1、锂电池发展简介锂离子电池是一种充电电池，它主要依靠锂离子在正极和负极之间移动来工作。在充放电过程中，Li+ 在两个电极之间往返嵌入和脱嵌：充电池时，Li+从正极脱嵌，经过电解质嵌入负极，负极处于富锂状态；放电时则相反。一般采用含有锂元素的材料作为电极的电池，是现代高性能电池的代表。发展历史早期锂电池锂离子电池(Li-ion Batteries)是锂电池发展而来。所以在介绍 Li-ion 之前，先介绍锂电池。举例来讲，以前照相机里用的扣式电池就属于锂电池。锂电池的正极材料是二氧化锰或亚硫酰氯，负极是锂。电池组装完成后电池即有电压不需充电。这种电池也可以充电，但循环性能不好，在充放电循环过程中容易
2、形成锂结晶，造成电池内部短路，所以一般情况下这种电池是禁止充电的。2炭材料锂电池后来，日本索尼公司发明了以炭材料为负极，以含锂的化合物作正极的锂电池，在充放电过程中，没有金属锂存在，只有锂离子，这就是锂离子电池。摇椅式电池我们通常所说的电池容量指的就是放电容量。在 Li-ion 的充放电过程中，锂离子处于从正极负极正极的运动状态。Li-ion Batteries 就像一把摇椅，摇椅的两端为电池的两极，而锂离子就象运动员一样在摇椅来回奔跑。所以Li-ion Batteries 又叫摇椅式电池。发展时间点1970 年代埃克森的 M.S.Whittingham 采用硫化钛作为正极材料，金属锂作为负极
3、材料，制成首个锂电池。1982 年伊利诺伊理工大学(the Illinois Institute of Technology)的R.R.Agarwal 和 J.R.Selman 发现锂离子具有嵌入石墨的特性，此过程是快速的，并且可逆。与此同时，采用金属锂制成的锂电池，其安全隐患备受关注，因此人们尝试利用锂离子嵌入石墨的特性制作充电电池。首个可用的锂离子石墨电极由贝尔实验室试制成功。1983 年 M.Thackeray、J.Goodenough 等人发 现锰尖晶石是优良的正极材料，具有低价、稳定和优良的导电、导锂性能。其分解温度高，且氧化性远低于钴酸锂，即使出现短路、过充电，也能够避免了燃烧、爆
4、炸的危险。1989 年，A.Manthiram 和 J.Goodenough 发现采用聚合阴离子的正极将产生更高的电压。1992 年索尼公司发布首个商用锂离子电池。随后，锂离子电池革新了消费电子产品的面貌。此类以钴酸锂作为正极材料的电池，至今仍是便携电子器件的主要电源。1996 年 Padhi 和 Goodenough 发现具有橄榄石结构的磷酸盐，如磷酸铁锂(LiFePO4)，比传统的正极材料更具安全性，尤其耐高温，耐过充电性能远超过传统锂离子电池材料。因此已成为当前主流的大电流放电的动力锂电池的正极材料。综观电池发展的历史，可以看出当前世界电池工业发展的三个特点，一是绿色环保电池迅猛发展，包
5、括锂离子蓄电池、氢镍电池等；二是一次电池向蓄电池转化，这符合可持续发展战略；三是电池进一步向小、轻、薄方向发展。在商品化的可充电池中，锂离子电池的比能量最高，特别是聚合物锂离子电池，可以实现可充电池的薄形化。正因为锂离子电池的体积比能量和质量比能量高，可充且无污染，具备当前电池工业发展的三大特点，因此在发达国家中有较快的增长。电信、信息市场的发展，特别是移动电话和笔记本电脑的大量使用，给锂离子电池带来了市场机遇。而聚合物锂离子电池以其在加工性能、质量、材料价格等方面的独特优势，将逐步取代液体电解质锂离子电池，而成为锂离子电池的主流。聚合物锂离子电池被誉为 “21 世纪的电池” ，将开辟蓄电池的
6、新时代，发展前景十分乐观。3组成部分钢壳/铝壳/圆柱/软包装系列：（1）正极活性物质一般为锰酸锂或者钴酸锂，镍钴锰酸锂材料，电动自行车则普遍用镍钴锰酸锂（俗称三元）或者三元+少量锰酸锂，纯的锰酸锂和磷酸铁锂则由于体积大、性能不好或成本高而逐渐淡出。导电集流体使用厚度10-20 微米的电解铝箔。（2）隔膜一种经特殊成型的高分子薄膜，薄膜有微孔结构，可以让锂离子自由通过，而电子不能通过。（3）负极活性物质为石墨，或近似石墨结构的碳，导电集流体使用厚度 7-15 微米的电解铜箔。（4）有机电解液溶解有六氟磷酸锂的碳酸酯类溶剂，聚合物的则使用凝胶状电解液。（5）电池外壳分为钢壳（方型很少使用） 、铝壳
7、、镀镍铁壳（圆柱电池使用） 、铝塑膜（软包装）等，还有电池的盖帽，也是电池的正负极引出端。根据锂离子电池所用电解质材料的不同，锂离子电池分为液态锂离子电池(Liquified Lithium-Ion Battery，简称为 LIB)和聚合物锂离子电池(Polymer Lithium-Ion Battery，简称为 PLB)。锂离子电池(Li-ion)可充电锂离子电池是目前手机、笔记本电脑等现代数码产品中应用最广泛的电池，但它较为“娇气” ，在使用中不可过充、过放(会损坏电池或使之报废)。因此，在电池上有保护元器件或保护电路以防止昂贵的电池损坏。锂离子电池充电要求很高，要保证终止电压精度在1%之
8、内，各大半导体器件厂已开发出多种锂离子电池充电的 IC，以保证安全、可靠、快速地充电。手机基本上都是使用锂离子电池。正确地使用锂离子电池对延长电池寿命是十分重要的。它根据不同的电子产品的要求可以做成扁平长方形、圆柱形、长方形及扣式，并且有由几个电池串联并联在一起组成的电池组。锂离子电池的额定电压，因为材料的变化，一般为 3.7V，磷酸铁锂（以下称磷铁）正极的则为 3.2V。充满电时的终止充电电压一般是 4.2V，磷铁 3.65V。锂离子电池的终止放电电压为 2.75V3.0V(电池厂给出工作电压范围或给出终止放电电压，各参数略有不同，一般为 3.0V，磷铁为 2.5V)。低于 2.5V（磷铁
9、2.0V）继续放电称为过放，过放对电池会有损害。钴酸锂类型材料为正极的锂离子电池不适合用作大电流放电，过大电流放电时会降低放电时间(内部会产生较高的温度而损耗能量)，并可能发生危险；但磷酸铁锂正极材料锂电池，可以以 20C 甚至更大（C 是电池的容量，如C=800mAh，1C 充电率即充电电流为 800mA）的大电流进行充放电，特别适合电动车使用。因此电池生产工厂给出最大放电电流，在使用中应小于最大放电电流。锂离子电池对温度有一定要求，工厂给出了充电温度范围、放电温度范围及保存温度范围，过压充电会造成锂离子电池永久性损坏。锂离子电池充电电流应根据电池生产厂的建议，并要求有限流电路以免发生过流(
10、过热)。一般常用的充电倍率为 0.25C1C。在大电流充电时往往要检测电池温度，以防止过热损坏电池或产生爆炸。锂离子电池充电分为两个阶段：先恒流充电，到接近终止电压时改为恒压充电。例一种 800mAh 容量的电池，其终止充电电压为 4.2V。电池以 800mA(充电率为 1C)恒流充电，开始时电池电压以较大的斜率升压，当电池电压接近4.2V 时，改成 4.2V 恒压充电，电流渐降，电压变化不大，到充电电流降为1/10-50C(各厂设定值不一，不影响使用)时，认为接近充满，可以终止充电(有的充电器到 1/10C 后启动定时器，过一定时间后结束充电)。工作状态和效率锂离子电池能量密度大，平均输出电
