CN112234190B - 一种铅基负极材料 - Google Patents

一种铅基负极材料 Download PDF

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CN112234190B
CN112234190B CN202011095974.4A CN202011095974A CN112234190B CN 112234190 B CN112234190 B CN 112234190B CN 202011095974 A CN202011095974 A CN 202011095974A CN 112234190 B CN112234190 B CN 112234190B
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compound
lead
electrode material
negative electrode
ionic compound
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CN112234190A (zh
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谢文青
曹江行
张军杰
梁攀飞
刘凯元
马廷丽
范美强
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China Jiliang University
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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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/582—Halogenides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G21/00—Compounds of lead
    • C01G21/006—Compounds containing, besides lead, two or more other elements, with the exception of oxygen or hydrogen
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
    • 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
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
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Abstract

本发明公开了一种铅基负极材料，为CsPbxM1‑xBry‑zNz；其中：M为锡、锗、锑、铜、铝、镁的一种或两种，x的摩尔数为0.001‑0.3；y的摩尔数为1‑6；N为氧、氟、氯、碘的一种或两种，z的摩尔数为0.001‑1；M和N以离子形式存在CsPbxM1‑ xBry‑zNz中；M和N来自一种化合物、两种化合物或多种化合物。该铅基负极材料具有很好的电化学性能，在电池领域具有很好的应用前景。

Description

一种铅基负极材料
技术领域
本发明专利涉及一种电极材料，具体涉及一种铅基负极材料。
背景技术
锂离子电池是目前发展迅猛的储能器件，已广泛用于手机、笔记本电脑、电动汽车等便携式电源。锂离子电池性能主要取决于嵌脱锂电极材料的性能。目前，商业化的锂离子电池负极材料石墨存在理论储锂容量低，易发生有机溶剂共嵌等问题，严重制约了锂离子电池的实际应用。寻找高比容量、高循环性能的负极材料是科研人员和企业极力解决的关键问题。
锂合金具有比容量高，导电性好等优点，是非常好的负极材料。大量文献报道了锡，硅，镍，铅等负极材料的研究进展。但从反应机理来看，锂合金脱嵌锂存在巨大的体积变化，导致电极材料脱落，影响负极材料的电化学性能。通过惰性金属与锡、硅等形成合金，利用惰性金属充当体积变化缓冲框架，可提高硅、锡等金属负极的电化学性能，比如SONY公司的NexelionTMSn-Co-C合金负极材料和美国3M的Si-Fe-M合金。但这两种合金组分的纳米性成本很高，限制了其产业应用。如何解决锂合金在脱嵌过程中的体积变化问题及成本问题，是实现其产业应用的关键。
发明内容
针对现有技术方案的缺陷，本发明的目的是提供一种铅基负极材料的设计。
本发明涉及一种铅基负极材料，为CsPbxM1-xBry-zNz；其中：M为锡、锗、锑、铜、铝、镁的一种或两种，x的摩尔数为0.001-0.3；y的摩尔数为1-6；N为氧、氟、氯、碘的一种或两种，z的摩尔数为0.001-1；
所述的M以离子形式存在CsPbxM1-xBry-zNz中；
所述的N以离子形式存在CsPbxM1-xBry-zNz中；
所述的M离子可以存在不同化合价；
所述的M和N来自一种化合物、两种化合物或多种化合物。
本专利设计的铅基负极材料CsPbxM1-xBry-zNz，主要是部分替代铅阳离子和溴阴离子；M可以是与锂形成合金，具备储锂功能的金属；也可以是单纯掺杂铅，改善铅储锂性能的金属；N的作用主要是与锂形成化合物，在铅基材料表面形成SEI膜，即保证了CsPbxM1-xBry- zNz在充放电过程中结构的稳定性；也提高了CsPbxM1-xBry-zNz的导电性能。N的范围并不局限于了氧离子、氟离子、氯离子和碘离子的一种或两种；也可扩大到硝酸根离子、硫酸根离子、硫离子的一种。
与现有技术相比，本发明专利提供的铅基负极材料CsPbxM1-xBry-zNz，具有以下优势：
1)制备工艺简单，采用钙钛矿制备工艺，可产业化生产；
2)铅基负极材料CsPbxM1-xBry-zNz在充放电过程中结构稳定，具有很好的循环性能；M和N的协同作用，极大地改善了CsPbxM1-xBry-zNz的导电率；
3)M和N的协同作用，有利于锂离子在CsPbxM1-xBry-zNz中的嵌入/脱出。极大提高了电极材料的比容量和倍率性能；该材料在锂离子电池领域具有很好的应用前景。
具体实施方式
为能进一步了解本发明的发明内容、特点及功效，兹举以下实施例详细说明如下：
实例1
一种铅基负极材料的成分设计，包括：
1)0.06mol CsCO3,0.06mol PbBr2,0.01mol SnF2；
2)0.06mol CsCO3,0.06mol PbBr2,0.01mol SnO；
3)0.06mol CsCO3,0.06mol PbBr2,0.005mol SnF2,0.005mol SnO；
上述材料加入其它常规盐类和试剂，加热制备铅基负极材料；该铅基材料具有很好的电化学性能，5Ag-1电流密度下，300次充放电循环，电化学容量大于200mAh/g。
实例2
一种铅基负极材料的成分设计，包括：
4)0.06mol CsCO3,0.06mol PbBr2,0.01mol MgF2；
5)0.06mol CsCO3,0.06mol PbBr2,0.01mol SnO2；
6)0.06mol CsCO3,0.06mol PbBr2,0.005mol AlCl3,0.005mol GeO；
上述材料加入其它常规盐类和试剂，加热制备铅基负极材料；该铅基材料具有很好的电化学性能，5Ag-1电流密度下，300次充放电循环，电化学容量大于200mAh/g。
实例3
一种铅基负极材料的成分设计，包括：
7)0.06mol CsCO3,0.06mol PbBr2,0.008mol MgI2,0.003mol GeO；
8)0.06mol CsCO3,0.06mol PbBr2,0.006mol SnO,0.004mol Sb2O3；
9)0.06mol CsCO3,0.06mol PbBr2,0.005mol AlCl3,0.005mol Sb2O5；
10)0.06mol CsCO3,0.06mol PbBr2,0.006mol SnF2,0.001mol CuO；
上述材料加入其它常规盐类和试剂，加热制备铅基负极材料；该铅基材料具有很好的电化学性能，5Ag-1电流密度下，300次充放电循环，电化学容量大于200mAh/g。
上述专利的具体实施方式是示例性的，是为了更好的使本领域技术人员能够理解本专利，不能理解为是对本专利包括范围的限制；只要是根据本专利所揭示精神的所作的任何等同变更或修饰，均落入本专利包括的范围。

