電源技術研究與設計高性能18650型鋰離子蓄電池張澤波，劉(liu)秀生，薛梅，楊清欣，汪繼強（信息產業部電(dian)(dian)子第十八研究所，天津300381）（LiNi0.8Co0.2O2）為正極，中間(jian)相炭微(wei)珠（MCMB）為負(fu)極的(de)18650型鋰離子蓄電(dian)(dian)池。電(dian)(dian)池的(de)放(fang)電(dian)(dian)容(rong)(rong)量(liang)分別大于1 700mAh電(dian)(dian)池比能量(liang)達到(dao)了130Wh/kg和350Wh/L.在室(shi)溫條(tiao)件下，0.5C電(dian)(dian)池的(de)循環壽命1000次(ci)時，其(qi)容(rong)(rong)量(liang)仍為初始容(rong)(rong)量(liang)的(de)60%.70%.以氧化鈷鋰為正極的(de)電(dian)(dian)池在一40°C.0.2C速率。終止電(dian)(dian)壓(ya)2.5V的(de)條(tiao)件下，放(fang)電(dian)(dian)容(rong)(rong)量(liang)為室(shi)溫容(rong)(rong)量(liang)的(de)60%.實驗(yan)結果表明，電(dian)(dian)池安全(quan)可靠。

　　鋰離子蓄(xu)電(dian)(dian)池(chi)(chi)自1991年商品化(hua)(hua)(hua)(hua)以來發展(zhan)迅速。目前它不(bu)(bu)但(dan)廣泛(fan)用(yong)于攝(she)象(xiang)機、筆記本電(dian)(dian)腦、蜂窩電(dian)(dian)話等便攜式電(dian)(dian)子(zi)設施(shi)，而且正(zheng)在成為電(dian)(dian)動車、軍(jun)事通訊、航(hang)天、航(hang)空(kong)領(ling)域電(dian)(dian)子(zi)設施(shi)的(de)候(hou)選(xuan)電(dian)(dian)源111.這就要求(qiu)電(dian)(dian)池(chi)(chi)具有更(geng)高(gao)的(de)比(bi)能(neng)量(liang)、更(geng)長的(de)工作壽命及(ji)良好的(de)高(gao)、低(di)溫放電(dian)(dian)特性。為此我們試驗了高(gao)性能(neng)的(de)正(zheng)極(ji)材料氧化(hua)(hua)(hua)(hua)鈷(gu)鋰、氧化(hua)(hua)(hua)(hua)鎳鈷(gu)鋰和(he)負極(ji)碳材料一中間相(xiang)炭微珠，對電(dian)(dian)池(chi)(chi)設計(ji)進(jin)行(xing)優化(hua)(hua)(hua)(hua)改(gai)進(jin)電(dian)(dian)極(ji)成型(xing)工藝(yi)，篩選(xuan)不(bu)(bu)同組分和(he)配(pei)比(bi)的(de)電(dian)(dian)液體系，研制出具有高(gao)性能(neng)的(de)18650型(xing)鋰離(li)子(zi)蓄(xu)電(dian)(dian)池(chi)(chi)。

　　以金屬鋰為負(fu)極(ji)(ji)(ji)，采(cai)用扣式電(dian)池試(shi)驗了正極(ji)(ji)(ji)材(cai)料LiCo2和LiNi0.8Co0.O2的充放電(dian)特性。充放電(dian)壓范圍3.充放電(dian)流密度0.2mA/cm2.研究了負(fu)極(ji)(ji)(ji)炭粉(fen)MCMB顆(ke)粒(li)度及(ji)其分(fen)布(bu)與電(dian)池容(rong)量(liang)及(ji)充放電(dian)效率的關系(xi)，并試(shi)驗了負(fu)電(dian)極(ji)(ji)(ji)成型工藝條件。

　　電(dian)液體(ti)(ti)系(xi)的(de)篩選對電(dian)解質為1mol/LLiPFf以(yi)碳酸(suan)乙烯酯(zhi)(zhi)（EC）為主體(ti)(ti)的(de)不同組分〔包括(kuo)碳酸(suan)二乙酯(zhi)(zhi)（DEC）碳酸(suan)二甲酯(zhi)(zhi)（DMC）碳酸(suan)乙甲酯(zhi)(zhi)（EMC）碳酸(suan)丙烯酯(zhi)(zhi)（PC）等(deng)〕和(he)比例的(de)多元電(dian)液體(ti)(ti)系(xi)進(jin)行試驗。研究(jiu)了其與電(dian)極材(cai)料的(de)相容(rong)性和(he)對電(dian)池(chi)容(rong)量。充放(fang)效率、盾環壽命。倍率特(te)性。溫度特(te)性的(de)影(ying)響。

