電源技術研究與設計高性能18650型鋰離子蓄電池張(zhang)澤波，劉秀生，薛梅，楊(yang)清欣，汪繼強（信息(xi)產(chan)業(ye)部電(dian)(dian)子第十八研究所，天津300381）（LiNi0.8Co0.2O2）為正(zheng)極(ji)，中間相炭微(wei)珠(zhu)（MCMB）為負(fu)極(ji)的(de)(de)(de)18650型鋰離子蓄電(dian)(dian)池。電(dian)(dian)池的(de)(de)(de)放(fang)電(dian)(dian)容(rong)(rong)量(liang)(liang)分(fen)別大于1 700mAh電(dian)(dian)池比能量(liang)(liang)達到了130Wh/kg和350Wh/L.在(zai)室(shi)溫條件下，0.5C電(dian)(dian)池的(de)(de)(de)循環壽命(ming)1000次時，其容(rong)(rong)量(liang)(liang)仍(reng)為初(chu)始容(rong)(rong)量(liang)(liang)的(de)(de)(de)60%.70%.以氧化鈷鋰為正(zheng)極(ji)的(de)(de)(de)電(dian)(dian)池在(zai)一40°C.0.2C速(su)率。終止電(dian)(dian)壓2.5V的(de)(de)(de)條件下，放(fang)電(dian)(dian)容(rong)(rong)量(liang)(liang)為室(shi)溫容(rong)(rong)量(liang)(liang)的(de)(de)(de)60%.實驗(yan)結果表明，電(dian)(dian)池安(an)全可(ke)靠。

　　鋰離子蓄(xu)電(dian)(dian)(dian)池(chi)(chi)自1991年(nian)商品化以來發展迅速。目(mu)前(qian)它不但廣泛用于攝(she)象機、筆記(ji)本電(dian)(dian)(dian)腦、蜂窩電(dian)(dian)(dian)話(hua)等(deng)便攜(xie)式電(dian)(dian)(dian)子(zi)設(she)施，而(er)且正在成(cheng)為(wei)電(dian)(dian)(dian)動車、軍事通訊、航天、航空(kong)領域電(dian)(dian)(dian)子(zi)設(she)施的(de)(de)候選電(dian)(dian)(dian)源111.這就要(yao)求(qiu)電(dian)(dian)(dian)池(chi)(chi)具(ju)有更高的(de)(de)比能量、更長的(de)(de)工(gong)作壽命及(ji)良好(hao)的(de)(de)高、低溫(wen)放電(dian)(dian)(dian)特性(xing)(xing)。為(wei)此我們試驗了高性(xing)(xing)能的(de)(de)正極材料氧化鈷(gu)鋰(li)、氧化鎳鈷(gu)鋰(li)和(he)負極碳材料一中間相炭微珠，對(dui)電(dian)(dian)(dian)池(chi)(chi)設(she)計進行(xing)優(you)化改進電(dian)(dian)(dian)極成(cheng)型工(gong)藝，篩選不同組分和(he)配(pei)比的(de)(de)電(dian)(dian)(dian)液體系，研制出具(ju)有高性(xing)(xing)能的(de)(de)18650型鋰(li)離子(zi)蓄(xu)電(dian)(dian)(dian)池(chi)(chi)。

　　以金屬鋰為負(fu)極，采用扣式電(dian)池試驗了正(zheng)極材料LiCo2和LiNi0.8Co0.O2的(de)充放(fang)電(dian)特性。充放(fang)電(dian)壓范圍3.充放(fang)電(dian)流密度0.2mA/cm2.研究(jiu)了負(fu)極炭(tan)粉MCMB顆粒度及(ji)其分布(bu)與電(dian)池容量及(ji)充放(fang)電(dian)效率的(de)關系，并試驗了負(fu)電(dian)極成型工(gong)藝(yi)條件。

　　電(dian)液體(ti)系的(de)篩選(xuan)對電(dian)解質(zhi)為1mol/LLiPFf以碳(tan)酸(suan)(suan)乙(yi)烯酯(zhi)(zhi)（EC）為主體(ti)的(de)不同組(zu)分〔包(bao)括碳(tan)酸(suan)(suan)二乙(yi)酯(zhi)(zhi)（DEC）碳(tan)酸(suan)(suan)二甲酯(zhi)(zhi)（DMC）碳(tan)酸(suan)(suan)乙(yi)甲酯(zhi)(zhi)（EMC）碳(tan)酸(suan)(suan)丙烯酯(zhi)(zhi)（PC）等〕和比(bi)例的(de)多元電(dian)液體(ti)系進行(xing)試驗(yan)。研究了(le)其與電(dian)極材料的(de)相容(rong)(rong)性和對電(dian)池容(rong)(rong)量。充(chong)放效率(lv)、盾環壽(shou)命。倍(bei)率(lv)特(te)性。溫度特(te)性的(de)影響。

