CN1144304C - 一种锂离子电池负极材料的制备方法、负极和电池 - Google Patents

一种锂离子电池负极材料的制备方法、负极和电池 Download PDF

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CN1144304C
CN1144304C CNB01123430XA CN01123430A CN1144304C CN 1144304 C CN1144304 C CN 1144304C CN B01123430X A CNB01123430X A CN B01123430XA CN 01123430 A CN01123430 A CN 01123430A CN 1144304 C CN1144304 C CN 1144304C
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CN1328350A (zh
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陈继涛
周恒辉
常文保
慈云祥
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Xianxing Science-Technology-Industry Co Ltd Beijing Univ
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Abstract

本发明涉及一种锂离子电池，尤其涉及一种锂离子电池负极材料包覆石墨的制备，以及采用此包覆盖石墨的负极和采用此负极的锂离子电池。用一定量苯萘共聚物包覆石墨，然后将包覆石墨在氮气气氛中热解，得到热解碳包覆的石墨负极材料，以该包覆石墨为负极，嵌锂过渡金属氧化物为正极，溶解在有机混合溶剂中的锂盐为电解液，聚丙烯多孔膜为隔膜，构成的锂离子电池，负极活性物质的嵌锂比容量大于330mAh·g-1。制备条件简单，安全，成本低，所制包覆石墨比容量高，有良好的循环性能。可广泛应用于用电领域。