11、压高。自放电小，好的电池，每月在2%以下（可恢复） 。没有记忆效应。工作温度范围宽为-2060。循环性能优越、可快速充放电、充电效率高达 100%，而且输出功率大。使用寿命长。不含有毒有害物质，被称为绿色电池。工作原理当对电池进行充电时，电池的正极上有锂离子生成，生成的锂离子经过电解液运动到负极。而作为负极的碳呈层状结构，它有很多微孔，达到负极的锂离子就嵌入到碳层的微孔中，嵌入的锂离子越多，充电容量越高。同样，当对电池进行放电时（即我们使用电池的过程） ，嵌在负极碳层中的锂离子脱出，又运动回正极。回正极的锂离子越多，放电容量越高。 一般锂电池充电电流设定在 0.2C 至 1C 之间，电流越大，
12、充电越快，同时电池发热也越大。而且，过大的电流充电，容量不够满，因为电池内部的电化学反应需要时间。就跟倒啤酒一样，倒太快的话会产生泡沫，反而不满。对电池来说，正常使用就是放电的过程。锂电池放电需要注意几点：第一，放电电流不能过大，过大的电流导致电池内部发热，有可能会造成永久性的损害。在手机上，这个倒是没有问题的，可以不考虑。第二，绝对不能过放电！锂电池最怕过放电，一旦放电电压低于 2.7V，将可能导致电池报废。好在手机电池内部都已经装了保护电路，电压还没低到损坏电池的程度，保护电路就会起作用，停止放电。从图上可以看出，电池放电电流越大，放电容量越小，电压下降更快。作用机理锂离子电池以碳素材料为
13、负极，以含锂的化合物作正极，没有金属锂存在，只有锂离子，这就是锂离子电池。锂离子电池是指以锂离子嵌入化合物为正极材料电池的总称。锂离子电池的充放电过程，就是锂离子的嵌入和脱嵌过程。在锂离子的嵌入和脱嵌过程中，同时伴随着与锂离子等当量电子的嵌入和脱嵌（习惯上正极用嵌入或脱嵌表示，而负极用插入或脱插表示） 。在充放电过程中，锂离子在正、负极之间往返嵌入/脱嵌和插入/脱插，被形象地称为“摇椅电池” 。Lithium battery developmentLithium ion battery is a rechargeable battery, it mainly rely on lithium i
14、on moves between the positive and negative to work. In the process of charging and discharging, Li + embedded back and forth between the two electrodes and embedded off: when the rechargeable battery, Li + embedded from the anode, after anode, electrolyte embedded in the cathode in the rich lithium
15、state; Discharge is the opposite. Commonly used as electrode materials containing lithium batteries, is the representative of modern high-performance batteriesThe development historyEarly lithium batteryLithium ion Batteries (Li - ion Batteries) is lithium battery. So before the introduction of Li -
16、 ion, introduces the first lithium battery. For example, in the camera before use it belong to lithium button cell battery. Lithium battery cathode material is manganese dioxide or thionyl chloride, lithium anode is. Battery assembly after the completion of the battery with voltage without charge. T
17、he battery can charge, but the loop performance is not good, easy to form the crystallization of lithium, in the process of charge and discharge cycle due to internal short circuit batteries, so usually is charging the battery. 2Carbon materials lithium batteryLater, SONY of Japan invented the carbo
18、n materials as anode, with lithium compounds as the anode of lithium battery, in the process of charging and discharging, no metal lithium exists, only lithium ion, that is the lithium ion battery.A rocking-chair batteriesWe usually mean by battery capacity is the discharge capacity. In Li - ion of
19、the charge and discharge process, the lithium ions in motion from the positive and negative to the anode. Li - ion Batteries is like a rocking chair, rocking chair at both ends of the poles for the battery, and lithium ion like athletes running back and forth in a rocking chair. So Li - ion Batterie
20、s, also called a rocking-chair Batteries.Development timeIn the 1970 s, M.S.W exxon hittingham using titanium sulfide as the anode material, metallic lithium as negative material, made the first lithium battery.University of Illinois Institute of Technology, 1982 (the Illinois Institute of Technolog
