CN114221024B - 一种锂离子电池 - Google Patents

一种锂离子电池 Download PDF

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CN114221024B
CN114221024B CN202210034517.7A CN202210034517A CN114221024B CN 114221024 B CN114221024 B CN 114221024B CN 202210034517 A CN202210034517 A CN 202210034517A CN 114221024 B CN114221024 B CN 114221024B
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Abstract

本申请涉及一种锂离子电池，其特征在于，采用Y‑CoFe2O4/γ‑MnO2作为负极材料，其制备工艺如下：将硝酸钴、硝酸铁以及醋酸钇溶于去离子水中，随后加入六亚甲基四胺和尿素，搅拌均匀，将混合液置于高压水热反应釜中进行水热反应，温度为180‑200摄氏度，反应时间为10‑20h；得到纳米球状的Y掺杂CoFe2O4；将Y掺杂CoFe2O4采用去离子水和乙醇交替洗涤，随后溶于乙二醇中形成悬浮液，在悬浮液中加入高锰酸钾和甘氨酸，90‑100摄氏度下加热回流12‑20h，产物在200‑400℃下煅烧30‑60min，从而得到纳米核壳球状的Y掺杂CoFe2O4/γ‑MnO2。

Description

一种锂离子电池
技术领域
本发明涉及锂离子二次电池，尤其是空心核壳球结构负极材料及其制备方法。
背景技术
随着传统的化石能源匮乏以及环境污染、气候变暖等问题日益加剧，环境友好的新型能源技术也成了目前开发和应用的热点之一；可充电锂离子二次电池由于工作电压高、比能量高、比功率高、循环寿命长、自放电小、无记忆效应等优点，已经被广泛应用在便携式电子设备、电动工具、储能装置、电动车以及混合电动车上。
纳米级过渡金属氧化物由于具有较高的理论比容量，近年来引起了广泛的关注。但是，将其作为负极材料存在一系列的问题：(1)电子导电性差；(2)循环过程中有明显的体积膨胀/收缩现象，从而造成电极材料的粉化，影响倍率和循环性能。
发明内容
一种锂离子电池，其特征在于，采用Y-CoFe2O4/γ-MnO2作为负极材料，其制备工艺如下：
将硝酸钴、硝酸铁以及醋酸钇溶于去离子水中，随后加入六亚甲基四胺和尿素，搅拌均匀，将混合液置于高压水热反应釜中进行水热反应，温度为180-200摄氏度，反应时间为10-20h；得到纳米球状的Y掺杂CoFe2O4；
将Y掺杂CoFe2O4采用去离子水和乙醇交替洗涤，随后溶于乙二醇中形成悬浮液，在悬浮液中加入高锰酸钾和甘氨酸，90-100摄氏度下加热回流12-20h，产物在200-400℃下煅烧30-60min，从而得到纳米核壳球状的Y掺杂CoFe2O4/γ-MnO2。
优选的，硝酸钴、硝酸铁以及醋酸钇的摩尔比为1:2：(0.05-0.1)；
优选的，硝酸钴、六亚甲基四胺和尿素的摩尔比为1：(0.1-1)：(0.1-1)；
优选的，纳米核壳球状的Y掺杂CoFe2O4/γ-MnO2粒径为10-30nm。
有益效果：
在水热过程中加入六亚甲基四胺和尿素，从而得到中空结构纳米级的Y掺杂CoFe2O4，纳米的中空结构具有较大的比表面积，不仅提高了材料与电解液的接触面积，从而提升锂离子的传输速度，并且便于MnO2的高度分散负载；Y掺入CoFe2O4的晶格中，有利于进一步提升离子传输效率；空心的结构解决了CoFe2O4在循环过程中容易粉化的问题，从而提高了电池的循环性能以及稳定性。
附图说明
附图1为本申请实施例1中Y掺杂CoFe2O4/γ-MnO2的SEM图。
具体实施方式
实施例1
将10mmol的硝酸钴、20mmol硝酸铁以及0.5mmol的醋酸钇溶于20ml去离子水中，随后加入3mmol六亚甲基四胺和8mmol尿素，搅拌均匀，将混合液置于高压水热反应釜中进行水热反应，温度为180摄氏度，反应时间为10h；得到中空纳米球状的Y掺杂CoFe2O4；
将Y掺杂CoFe2O4采用去离子水和乙醇交替洗涤，随后溶于20ml乙二醇中形成悬浮液，在悬浮液中加入3mmol高锰酸钾和1mmol甘氨酸，100摄氏度下加热回流12h，产物在250℃下煅烧30min，从而得到纳米核壳球状的Y掺杂CoFe2O4/γ-MnO2。
对比例1
将10mmol的硝酸钴、20mmol硝酸铁以及0.5mmol的醋酸钇溶于20ml去离子水中，随后加入3mmol六亚甲基四胺和8mmol尿素，搅拌均匀，将混合液置于高压水热反应釜中进行水热反应，温度为180摄氏度，反应时间为10h；产物在250℃下煅烧30min，得到中空纳米球状的Y掺杂CoFe2O4。
对比例2
在20ml乙二醇中加入3mmol高锰酸钾和1mmol甘氨酸，100摄氏度下加热回流12h，产物在250℃下煅烧30min，从而得到γ-MnO2。
对比例3
其与对比例1的区别在于并未加入醋酸钇。
将以上实施例和对比例的活性材料与导电剂乙炔黑、粘结剂PVDF以8:1:1的比例混合浆料，将浆料涂覆于集流体上。以其作为负极，锂片为对电极，PP为隔膜，1M LiPF6-EC/DMC/DMC(体积比1:1:1)为电解液组成扣式电池。
Figure BDA0003467771120000011
Figure BDA0003467771120000021
尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的范围由所附权利要求及其等同物限定。

Claims (3)

1.一种锂离子电池，其特征在于，采用Y-CoFe2O4/γ-MnO2作为负极材料，其制备工艺如下：
将硝酸钴、硝酸铁以及醋酸钇溶于去离子水中，随后加入六亚甲基四胺和尿素，搅拌均匀，将混合液置于高压水热反应釜中进行水热反应，温度为180-200摄氏度，反应时间为10-20h；得到中空纳米球状的Y掺杂CoFe2O4；
将Y掺杂CoFe2O4采用去离子水和乙醇交替洗涤，随后溶于乙二醇中形成悬浮液，在悬浮液中加入高锰酸钾和甘氨酸，90-100摄氏度下加热回流12-20h，产物在200-400℃下煅烧30-60min，从而得到纳米核壳球状的Y掺杂CoFe2O4/γ-MnO2；硝酸钴、硝酸铁以及醋酸钇的摩尔比为1:2：（0.05-0.1）；硝酸钴、六亚甲基四胺和尿素的摩尔比为1：（0.1-1）：（0.1-1）。
2.根据权利要求1所述的一种锂离子电池，纳米核壳球状的Y掺杂CoFe2O4/γ-MnO2粒径为10-30nm。
3.根据权利要求1所述的一种锂离子电池，高锰酸钾和甘氨酸的摩尔比为1：（0.1-2）。
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