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一种锂离子电池负极材料的制备方法、负极和电池
技术领域：本发明涉及一种锂离子电池，尤其涉及一种锂离子电池负极材料包覆石墨的制备，以及采用此包覆石墨的负极和采用此负极的锂离子电池。
背景技术：从锂离子电池问世以来，其负极材料一直作为材料研究的热点。目前的研究主要集中在碳材料和一些金属氧化物方面，虽然人们不断研究出一些高比容量的新型负极材料，但从商品化的角度来说，焦炭和石墨在价格性能比方面有着很大的优势，比较而言，石墨以其良好的电压平台和较高的比容量为产业界所关注。
石墨具有高的结晶度，嵌锂石墨属离子型石墨层间化合物，其一阶化合物分子式为LiC6，理论容量为372mAh·g-1(372毫安·小时/克)，锂的嵌入与脱嵌反应发生在0-0.25伏(相对于Li/Li+)，具有良好的电压平台。但是，由于石墨层间作用力弱，与电解液相容性较差，在充放电过程中会发生溶剂分子进入石墨层，从而引起表层剥落，电解液继续和新的表层反应，致使石墨的循环性能较差，因此，用石墨作为锂离子电池负极材料，其性能有一定的局限性。因此，人们通过各种方法对石墨进行结构修饰，即用物理或化学方法改性石墨，从而提高其电化学性能。Wu，Y.P.等用对石墨进行氧化的方法来提高其性能(E.Electrochem.Commun.2000，2，272)，Tsumura，T.等(Solid State Ionics2000，135，209)和Yoshio，M.等(J.of the Electrochemical Soc.2000，147，1245)用包覆的方法对石墨进行改性，但其距实用化还有一定距离。
发明内容：本发明的目的是提供一种包覆石墨的制备方法，克服石墨易脱落、循环性差的、稳定容量不高等缺点，提高其可逆嵌锂比容量及其与电解液的相容性。
本发明的目的还在于提供一种以上述包覆石墨为材料的负极和包括该负极的锂离子电池。
本发明的锂电池负极包覆石墨的制备方法，其步骤包括
1)将合成的苯萘共聚物和石墨混合，在混合机上混合1～5小时；
2)将混合均匀后的材料放入热解炉，在流速为1～5升/分钟的惰性气体流保护中加热处理，升温速率为每分钟1～20℃；
3)在600--900℃维持0.5～48小时，然后降至室温20℃。
上述苯萘共聚物所占的比例为10-25％。惰性气体为氮气或氩气。
本发明的锂电池负极，包括包覆石墨，导电剂和黏结剂，它们的重量比依次为：99.4-74％∶0.5-16％∶0.1-10％。
导电剂选自石墨或者炭黑，或者它们的混合物，其混合重量依次为(1-2)∶(2-3)；黏结剂选自聚四氟乙烯或聚偏氟乙烯。
当导电剂为炭黑，黏结剂为聚四氟乙烯，包覆石墨、炭黑、聚四氟乙烯重量比依次可为10∶1∶1。
本发明的锂电池，包括负极，正极，电解液，隔膜，正极由嵌锂的过渡金属氧化物构成，电解液为浓度为一摩尔每升的锂盐的有机混合溶剂溶液，隔膜为高分子聚合物微孔薄膜。
上述过渡金属氧化物选自钴酸锂、镍酸锂、锰酸锂；锂盐选自高氯酸锂、六氟磷酸锂；有机溶剂选自碳酸乙烯酯、碳酸二乙酯、碳酸二甲酯；隔膜为聚丙烯微孔薄膜。
当上述有机溶剂为两种组合时，体积比可为(1∶9)-(9∶1)，或当为三种组合时，体积比为1∶1∶1。
上述电解液为浓度为一摩尔每升的高氯酸锂的碳酸乙烯酯和碳酸二乙酯混合溶液，或碳酸乙烯酯和碳酸二甲酯混合液，混合比为1∶1。
所述电池的负极包括苯萘共聚物热解碳包覆石墨、炭黑和聚偏氟乙烯，它们的重量比依次为10∶1∶1。
本发明的优点是：
(1).制备包覆石墨方法简单、安全性好、成本低；
(2).所制备的包覆石墨和导电剂、黏结剂混合制成碳负极，具有高度的可逆性；
(3).所制备的包覆石墨可逆比容量大于330mAh·g-1，与电解液相容性好，有良好的循环性。
按照本发明制备的包覆石墨，其XRD衍射分析表明，2θ在43°的峰比包覆前增高(见图1)；
本发明的锂离子电池用途广泛，包括：用于移动电话、笔记本电脑、摄像机、电动自行车、电动汽车、电动玩具等，因其可制成大小不同的各种形状，适用于各种用电领域使用。
附图说明：
图1包覆前后石墨样品X射线衍射(XRD)图谱  a)包覆前  b)包覆后
具体实施方式：
实施例1：
将18克天然石墨和2克苯萘共聚物混合，在混料机上混合2小时，在5升/分钟的氮气气氛下，以10℃/分钟的速率升至800℃，保持该温度1.0小时，然后降温至20℃。所得热解碳按下述方法制备电极。
称取10克碳，加入1克炭黑，1克聚四氟乙烯，研磨均匀后，制成电极，以LiCoO2为正极，溶解在碳酸乙酯+碳酸二乙酯(体积比1∶1)混合溶剂中的1.0摩尔/升LiClO4为电解液，聚丙烯微孔薄膜为隔膜，组装成模型电池，按25mA/(克碳)的速率充电至4.2伏，放电至2.7伏，测得碳活性物质的可逆比容量为340mAh·g-1。
实施例2：
将15克人造石墨和5克苯萘共聚物混合，在混料机上混合3小时，在5升/分钟的氮气气氛下，以10℃/分钟的速率升至900℃，保持该温度3.0小时，然后降温至20℃。所得碳样按实例1的方法制备电极片并组装成电池后测定可逆比容量为355mAh·g-1。
实施例3：
按实例1的方法制备碳材料，按下面方法制备碳电极：称取10克碳，加入1克炭黑，1克聚偏氟乙烯，研磨均匀后，制成电极。按实例1的方法组装成电池后测定可逆比容量为345mAh·g-1。
实施例4：
按实例1的方法制备碳材料和碳电极，用溶解在碳酸乙酯+碳酸二甲酯(体积比1∶1)混合溶剂中的1.0摩尔/升LiPF6为电解液，按实例1的方法测定可逆比容量为343mAh·g-1。
实施例5：
按实例1的方法制备碳材料和碳电极，正极采用锰酸锂，按照实施例1的方法组装电池测定可逆比容量为340mAh·g-1。