21、y) of R.R.A garwal and J.R.S elman found embedded lithium ion has the properties of the graphite, the process is quick, and reversible. At the same time, made of metallic lithium lithium batteries, much attention has been paid to its safety problems, so people try to take advantage of the characteri
22、stics of lithium ion embedded graphite production of rechargeable batteries. The first available lithium-ion graphite electrode successfully trial-produced by bell LABS.In 1983 m. hackeray, J.G oodenough people such as hair Galaxite now is a good positive materials, with low price, stable and good c
23、onductive lithium, guide performance. Its decomposition temperature is high, and oxidation is far lower than the cobalt acid lithium, even if a short circuit, over charge, also can avoid the risk of combustion and explosion.In 1989, arjun anthiram and J.G oodenough anionic polymerization is found th
24、at the positive will generate higher voltage.SONY in 1992 published the first commercial lithium-ion batteries. Subsequently, lithium ion batteries have revolutionized the face of consumer electronics products. Such as cobalt acid lithium as the anode material of battery, is still the main power sup
25、ply of portable electronic devices.Padhi and Goodenough found 1996 has olivine structure of phosphate, such as lithium iron phosphate (LiFePO4), more security than traditional positive electrode materials, especially high temperature resistance, resistance to overcharge performance than traditional
26、lithium-ion battery materials. Therefore has become the current mainstream of large current discharge power lithium battery cathode material.Throughout the history of the development of battery, we can see that the three characteristics on the development of battery industry in the world, and one is
27、 the rapid development of green environmental protection battery, including lithium ion batteries, nickel-metal hydride batteries, etc.; Two is a battery to battery, it conforms to the sustainable development strategy; 3 it is battery further development in the direction of small, light and thin. In
28、 the commercialization of rechargeable batteries, lithium ion battery has the highest specific energy, especially the polymer lithium ion battery, can thin type of rechargeable battery. Because of the volume of lithium ion battery is high specific energy and mass, rechargeable and pollution-free, po
29、ssess three characteristics of current battery industry development, so have faster growth in the developed countries. Telecom, the development of information market, especially the use of mobile phones and laptop computers, has brought the lithium ion battery market opportunities. And polymer lithi
30、um ion battery with its processing performance, quality, the unique advantages of material price and so on, will gradually replace the liquid electrolyte for lithium ion batteries, and become the mainstream of the lithium ion battery. Polymer lithium ion battery has been hailed as a “battery“ in the