Claims (1)

1.一种锂离子电池用铅基负极材料，是以CsCO3、PbBr2、含M离子化合物和含N离子化合物为原料加热制备的产物，为CsPbxM1-xBry-zNz；M和N 可以来自一种化合物、两种化合物或多种化合物；含M离子化合物为含锡离子化合物、含锗离子化合物和含锑离子化合物的一种或两种；含锡离子化合物为SnO2、SnO和SnF2的一种或两种；含锗离子化合物为GeO；含锑离子化合物为Sb2O3和Sb2O5的一种或两种；含N离子化合物为含氧离子化合物、含氟离子化合物和含碘离子化合物的一种或两种；含氧离子化合物为SnO2、SnO、GeO、Sb2O3和Sb2O5的一种或两种；含氟离子化合物为SnF2和MgF2的一种或两种；含碘离子化合物为MgI2；Pb占Pb和M总摩尔数的0.001-0.3,N占Br摩尔数的0.001-1。
CN202011095974.4A 2020-10-14 2020-10-14 一种铅基负极材料 Expired - Fee Related CN112234190B (zh)

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CN107325812A (zh) * 2017-07-03 2017-11-07 苏州虹霞晶体科技有限公司 一种钙钛矿结构发光材料及其基于抗溶剂的生产方法
KR102017797B1 (ko) * 2017-11-21 2019-09-03 중앙대학교 산학협력단 CsPbBr3/PbSe 나노 복합체 합성
CN108511706A (zh) * 2018-03-13 2018-09-07 合肥国轩高科动力能源有限公司 一种锂电池用二维无机钙钛矿负极材料的制备方法
CN108455660A (zh) * 2018-03-13 2018-08-28 合肥国轩高科动力能源有限公司 一种固-液相反应制备二维无机钙钛矿负极材料的方法
CN108682791B (zh) * 2018-03-23 2021-04-02 合肥国轩高科动力能源有限公司 一种气相法制备层状结构无机钙钛矿负极材料的方法
CN109065834B (zh) * 2018-07-12 2021-07-09 合肥国轩高科动力能源有限公司 一种锂离子用无机钙钛矿衍生相作负极材料的制备方法
CN111384361B (zh) * 2018-12-29 2021-08-20 北京大学 一种二维有机钙钛矿锂离子电池电极及其制备方法
CN110589876A (zh) * 2019-08-16 2019-12-20 南京理工大学 一种掺杂卤素钙钛矿铁电材料及其全无机柔性光探测器
CN110854366B (zh) * 2019-11-12 2022-04-15 东南大学 一种新型锂离子电池CsPbBr3/CNT钙钛矿复合材料及其制备方法

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