1、A123Systems Confidential Information Copyright 2007 A123 Systems,Inc.All rights reserved.Do not reproduce or distribute outside of A123Systems without written authorization.power.safety.life.高自放电培训杭道金2010-10-19A123Systems Confidential Information Copyright 2007 A123 Systems,Inc.All rights reserved.D
2、o not reproduce or distribute outside of A123Systems without written authorization.power.safety.life.目录 1.什么是高自放电2.为什么要控制高自放电3.高自放电基础知识4.高自放电来源5.结束语 A123Systems Confidential Information Copyright 2007 A123 Systems,Inc.All rights reserved.Do not reproduce or distribute outside of A123Systems without
3、written authorization.power.safety.life.何为高自放电?HSD:high self discharge 电池老化前满充电Cell full capacity before aging电池老化后残留容量C1再充电后放电容量C2SD（自放电）=(C2-C1)/C2*100%高自放电:SD X%(spec.)A123Systems Confidential Information Copyright 2007 A123 Systems,Inc.All rights reserved.Do not reproduce or distribute outside o
4、f A123Systems without written authorization.power.safety.life.为什么要控制高自放电1.A123 2009年因为高自放电损失 26650 损失:约20万颗 32113 损失:约1万颗 总损失=130万美元 2009 高自放电=15辆 BWM Z4A123Systems Confidential Information Copyright 2007 A123 Systems,Inc.All rights reserved.Do not reproduce or distribute outside of A123Systems with
5、out written authorization.power.safety.life.impurityimage electrodeEL电极中的不纯物在电解液环境中反应，导致原电池放电容量衰减高自放电类型：1.原电池反应2.因为金属内部短路 物理短路 化学短路主要原因 3.SEI 行程的不可逆容量原因Metal contamination 正极隔膜 负极Metal ion(Mn+)在正极氧化在负极还原正极金属污染物short因为正极表面污染物-化学内部短路Mn+e-M2.控制高自放电因为安全要求为什么要控制高自放电A123Systems Confidential Information Co
6、pyright 2007 A123 Systems,Inc.All rights reserved.Do not reproduce or distribute outside of A123Systems without written authorization.power.safety.life.Temp.700 过热：电池温度 正极临界温度自放电检查 防治过热，排除内部短路的电池正极 温度 放热 LiCoO2256769J/gLiNiO22101420J/gLiMnO2345235J/gLiFePO2480550wh/kg各种锂离子电池过热温度微短稳定温度(LimnO2)（345）短路
7、温度（700）发生内部短路时有极大地风险导致电池过热为什么要控制高自放电2.控制高自放电因为安全要求A123Systems Confidential Information Copyright 2007 A123 Systems,Inc.All rights reserved.Do not reproduce or distribute outside of A123Systems without written authorization.power.safety.life.负极正极隔膜rMetal Contamination M1.正极表面金属正极表面金属2.污染物在电池充电时在正极表面被
8、氧化，变成离子进入溶液，污染物在电池充电时在正极表面被氧化，变成离子进入溶液，在在电场电场作用作用下移动到负下移动到负极，并在负极表面得到电池被还原成金属，不断地长大，刺穿隔膜，形成短路，表现为极，并在负极表面得到电池被还原成金属，不断地长大，刺穿隔膜，形成短路，表现为高高自放电。自放电。M xeM x+金属氧化成离子M x+M x+移动到负极表面因为电场作用M x+M x+xeM在负极被还原成金属M M x+M M 金属在对应的位置迅速长大刺穿隔膜导致自放电12345高自放电知识高自放电的电池一定能在隔膜和负极表面找到相应证据正极表面的金属最易造成自放电高自放电金属:铁、铬、镍、铜、锌等原理
9、A123Systems Confidential Information Copyright 2007 A123 Systems,Inc.All rights reserved.Do not reproduce or distribute outside of A123Systems without written authorization.power.safety.life.将不锈钢粉放入26650正极并卷好充到3.6V 并12小时拆解电池分析在电池内部放入不锈钢粉实验不锈钢成分结果t 一致不锈钢粉在正极表面，充放电时溶解到电解液中，并在负极表面许出高自放电知识实验 A123Systems
10、 Confidential Information Copyright 2007 A123 Systems,Inc.All rights reserved.Do not reproduce or distribute outside of A123Systems without written authorization.power.safety.life.即使我们肉眼都发现不了的微小的金属污染物都能导致高自放电，实验表明颗粒(5 um)非常容易产生电池内部短路隔膜负极放大四十倍后放大四十倍后隔膜负极相机照片相机照片小黑点放大后高自放电知识测试A123Systems Confidential
11、Information Copyright 2007 A123 Systems,Inc.All rights reserved.Do not reproduce or distribute outside of A123Systems without written authorization.power.safety.life.不锈钢 铁 黄铜 隔膜负极EDX 0.001.002.003.004.005.006.007.008.009.0010.00keV0140500100015002000250030003500400045005000CountsCKaOKaFKaAlKaSiKaPKa