31、 21st century, will set up a new era of battery, the development prospect is very optimistic.Part of theThe steel/aluminum shell/cylindrical/flexible packaging series:- (1) the positive active material is commonly or cobalt acid lithium manganese acid lithium nickel manganese cobalt acid lithium mat
32、erials, electric bicycle is common to use lithium cobalt nickel manganese acid (commonly known as the three yuan) or three yuan plus a small amount of manganese acid lithium, pure manganese acid lithium and lithium iron phosphate is due to the large size, high performance is bad or cost gradually fa
33、de out. Conductive set fluid using electrolytic aluminum foil thickness of 10-20 microns.(2) - a specially shaped diaphragm of polymer thin films, the film has a microporous structure, can let the lithium ions through freely, and electronic cannot pass.(3) negative - active substances for graphite,
34、or approximate graphite carbon structure, fluid using conductive set of electrolytic copper foil thickness 7 to 15 microns.(4) dissolved organic electrolyte - six fluoride phosphate lithium carbonate solvent type, use the gel polymer electrolyte.(5) battery shell, divided into steel shell (square) i
35、s rarely used, aluminum, nickel plated iron shell (cylindrical battery), aluminum-plastic film (flexible packaging) and so on, and the battery cap, and is negative terminal of the battery.According to the electrolyte materials that are used in Lithium Ion batteries, Lithium Ion batteries are divided
36、 into liquid Lithium Ion Battery (Liquified Lithium - Ion , referred to as the LIB) and Polymer Lithium Ion batteries, Polymer Lithium - Ion , for PLB).Lithium ion batteries (Li - ion)Rechargeable lithium ion batteries is the modern digital products, such as mobile phones, laptops, the most widely u
37、sed in battery, but it is relatively “temperamental“, in use do not overcharge, discharge (can damage the battery or scrap). As a result, have protection components or protection circuit on the battery to prevent damage of expensive battery. High demand for lithium ion batteries, to ensure the termi
38、nation voltage accuracy within + / - 1%, the semiconductor device factory has developed a variety of lithium ion battery charging IC, to ensure safe, reliable and fast charging.Mobile phones are basically use lithium ion batteries. Proper use of lithium ion battery is very important to extend batter
39、y life. It according to the requirements of different electronic products can be made flat rectangular, cylindrical, rectangular and button, and there are composed of several parallel in series with the battery pack. Rated voltage of the lithium ion battery, because the change of the material, gener
40、ally 3.7 V, (hereinafter referred to as phosphorus iron) lithium iron phosphate anode was 3.2 V. Charged when the termination of charging voltage is 4.2 V, 3.65 V phosphorus iron. The termination of lithium ion battery discharge voltage of 2.75 V to 3.0 V (battery or termination of the discharge vol