　　電(dian)(dian)池工(gong)藝(yi)(yi)參(can)數的(de)(de)(de)設(she)計和電(dian)(dian)極(ji)(ji)的(de)(de)(de)制(zhi)作根據材料的(de)(de)(de)試驗結果，設(she)計了(le)電(dian)(dian)池正(zheng)負(fu)極(ji)(ji)活(huo)性物質的(de)(de)(de)配比(bi)及電(dian)(dian)極(ji)(ji)的(de)(de)(de)工(gong)藝(yi)(yi)參(can)數。將正(zheng)極(ji)(ji)活(huo)性物質與一定比(bi)例的(de)(de)(de)添加(jia)劑均(jun)勻(yun)混和，加(jia)到聚(ju)偏二(er)氟乙烯/N甲基(ji)吡(bi)咯(ge)烷(wan)酮（PVDF/NMP）粘結液中，攪拌均(jun)勻(yun)，制(zhi)成正(zheng)極(ji)(ji)漿料，均(jun)勻(yun)涂于鋁箔基(ji)體上。經過烘干。壓片(pian)。裁片(pian)等工(gong)藝(yi)(yi)制(zhi)成正(zheng)電(dian)(dian)極(ji)(ji)。按同樣方法制(zhi)成負(fu)電(dian)(dian)極(ji)(ji)。

　　負電極基體(ti)為(wei)銅箔。

　　電池的制(zhi)作及(ji)實驗(yan)合隔膜卷繞成極(ji)芯，電(dian)(dian)(dian)液為1mol/LLiPFf/EC+DEC+DMC，制(zhi)成18650型電(dian)(dian)(dian)池(chi)(chi)。電(dian)(dian)(dian)池(chi)(chi)采用恒流限(xian)(xian)壓(ya)(ya)、直壓(ya)(ya)限(xian)(xian)流的充(chong)電(dian)(dian)(dian)機(ji)電(dian)(dian)(dian)源技術(shu)制(zhi)，充(chong)放(fang)電(dian)(dian)(dian)壓(ya)(ya)范圍為2.75~4. 1V.電(dian)(dian)(dian)池(chi)(chi)化成電(dian)(dian)(dian)流為0.2C，循環壽命試(shi)驗(yan)的電(dian)(dian)(dian)流為1A.按ICR18650電(dian)(dian)(dian)池(chi)(chi)的技術(shu)條件，進(jin)行(xing)了電(dian)(dian)(dian)池(chi)(chi)的倍率（1 C）、低溫(wen)（一20C、一30C、一40C）、循環壽命試(shi)驗(yan)及(ji)安(an)(an)全(quan)特性(xing)試(shi)驗(yan)。其中安(an)(an)全(quan)特性(xing)試(shi)驗(yan)包括過充(chong)（3C充(chong)電(dian)(dian)(dian)、限(xian)(xian)壓(ya)(ya)10V）、短(duan)路（電(dian)(dian)(dian)阻小(xiao)于50線路內短(duan)接）、沖擊（10kg重物、2/3m 5mm尖針刺透）、熱箱（150°C環境下放(fang)置）等。所有試(shi)驗(yan)數(shu)據由計算機(ji)自動采集，試(shi)驗(yan)現象遠程可視化監(jian)控記錄。電(dian)(dian)(dian)池(chi)(chi)的電(dian)(dian)(dian)性(xing)能試(shi)驗(yan)在(zai)ArbinBT-2401自動充(chong)放(fang)電(dian)(dian)(dian)儀上進(jin)行(xing)。

　　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(qi)表面生(sheng)成一(yi)層固體電解質(zhi)保護膜，消耗一(yi)定量(liang)的正(zheng)極活(huo)性(xing)(xing)物質(zhi)成為不可逆容量(liang)。米(mi)用LiNi0.Co0.O2作(zuo)正(zheng)極時，電池設計不必考慮過多(duo)增加正(zheng)極活(huo)性(xing)(xing)物質(zhi)量(liang)。