12、SKaSKbClKaClKbKKaKKbCaKaCaKbCrLlCrLaCrKaCrKbFeLlFeLaFeKescFeKaFeKbNiLlNiLaNiKaNiKbCuLlCuLaCuKaCuKbZnLlZnLaZnKaZnKb0.001.002.003.004.005.006.007.008.009.0010.00keV009080016002400320040004800560064007200CountsCKaNKaOKaFKaNaKaM gKaAlKaSiKaPKaSKaSKbClKaClKbKKaKKbCaKaCaKbTiLlTiLaTiKaTiKbCrLlCrLaCrKaCrKbF
13、eLlFeLaFeKescFeKaFeKbNiLlNiLaNiKaNiKbCuLlCuLaCuKaCuKbZnLlZnLaZnKaZnKbAgLaAgLbAgLb2SnLlSnLaSnLbSnLb2SnLrSnLr2,0.001.002.003.004.005.006.007.008.009.0010.00keV01208001600240032004000480056006400CountsCKaOKaFKaAlKaSiKaPKaSKaSKbClKaClKbKKaKKbCaKaCaKbCrLlCrLaCrKaCrKbFeLlFeLaFeKescFeKaFeKbNiLlNiLaNiKaNiKb
14、CuLlCuLaCuKaCuKbZnLlZnLaZnKaZnKb测试 高自放电知识A123Systems Confidential Information Copyright 2007 A123 Systems,Inc.All rights reserved.Do not reproduce or distribute outside of A123Systems without written authorization.power.safety.life.污染来源:原材料 过程 机器 环境 O O O 任何导致污染的源头都应当被找出并改正 能到导致高自放电的污染源A123Systems C
15、onfidential Information Copyright 2007 A123 Systems,Inc.All rights reserved.Do not reproduce or distribute outside of A123Systems without written authorization.power.safety.life.能到导致高自放电的污染源干燥气封口发现不锈钢颗粒环境 空调风管镀锌，有水分时会导致Zn脱落，导致高自放电门的来回移动会是合页产生金属粉尘A123Systems Confidential Information Copyright 2007 A1
16、23 Systems,Inc.All rights reserved.Do not reproduce or distribute outside of A123Systems without written authorization.power.safety.life.环境 闭门器会导致不锈钢粉移动的开关会产生不锈钢粉尘 柜子的磁吸会产生金属粉尘桌角与角铁碰撞会产生金属粉尘能到导致高自放电的污染源A123Systems Confidential Information Copyright 2007 A123 Systems,Inc.All rights reserved.Do not re
17、produce or distribute outside of A123Systems without written authorization.power.safety.life.crash 金属handle of cutter is loose and emiss particle when it is using软管上的螺丝在切刀运行时会碰到机器导致金属粉尘(Fe 和不锈钢）卷绕机的皮带切刀的把手松，当被使用时会碰到螺丝电池厂设备气缸运行时黑色物质能到导致高自放电的污染源A123Systems Confidential Information Copyright 2007 A123
18、Systems,Inc.All rights reserved.Do not reproduce or distribute outside of A123Systems without written authorization.power.safety.life.螺栓和螺母碰撞会产生不锈钢粉尘 生锈的镊子产生Fe极耳焊接时产生的铜粉磨损的工具刮伤的滚轴电池厂设备能到导致高自放电的污染源A123Systems Confidential Information Copyright 2007 A123 Systems,Inc.All rights reserved.Do not reproduc
19、e or distribute outside of A123Systems without written authorization.power.safety.life.消音器黄铜会导致高自放电，需要被更滑不锈钢产生于碰撞顶针产生不锈钢电池厂设备能到导致高自放电的污染源A123Systems Confidential Information Copyright 2007 A123 Systems,Inc.All rights reserved.Do not reproduce or distribute outside of A123Systems without written auth
20、orization.power.safety.life.正极搅拌桨损伤产生不锈钢黄铜链接头浆料搅拌罐下方的接头生锈产生Fe 和不锈钢冷却水阀产生Fe绣搅拌罐底部的法兰生锈导致不锈钢污染预混罐上部轴生锈PVDF 接头Zn污染预混罐导致的不锈钢污染涂布工厂能到导致高自放电的污染源A123Systems Confidential Information Copyright 2007 A123 Systems,Inc.All rights reserved.Do not reproduce or distribute outside of A123Systems without written aut
21、horization.power.safety.life.铝箔卷芯生锈导致铁铝箔卷支撑架被磨损涂布机运转时齿轮和链条摩擦涂布开始位置生锈的芯轴收卷生锈部件导致不锈钢污染分切机度Zn分切收卷磨损导致不锈钢污染涂布厂设备能到导致高自放电的污染源A123Systems Confidential Information Copyright 2007 A123 Systems,Inc.All rights reserved.Do not reproduce or distribute outside of A123Systems without written authorization.power.safety.life.结束语所有的存在或可能或导致高自放电的发生源都要被发现和解决请大家多看 多想 多行动
