電源技術研究與設計高性能18650型鋰離子蓄電池張(zhang)澤波，劉秀(xiu)生，薛梅，楊清欣(xin)，汪繼強（信息產(chan)業部(bu)電子第十八研究所，天(tian)津300381）（LiNi0.8Co0.2O2）為(wei)正(zheng)(zheng)極，中間相炭微珠（MCMB）為(wei)負(fu)極的(de)(de)18650型鋰(li)離子蓄電池(chi)(chi)(chi)。電池(chi)(chi)(chi)的(de)(de)放電容(rong)(rong)量(liang)(liang)分別大于1 700mAh電池(chi)(chi)(chi)比能量(liang)(liang)達到(dao)了130Wh/kg和350Wh/L.在(zai)(zai)室(shi)溫條(tiao)件下，0.5C電池(chi)(chi)(chi)的(de)(de)循環壽命1000次時，其容(rong)(rong)量(liang)(liang)仍為(wei)初始(shi)容(rong)(rong)量(liang)(liang)的(de)(de)60%.70%.以氧化鈷鋰(li)為(wei)正(zheng)(zheng)極的(de)(de)電池(chi)(chi)(chi)在(zai)(zai)一40°C.0.2C速率。終止電壓2.5V的(de)(de)條(tiao)件下，放電容(rong)(rong)量(liang)(liang)為(wei)室(shi)溫容(rong)(rong)量(liang)(liang)的(de)(de)60%.實驗結果表明(ming)，電池(chi)(chi)(chi)安全可(ke)靠。

　　鋰離子蓄(xu)電(dian)(dian)池(chi)(chi)自1991年商品化(hua)(hua)(hua)以來發展迅速。目前它不(bu)但(dan)廣泛(fan)用(yong)于攝象機、筆記本電(dian)(dian)腦、蜂窩電(dian)(dian)話等便攜(xie)式電(dian)(dian)子設施，而且正(zheng)在(zai)成為電(dian)(dian)動車、軍事通(tong)訊、航(hang)(hang)天、航(hang)(hang)空領(ling)域電(dian)(dian)子設施的(de)(de)候選電(dian)(dian)源111.這就要(yao)求(qiu)電(dian)(dian)池(chi)(chi)具(ju)(ju)有(you)更(geng)高的(de)(de)比能(neng)量、更(geng)長的(de)(de)工作(zuo)壽命及良好的(de)(de)高、低溫放電(dian)(dian)特性。為此我們(men)試驗了高性能(neng)的(de)(de)正(zheng)極(ji)材料氧(yang)化(hua)(hua)(hua)鈷鋰、氧(yang)化(hua)(hua)(hua)鎳鈷鋰和負極(ji)碳材料一中間相(xiang)炭微珠，對電(dian)(dian)池(chi)(chi)設計進行優化(hua)(hua)(hua)改進電(dian)(dian)極(ji)成型(xing)工藝，篩選不(bu)同組分和配(pei)比的(de)(de)電(dian)(dian)液體系，研(yan)制出具(ju)(ju)有(you)高性能(neng)的(de)(de)18650型(xing)鋰離子蓄(xu)電(dian)(dian)池(chi)(chi)。

　　以金屬鋰為負(fu)極，采用扣式電(dian)池(chi)試(shi)驗了(le)正極材(cai)料LiCo2和LiNi0.8Co0.O2的充(chong)放(fang)(fang)電(dian)特性。充(chong)放(fang)(fang)電(dian)壓范圍3.充(chong)放(fang)(fang)電(dian)流密(mi)度0.2mA/cm2.研(yan)究了(le)負(fu)極炭粉MCMB顆粒度及(ji)(ji)其分布與電(dian)池(chi)容量及(ji)(ji)充(chong)放(fang)(fang)電(dian)效率的關系，并試(shi)驗了(le)負(fu)電(dian)極成(cheng)型工藝條(tiao)件。

　　電(dian)(dian)(dian)液(ye)(ye)體系(xi)(xi)的篩(shai)選對電(dian)(dian)(dian)解質(zhi)為1mol/LLiPFf以碳(tan)酸乙(yi)烯酯(zhi)（EC）為主(zhu)體的不同組分(fen)〔包括碳(tan)酸二(er)乙(yi)酯(zhi)（DEC）碳(tan)酸二(er)甲酯(zhi)（DMC）碳(tan)酸乙(yi)甲酯(zhi)（EMC）碳(tan)酸丙烯酯(zhi)（PC）等〕和比例的多元電(dian)(dian)(dian)液(ye)(ye)體系(xi)(xi)進行(xing)試驗。研究了其與電(dian)(dian)(dian)極材料的相容性(xing)(xing)和對電(dian)(dian)(dian)池容量。充放(fang)效(xiao)率、盾環壽命。倍(bei)率特(te)(te)性(xing)(xing)。溫度特(te)(te)性(xing)(xing)的影響。