　　平均(jun)每次循環(huan)(huan)容(rong)降0.04%.電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)以(yi)1C、2C速率(lv)放(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)容(rong)量分別為初始容(rong)量的(de)99.4%和98. 9%.電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)具有(you)良(liang)好的(de)低溫(wen)放(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)特性，在(zai)(zai)一MCMLiCoO2電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)倍(bei)率(lv)放(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)曲線(xian)(xian)°以(yi)0. 30時(shi)，以(yi)率(lv)放(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)容(rong)量達(da)到(dao)了(le)(le)初始容(rong)量的(de)80%；在(zai)(zai)一40時(shi)以(yi)0.2C速率(lv)放(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)達(da)到(dao)了(le)(le)初始容(rong)量的(de)60%.電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)良(liang)好的(de)低溫(wen)放(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)特性主要是電(dian)(dian)(dian)(dian)(dian)(dian)極(ji)材料和電(dian)(dian)(dian)(dian)(dian)(dian)MCMLiCoO2電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)低溫(wen)放(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)峨液共同(tong)作用(yong)的(de)結果(guo)。尤負極(ji)的(de)18650型(xing)鋰離子蓄電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)放(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)特性曲線(xian)(xian)。電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)的(de)放(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)容(rong)量大于1700mAh，電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)在(zai)(zai)室溫(wen)、充放(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)壓(ya)2.75放(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)效率(lv)由87%提(ti)高到(dao)90.6%.并且在(zai)(zai)優(you)化的(de)電(dian)(dian)(dian)(dian)(dian)(dian)液體系中，電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)的(de)充放(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)效率(lv)可提(ti)高到(dao)近92%.通過改進電(dian)(dian)(dian)(dian)(dian)(dian)極(ji)成(cheng)型(xing)加工(gong)工(gong)藝，提(ti)高了(le)(le)電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)循環(huan)(huan)的(de)穩定性。

　　~是(shi)以Li-CoO2為正極、MCMB為負(fu)極的(de)18650型鋰離子蓄電池的(de)放電特(te)性曲線。

　　41V、1A放電電流、100%DOD條(tiao)件下，循(xun)環(huan)壽(shou)命(ming)超過1000次(ci)，平均每次(ci)循(xun)環(huan)容(rong)(rong)降0.04%.電(dian)(dian)(dian)(dian)池(chi)良好的(de)循(xun)環(huan)壽(shou)命(ming)主要得益于電(dian)(dian)(dian)(dian)極(ji)在電(dian)(dian)(dian)(dian)解液中(zhong)的(de)穩(wen)定性31.電(dian)(dian)(dian)(dian)池(chi)以1C、2C速率(lv)(lv)放電(dian)(dian)(dian)(dian)容(rong)(rong)量(liang)分別為(wei)(wei)初(chu)(chu)(chu)始(shi)(shi)容(rong)(rong)量(liang)的(de)945%和89.8%.電(dian)(dian)(dian)(dian)池(chi)在一由圖可知，放電(dian)(dian)(dian)(dian)容(rong)(rong)量(liang)大于1550mAh，電(dian)(dian)(dian)(dian)池(chi)在室溫、充放電(dian)(dian)(dian)(dian)壓(ya)2.75~41V、1A放電(dian)(dian)(dian)(dian)電(dian)(dian)(dian)(dian)流、100%DOD條(tiao)件下，循(xun)環(huan)壽(shou)命(ming)超過1000次(ci)，C時(shi)以0.2C速率(lv)(lv)放電(dian)(dian)(dian)(dian)容(rong)(rong)量(liang)為(wei)(wei)初(chu)(chu)(chu)始(shi)(shi)容(rong)(rong)量(liang)的(de)80. 5%，一30C時(shi)放電(dian)(dian)(dian)(dian)容(rong)(rong)量(liang)為(wei)(wei)初(chu)(chu)(chu)始(shi)(shi)容(rong)(rong)量(liang)的(de)57.1%. ~2為(wei)(wei)電(dian)(dian)(dian)(dian)池(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(shi)lowtemperature驗中，電池(chi)的取(qu)溫度低于120C無起火、爆炸研究與設(she)計現象發生(sheng)，安(an)全可靠。這是因為在電池(chi)的設(she)計及制作中，從材料、結構(gou)、安(an)全裝置等多方(fang)面采取(qu)了安(an)全保護措(cuo)施。

　　3結(jie)論通過試(shi)驗和(he)選擇電(dian)(dian)極(ji)材料，改(gai)進電(dian)(dian)極(ji)成型工(gong)藝，篩選電(dian)(dian)液體系，優化電(dian)(dian)池(chi)設計(ji)和(he)安(an)全設計(ji)，研(yan)制成了(le)為正極(ji)、MCMB為負極(ji)的(de)(de)18650型鋰(li)離(li)子(zi)蓄(xu)電(dian)(dian)池(chi)。電(dian)(dian)池(chi)具有較高的(de)(de)放(fang)電(dian)(dian)容量(liang)和(he)1700mAh）高的(de)(de)比能量(liang)（130Wh/kg和(he)350Wh/L）長(chang)的(de)(de)工(gong)作壽命（1 000次）和(he)良好的(de)(de)低溫放(fang)電(dian)(dian)性能（一(yi)40°C）。電(dian)(dian)池(chi)工(gong)作安(an)全可靠，能滿足不同領(ling)域對(dui)電(dian)(dian)池(chi)的(de)(de)特殊要求。

                                                                                                                                  本文(wen)摘(zhai)自于中國鋰電網