Claims (11)

1.一种锂电池负极包覆石墨的制备方法，其步骤包括
1)将合成的苯萘共聚物和石墨混合，在混合机上混合1～5小时；
2)将混合均匀后的材料放入热解炉，在流速为1～5升/分钟的惰性气体流保护中加热处理，升温速率为每分钟1～20℃；
3)在600--900℃维持0.5～48小时，然后降至室温20℃。
2.如权利要求1所述的锂电池负极包覆石墨的制备方法，其特征在于苯萘共聚物所占的比例为10-25％。
3.如权利要求1所述的锂电池负极包覆石墨的制备方法，其特征在于惰性气体为氮气或氩气。
4.一种采用权利要求1所述制备方法制得包覆石墨的锂电池负极，包括包覆石墨，导电剂和黏结剂，其特征在于所述包覆石墨，导电剂和黏结剂重量比依次为：99.4-74％∶0.5-16％∶0.1-10％。
5.一种如权利要求4所述的锂电池负极，其特征在于导电剂选自石墨或者炭黑，或者它们的混合物，其混合重量依次为(1-2)∶(2-3)；黏结剂选自聚四氟乙烯或聚偏氟乙烯。
6.一种如权利要求5所述的锂电池负极，其特征在于导电剂为炭黑，黏结剂为聚四氟乙烯，包覆石墨、炭黑、聚四氟乙烯重量比依次为10∶1∶1。
7.一种采用权利要求4所述锂电池负极的锂电池，包括负极，正极，电解液，隔膜，其特征在于正极由嵌锂的过渡金属氧化物构成，电解液为浓度为一摩尔每升的锂盐的有机混合溶剂溶液，隔膜为高分子聚合物微孔薄膜。
8.一种如权利要求7所述的锂电池，其特征在于过渡金属氧化物选自钴酸锂、镍酸锂、锰酸锂；锂盐选自高氯酸锂、六氟磷酸锂或二者混合物；有机溶剂选自碳酸乙烯酯、碳酸二乙酯和碳酸二甲酯的任意一种或者几种混合物；隔膜为聚丙烯微孔薄膜。
9.一种如权利要求8所述的锂电池，其特征在于有机溶剂为两种组合时的体积比为(1∶9)-(9∶1)，或为三种组合时的体积比为1∶1∶1。
10.一种如权利要求7所述的锂电池，其特征在于电解液为浓度为一摩尔每升的高氯酸锂的碳酸乙烯酯和碳酸二乙酯混合溶液，或碳酸乙烯酯和碳酸二甲酯混合液，混合比为1∶1。
11.一种如权利要求7所述的锂电池，其特征在于所述电池的负极包括苯萘共聚物热解碳包覆石墨、炭黑和聚偏氟乙烯，它们的重量比依次为10∶1∶1。
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KR100642053B1 (ko) * 2005-03-25 2006-11-10 한국타이어 주식회사 다공성 봉투가 배치된 전지
CN104979530B (zh) * 2014-08-29 2017-05-10 湖北工程学院 一种天然石墨基复合电极材料的制备方法
CN112786871B (zh) * 2021-02-18 2022-03-29 Oppo广东移动通信有限公司 硅基负极材料及其制备方法、负极、电池和电子设备
CN117374515B (zh) * 2023-12-06 2024-04-19 天津力神电池股份有限公司 具有锂离子容量补偿作用的隔膜及其制备方法和电池

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CN1326267C (zh) * 2005-05-27 2007-07-11 深圳市贝特瑞电子材料有限公司 锂离子电池复合碳负极材料及其制备方法

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