。将氧化物薄膜置于高温烧结炉中，在氧气氛下，700℃温度退火60分钟，即得具有α-NaFeO2层状结构的LiNi0.80Co0.20O2薄膜。重复“匀胶→加热→退火”过程9次，经测试所得薄膜的厚度为0.5μm。在50μA/cm2电流、3.0～4.2V电压范围内，以浓度为1mol/l LiClO4/EC+DMC(碳酸乙烯酯+碳酸二甲方酯1∶1体积比)为电解液，对电极为锂片，所制得的LiNi0.80Co0.20O2薄膜首次放电容量达58.4μAh/cm2·μm，50次循环之后，放电容量为45.6μAh/cm2·μm，显示其良好的循环性能。
实施例2：
LiNiO2薄膜制备：准确称取Li(CH3COCH2COCH2)0.5817g，Ni(CH3COCH2COCH2)2·4H2O 1.5903g，溶入10ml叔丁醇和6.1ml醋酸的混合溶剂中，完全溶解后制成溶胶。采用匀胶的方法将所制得的溶胶涂敷在经过打磨、抛光的Pt基体上，制得凝胶薄膜。匀胶转速为3000转/分，匀胶时间为30秒。将所得凝胶薄膜在平板电炉上于380℃温度加热5min，使溶剂蒸发，并将Li、Ni、Co的有机盐分解成氧化物薄膜。将氧化物薄膜置于高温烧结炉中，在氧气氛下，750℃温度退火60分钟，即得具有α-NaFeO2层状结构的LiNiO2薄膜。重复“匀胶→加热→退火”过程9次，经测试所得薄膜的厚度为0.5μm。在50μA/cm2电流、3.0～4.2V电压范围内，以1M LiClO4/EC+DMC(1∶1体积比)为电解液，对电极为锂片，所制得的LiNiO2薄膜首次放电容量达49.4μAh/cm2·μm，50次循环之后，放电容量为30.5μAh/cm2·μm。

Claims (3)

1、一种全固态薄膜锂微电池用正极薄膜的制备方法，该薄膜材料为LiNi1-xCoxO2，x的值为0≤x＜1.0，其特征是制备步骤为：
步骤1、以乙酰丙酮锂，乙酰丙酮镍，醋酸钴为原料，按所制备的LiNi1-xCoxO2，0≤x＜1.0中Li、Ni、Co的摩尔比为Li/(Ni+Co)＝1.00～1.05∶1.00准确称量各原料，溶于醋酸与醇类的摩尔比为1∶1的混合溶剂中制成溶胶；
步骤2、将步骤1制成的溶胶涂敷在具有Pt或Au表面的基体上制得凝胶薄膜，经过350～400℃预分解，再在650～750℃温度氧气氛中退火10～60min即得一层LiNi1-xCoxO2薄膜；
步骤3、重复步骤2的匀胶→加热→退火制备过程，直到所需薄膜厚度为止。
2、按权利要求1所说的全固态薄膜锂微电池用正极薄膜的制备方法，其特征是所说的溶胶涂敷采用的方法为匀胶法。
3、按权利要求1所说的全固态薄膜锂微电池用正极薄膜的制备方法，其特征是所说的醇类包括：甲醇、乙醇、丙醇、丁醇、2-甲氧基乙二醇、及所述醇的两种和两种以上的混合醇。
CNB2005100183573A 2005-03-09 2005-03-09 全固态锂微电池正极薄膜制备方法 Expired - Fee Related CN1293653C (zh)

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CN101640265B (zh) * 2009-07-13 2011-09-07 北京安华联合能源科技有限责任公司 一种纳米银颗粒分散LiFePO4薄膜锂离子电池正极制备方法
CN102456926B (zh) * 2010-10-28 2014-10-22 华东师范大学 一种新型三维锂离子电池的构建方法

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CN1567620A (zh) * 2003-06-25 2005-01-19 南都瑞宝能源科技（上海）有限公司 锂离子电池用正极材料镍钴酸锂及其制备方法
CN1571188A (zh) * 2003-07-25 2005-01-26 桂林工学院 掺杂锰酸锂粉体的相转移合成方法

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US5153081A (en) * 1989-07-28 1992-10-06 Csir Lithium manganese oxide compound
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AU2002100000A4 (en) * 2002-01-02 2002-03-07 Dou, Shi Xue Cathode materials for rechargeable lithium batteries and a process for production
CN1567620A (zh) * 2003-06-25 2005-01-19 南都瑞宝能源科技（上海）有限公司 锂离子电池用正极材料镍钴酸锂及其制备方法
CN1571188A (zh) * 2003-07-25 2005-01-26 桂林工学院 掺杂锰酸锂粉体的相转移合成方法

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