　　電(dian)(dian)池(chi)工(gong)(gong)藝(yi)參數的(de)設計(ji)和電(dian)(dian)極(ji)的(de)制(zhi)作根據材料的(de)試驗結果(guo)，設計(ji)了電(dian)(dian)池(chi)正負極(ji)活性(xing)物(wu)質的(de)配比(bi)及電(dian)(dian)極(ji)的(de)工(gong)(gong)藝(yi)參數。將正極(ji)活性(xing)物(wu)質與(yu)一定(ding)比(bi)例的(de)添加劑均勻(yun)(yun)混和，加到聚偏二氟乙烯/N甲基(ji)吡咯烷酮（PVDF/NMP）粘結液中，攪拌均勻(yun)(yun)，制(zhi)成正極(ji)漿料，均勻(yun)(yun)涂于鋁(lv)箔基(ji)體上。經過烘干。壓片(pian)。裁片(pian)等工(gong)(gong)藝(yi)制(zhi)成正電(dian)(dian)極(ji)。按同樣方法制(zhi)成負電(dian)(dian)極(ji)。

　　負電極(ji)基(ji)體為銅箔。

　　電池的制作及實(shi)驗(yan)(yan)合隔膜卷繞成極芯，電(dian)(dian)(dian)液為(wei)1mol/LLiPFf/EC+DEC+DMC，制成18650型電(dian)(dian)(dian)池(chi)(chi)。電(dian)(dian)(dian)池(chi)(chi)采用恒流(liu)限壓(ya)、直壓(ya)限流(liu)的充電(dian)(dian)(dian)機(ji)電(dian)(dian)(dian)源技術(shu)制，充放(fang)電(dian)(dian)(dian)壓(ya)范(fan)圍為(wei)2.75~4. 1V.電(dian)(dian)(dian)池(chi)(chi)化成電(dian)(dian)(dian)流(liu)為(wei)0.2C，循(xun)環(huan)(huan)壽命試驗(yan)(yan)的電(dian)(dian)(dian)流(liu)為(wei)1A.按ICR18650電(dian)(dian)(dian)池(chi)(chi)的技術(shu)條(tiao)件(jian)，進(jin)行了電(dian)(dian)(dian)池(chi)(chi)的倍(bei)率(lv)（1 C）、低溫（一(yi)(yi)20C、一(yi)(yi)30C、一(yi)(yi)40C）、循(xun)環(huan)(huan)壽命試驗(yan)(yan)及安全特性(xing)(xing)(xing)試驗(yan)(yan)。其(qi)中安全特性(xing)(xing)(xing)試驗(yan)(yan)包(bao)括(kuo)過充（3C充電(dian)(dian)(dian)、限壓(ya)10V）、短(duan)路（電(dian)(dian)(dian)阻小于50線(xian)路內短(duan)接(jie)）、沖擊(ji)（10kg重物(wu)、2/3m 5mm尖(jian)針刺透）、熱箱（150°C環(huan)(huan)境下(xia)放(fang)置）等。所(suo)有(you)試驗(yan)(yan)數據由計算機(ji)自動采集，試驗(yan)(yan)現象(xiang)遠程可視化監控記錄。電(dian)(dian)(dian)池(chi)(chi)的電(dian)(dian)(dian)性(xing)(xing)(xing)能試驗(yan)(yan)在(zai)ArbinBT-2401自動充放(fang)電(dian)(dian)(dian)儀(yi)上進(jin)行。

　　以LiNi2為主體的三方晶系結構。LiNi0.8C0.22材料的第一次充放電比容量分別為180mAh/g和150mAh/g這明顯高于LiC2的比容量。而且它的第一次高的充電容量為電池的設計提供了良好的基礎。因為鋰離子蓄電池的碳電極在第一次充電時，要在其表面(mian)生成一層固體電(dian)(dian)解質(zhi)保護膜(mo)，消(xiao)耗(hao)一定量(liang)(liang)的正極(ji)活性(xing)物(wu)質(zhi)成為不可逆容(rong)量(liang)(liang)。米用LiNi0.Co0.O2作(zuo)正極(ji)時，電(dian)(dian)池設計不必考(kao)慮過多增加(jia)正極(ji)活性(xing)物(wu)質(zhi)量(liang)(liang)。

