CN103746096A - 一种碳硫复合正极材料及其制备方法 - Google Patents

一种碳硫复合正极材料及其制备方法 Download PDF

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CN103746096A
CN103746096A CN201310696654.8A CN201310696654A CN103746096A CN 103746096 A CN103746096 A CN 103746096A CN 201310696654 A CN201310696654 A CN 201310696654A CN 103746096 A CN103746096 A CN 103746096A
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positive pole
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sulphur
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梁兴华
曾帅波
刘于斯
史琳
叶超超
刘天骄
华晓鸣
宋清清
刘浩
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Guangxi University of Science and Technology
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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
    • H01M4/362—Composites
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
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    • 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
    • H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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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
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Abstract

本发明公开一种碳硫复合正极材料，包括活性炭和硫，其特点在于，所述硫填充在所述活性炭的孔道中，述碳硫复合正极材料还掺有氧化镍。该复合正极材料可用于锂硫电池的正极，可以改善锂硫电池的循环充放电性能，减少了锂硫聚合物的产生，避免锂硫不可逆的反应。

Description

一种碳硫复合正极材料及其制备方法
技术领域
本发明属于锂硫电池领域，涉及一种用于锂硫电池的碳硫复合正极材料及其制备方法。
背景技术
便携式电子通信设备的发展对其所用的化学电源性能提出了更高的要求，尤其对电池的比能要求越来越高。作为锂离子电池的一种，锂/硫电池的理论比容量为1675 mAh/g，并且作为正极材料的单质硫具有来源丰富、价格便宜、对环境友好、电池安全性好等优点，因此锂硫电池被认为是下一代能提供高比能的最具潜力的电池体系。但是由于单质硫是典型的电子和离子绝缘体，还原过程产生的中间体多聚硫化物易溶于有机液态电解液，部分溶解的多聚硫化物扩散到达金属锂阳极表面与其发生自放电反应，加速锂的腐蚀，生成无序的Li2S2和Li2S为部分不可逆反应，这一系列的问题都导致电极活性物质利用率低和电池循环性能差。现有技术中已有采用有机硫化物或硫复合物PDDTB, PDTDA, PABTH, FeS2和CuS代替单质硫来解决上述问题，但是这类化合物的理论比容量低于单质硫的30%，因而限制了这类材料的应用。
发明内容
本发明的目的是解决现有单质硫作为正极材料时电池循环性能差的问题，提供一种碳硫复合正极材料及其制备方法。
本发明实现上述目的所采用的技术方案如下：
一种碳硫复合正极材料，包括活性炭和硫，其特点在于，所述硫填充在所述活性炭的孔道中，述碳硫复合正极材料还掺有氧化镍。
进一步，包括将活性炭与硫混合，在惰性气氛下，于120～300℃保温3～20小时后，再加入氧化镍混合研磨，得到所述碳硫复合正极材料。
进一步，所述活性炭与硫的质量比为1：（0.5～2）。
进一步，所述氧化镍与活性炭的质量比为1：1。
进一步，所述氧化镍优选为纳米氧化镍。
附图说明
图1为本发明所述C/S复合材料的充放电循环图。
图2为本发明所述C/S复合材料的电镜图。
具体实施方式
以下结合附图对本发明的优选实施例做进一步详细说明。
实施例1
将活性炭（分析纯）和单质硫（分析纯）按1:1的质量比在球磨机中研磨均匀后，放入真空干燥箱中，冲入氩气约20min，以排除里面的空气，避免高温下硫被氧化。然后在流动的氮气气氛下，把活性炭与单质硫混合物加热到155℃左右，在此温度下保持10小时，然后再将温度升高到250度左右，在此温度下保持3h，产物再用球磨机球磨10h，得到的黑色产物再与纳米氧化镍（按活性炭：氧化镍质量比为1：1）混合用球磨机球磨10h，超声振动，分散均匀，得到C/S复合材料。
电池性能的表征：将所得的复合材料与聚偏二氟乙烯（PVDF）按照质量比80: 10称量，以N-甲基吡咯烷酮为溶剂调制成均匀浆状，涂布后进行烘干压片，裁片制成正极片，锂片作为负极片，1mol/L的LiPF6的EC/DNC（碳酸乙烯酯/碳酸丁烯酯，体积1:1）做为电解液，隔膜Celgard2300，组装成扣式电池。
图1为复合材料的充放电循环图，由图可以看出，所得C/S复合材料（A）在第20次循环时，容量保持率仍有93.04%，而单质硫（B）在第20次循环时，容量保持率只有43%。可见本发明可明显改善锂硫电池的循环性能，且衰减幅度更小。
图2为所述C/S复合材料的电镜图。从图中可清晰的看见纳米氧化镍已经附着在单质硫的周围，平且通过碳的搭桥，进入之间的间隙。

Claims (5)

1.一种碳硫复合正极材料，包括活性炭和硫，其特征在于，所述硫填充在所述活性炭的孔道中，述碳硫复合正极材料还掺有氧化镍。
2.权利要求1所述碳硫复合正极材料的制备方法，其特征在于，包括将活性炭与硫混合，在惰性气氛下，于120～300℃保温3～20小时后，再加入氧化镍混合研磨，得到所述碳硫复合正极材料。
3.根据权利要求2所述碳硫复合正极材料的制备方法，其特征在于，所述活性炭与硫的质量比为1：（0.5～2）。
4.根据权利要求2所述碳硫复合正极材料的制备方法，其特征在于，所述氧化镍与活性炭的质量比为1：1。
5.根据权利要求2所述碳硫复合正极材料的制备方法，其特征在于，所述氧化镍为纳米氧化镍。
CN201310696654.8A 2013-12-18 2013-12-18 一种碳硫复合正极材料及其制备方法 Pending CN103746096A (zh)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105006553A (zh) * 2015-07-11 2015-10-28 中国计量学院 一种硫/碳/氧化物复合电极材料的制备方法
CN108063224A (zh) * 2017-11-20 2018-05-22 南开大学 硫/金属氧化物复合的锂硫电池的正极材料及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1384556A (zh) * 2002-04-17 2002-12-11 中国科学院上海微系统与信息技术研究所 二次电化学电源正极用纳米单质硫复合材料及其制备方法
KR20040011629A (ko) * 2002-07-27 2004-02-11 한국과학기술원 마그네슘-니켈 산화물이 포함된 리튬유황이차전지용 양극및 이를 포함하는 리튬유황이차전지
CN103000934A (zh) * 2011-09-16 2013-03-27 苏州宝时得电动工具有限公司 锂硫电池

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1384556A (zh) * 2002-04-17 2002-12-11 中国科学院上海微系统与信息技术研究所 二次电化学电源正极用纳米单质硫复合材料及其制备方法
KR20040011629A (ko) * 2002-07-27 2004-02-11 한국과학기술원 마그네슘-니켈 산화물이 포함된 리튬유황이차전지용 양극및 이를 포함하는 리튬유황이차전지
CN103000934A (zh) * 2011-09-16 2013-03-27 苏州宝时得电动工具有限公司 锂硫电池

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105006553A (zh) * 2015-07-11 2015-10-28 中国计量学院 一种硫/碳/氧化物复合电极材料的制备方法
CN105006553B (zh) * 2015-07-11 2017-06-23 中国计量学院 一种硫/碳/氧化物复合电极材料的制备方法
CN108063224A (zh) * 2017-11-20 2018-05-22 南开大学 硫/金属氧化物复合的锂硫电池的正极材料及其制备方法

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Application publication date: 20140423