41、tage, voltage range is given the parameters is slightly different, generally 3.0 V, phosphorus iron as 2.5 V). Below 2.5 V (2.0 V) phosphorus iron continue to discharge called discharge, discharge the battery will be damage.Cobalt acid lithium type material for the anode of lithium ion battery is no
42、t suitable for used as large current discharge, large current discharge will reduce the discharge time (internal will produce high temperature and energy losses), and may be dangerous; But lithium batteries, lithium iron phosphate battery anode materials with 20 C can even bigger (C is the capacity
43、of the battery, such as C = 800 mah, 1 C charge rate the charging current is 800 ma) of large current charge and discharge, especially suitable for electric vehicle use. So the battery production factories give maximum discharge current, in use should be less than the maximum discharge current. Lith
44、ium ion batteries have certain requirements for temperature, plant the charging temperature, discharge temperature range and temperature range, overvoltage rechargeable lithium-ion batteries, permanent damage. Lithium ion battery charging current should be on the advice of the battery factory, and a
45、sk the limited current circuit in order to avoid happened flow (overheating). General common charging ratio is 0.25 C 1 C. Tend to detect when large current charging the battery temperature, to prevent overheating damage to the battery or explosion.Lithium ion batteries are divided into two stages:
46、the first constant current charging, to about the termination voltage to constant voltage charging. Example a 800 mah battery, the capacity of its termination of charging voltage of 4.2 V. Battery at 800 ma (charge rate for 1 c) constant current charging, battery voltage with a larger slope booster
47、at the beginning, when the battery voltage close to 4.2 V to 4.2 V constant voltage charging, gradual decline current, voltage change is not big, the charging current to 1/10-50 c (GeChang have different value, does not affect use), close to full, may terminate charging (some charger to start the ti
48、mer after 1/10 c, after a certain time end charging).Working status and efficiencyLithium ion battery has a large energy density, the average output voltage. Uniformity, good batteries, under 2% (recoverable) a month. No memory effect. Wide working temperature range for - 20 60 . Loop performance is
49、 superior, can fast charge and discharge, charging efficiency is as high as 100%, and the output power. Long service life. Does not contain toxic and harmful substances, known as the green cells.The working principle ofWhen charging the battery, the battery has lithium ions generated in the anode, lithium ions generated through the electrolyte to the negative movement. As a cathode carbon layer structure, it has many pores, reach the cathode of lithium ion is embedded into the microporous carbon layer, the embedded lithium ion, the more the higher the charge