　　平均每次循環(huan)容(rong)(rong)(rong)降0.04%.電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)(chi)以(yi)1C、2C速率(lv)放(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)容(rong)(rong)(rong)量分(fen)別(bie)為初始容(rong)(rong)(rong)量的99.4%和98. 9%.電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)(chi)具(ju)有良好(hao)(hao)的低溫(wen)(wen)放(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)特性(xing)，在一MCMLiCoO2電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)(chi)倍率(lv)放(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)曲(qu)線°以(yi)0. 30時，以(yi)率(lv)放(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)容(rong)(rong)(rong)量達到了(le)初始容(rong)(rong)(rong)量的80%；在一40時以(yi)0.2C速率(lv)放(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)達到了(le)初始容(rong)(rong)(rong)量的60%.電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)(chi)良好(hao)(hao)的低溫(wen)(wen)放(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)特性(xing)主要(yao)是電(dian)(dian)(dian)(dian)(dian)極材(cai)料和電(dian)(dian)(dian)(dian)(dian)MCMLiCoO2電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)(chi)低溫(wen)(wen)放(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)峨液共(gong)同作(zuo)用的結果。尤負極的18650型鋰離子(zi)蓄(xu)電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)(chi)放(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)特性(xing)曲(qu)線。電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)(chi)的放(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)容(rong)(rong)(rong)量大于1700mAh，電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)(chi)在室(shi)溫(wen)(wen)、充放(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)壓2.75放(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)效率(lv)由87%提高到90.6%.并且在優化的電(dian)(dian)(dian)(dian)(dian)液體系中，電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)(chi)的充放(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)效率(lv)可提高到近92%.通過改(gai)進(jin)電(dian)(dian)(dian)(dian)(dian)極成型加工(gong)工(gong)藝，提高了(le)電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)(chi)循環(huan)的穩定性(xing)。

　　~是以Li-CoO2為(wei)正極(ji)、MCMB為(wei)負(fu)極(ji)的18650型(xing)鋰離子蓄電池的放電特性(xing)曲(qu)線(xian)。

　　41V、1A放電電流、100%DOD條(tiao)件(jian)下(xia)，循環壽(shou)(shou)命超(chao)過(guo)1000次，平均每次循環容(rong)(rong)降0.04%.電(dian)(dian)池(chi)(chi)良好的(de)循環壽(shou)(shou)命主要(yao)得益(yi)于(yu)電(dian)(dian)極在電(dian)(dian)解(jie)液中的(de)穩定性31.電(dian)(dian)池(chi)(chi)以1C、2C速(su)率放電(dian)(dian)容(rong)(rong)量分別(bie)為初(chu)(chu)(chu)始容(rong)(rong)量的(de)945%和89.8%.電(dian)(dian)池(chi)(chi)在一由(you)圖可知，放電(dian)(dian)容(rong)(rong)量大于(yu)1550mAh，電(dian)(dian)池(chi)(chi)在室溫(wen)、充放電(dian)(dian)壓2.75~41V、1A放電(dian)(dian)電(dian)(dian)流、100%DOD條(tiao)件(jian)下(xia)，循環壽(shou)(shou)命超(chao)過(guo)1000次，C時(shi)以0.2C速(su)率放電(dian)(dian)容(rong)(rong)量為初(chu)(chu)(chu)始容(rong)(rong)量的(de)80. 5%，一30C時(shi)放電(dian)(dian)容(rong)(rong)量為初(chu)(chu)(chu)始容(rong)(rong)量的(de)57.1%. ~2為電(dian)(dian)池(chi)(chi)的(de)安全特性試驗曲線。

　　電池低溫放電曲線過充、短路、沖擊等項試lowtemperature驗中(zhong)，電(dian)池的取(qu)溫度低于120C無起火、爆炸研究與設計現象發生，安全可靠。這是因為在電(dian)池的設計及制作(zuo)中(zhong)，從材料(liao)、結(jie)構、安全裝置等多方(fang)面(mian)采取(qu)了安全保(bao)護措施。

　　3結(jie)論通(tong)過試驗和選擇電(dian)(dian)(dian)極(ji)材(cai)料，改進電(dian)(dian)(dian)極(ji)成型工(gong)藝，篩選電(dian)(dian)(dian)液體(ti)系，優化電(dian)(dian)(dian)池設計和安全設計，研(yan)制(zhi)成了為正(zheng)極(ji)、MCMB為負極(ji)的(de)18650型鋰離子蓄電(dian)(dian)(dian)池。電(dian)(dian)(dian)池具有較高的(de)放電(dian)(dian)(dian)容量和1700mAh）高的(de)比(bi)能(neng)(neng)量（130Wh/kg和350Wh/L）長的(de)工(gong)作壽(shou)命(ming)（1 000次）和良好的(de)低溫放電(dian)(dian)(dian)性(xing)能(neng)(neng)（一40°C）。電(dian)(dian)(dian)池工(gong)作安全可靠，能(neng)(neng)滿足不同領域對(dui)電(dian)(dian)(dian)池的(de)特殊要(yao)求。

                                                                                                                                  本文(wen)摘自于中國鋰電網