　　電(dian)(dian)(dian)池(chi)工藝(yi)參(can)數(shu)的設計和電(dian)(dian)(dian)極(ji)的制作根據材(cai)料(liao)的試驗結果(guo)，設計了電(dian)(dian)(dian)池(chi)正負(fu)極(ji)活性物質(zhi)的配(pei)比及電(dian)(dian)(dian)極(ji)的工藝(yi)參(can)數(shu)。將正極(ji)活性物質(zhi)與一定比例的添加(jia)劑均勻(yun)混和，加(jia)到聚偏(pian)二氟乙烯/N甲基(ji)(ji)吡(bi)咯烷酮（PVDF/NMP）粘結液中，攪拌均勻(yun)，制成正極(ji)漿料(liao)，均勻(yun)涂(tu)于鋁箔基(ji)(ji)體(ti)上。經過烘干。壓片。裁片等(deng)工藝(yi)制成正電(dian)(dian)(dian)極(ji)。按同(tong)樣(yang)方法制成負(fu)電(dian)(dian)(dian)極(ji)。

　　負電極基體(ti)為銅箔。

　　電池的制(zhi)(zhi)作及實驗合隔(ge)膜卷(juan)繞(rao)成(cheng)(cheng)極芯，電(dian)(dian)(dian)(dian)(dian)(dian)液為1mol/LLiPFf/EC+DEC+DMC，制(zhi)(zhi)成(cheng)(cheng)18650型電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)(chi)。電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)(chi)采(cai)(cai)用恒流限壓、直壓限流的充(chong)電(dian)(dian)(dian)(dian)(dian)(dian)機(ji)電(dian)(dian)(dian)(dian)(dian)(dian)源技術制(zhi)(zhi)，充(chong)放(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)壓范圍為2.75~4. 1V.電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)(chi)化成(cheng)(cheng)電(dian)(dian)(dian)(dian)(dian)(dian)流為0.2C，循環(huan)壽命試驗的電(dian)(dian)(dian)(dian)(dian)(dian)流為1A.按ICR18650電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)(chi)的技術條件，進(jin)行了電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)(chi)的倍率（1 C）、低(di)溫（一20C、一30C、一40C）、循環(huan)壽命試驗及安全特性(xing)試驗。其中(zhong)安全特性(xing)試驗包(bao)括過充(chong)（3C充(chong)電(dian)(dian)(dian)(dian)(dian)(dian)、限壓10V）、短(duan)路（電(dian)(dian)(dian)(dian)(dian)(dian)阻(zu)小于50線路內短(duan)接）、沖擊（10kg重物、2/3m 5mm尖(jian)針刺透(tou)）、熱箱（150°C環(huan)境(jing)下放(fang)(fang)置）等。所有試驗數據由計算(suan)機(ji)自(zi)動采(cai)(cai)集，試驗現象遠程可(ke)視化監(jian)控記(ji)錄。電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)(chi)的電(dian)(dian)(dian)(dian)(dian)(dian)性(xing)能試驗在ArbinBT-2401自(zi)動充(chong)放(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)儀上進(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(biao)面生成一層固體(ti)電解質保護膜，消耗一定(ding)量(liang)的(de)正(zheng)極活性物(wu)質成為不可逆容(rong)量(liang)。米用LiNi0.Co0.O2作正(zheng)極時，電池設計不必考慮過多(duo)增加(jia)正(zheng)極活性物(wu)質量(liang)。

　　平均每次(ci)循環容(rong)(rong)(rong)降0.04%.電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)池以(yi)(yi)1C、2C速(su)率(lv)放(fang)(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)容(rong)(rong)(rong)量(liang)(liang)(liang)分別為初(chu)始(shi)容(rong)(rong)(rong)量(liang)(liang)(liang)的(de)(de)(de)99.4%和98. 9%.電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)池具有良(liang)好(hao)(hao)的(de)(de)(de)低溫(wen)(wen)放(fang)(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)特性，在(zai)一(yi)MCMLiCoO2電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)池倍率(lv)放(fang)(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)曲線°以(yi)(yi)0. 30時，以(yi)(yi)率(lv)放(fang)(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)容(rong)(rong)(rong)量(liang)(liang)(liang)達到(dao)(dao)了(le)初(chu)始(shi)容(rong)(rong)(rong)量(liang)(liang)(liang)的(de)(de)(de)80%；在(zai)一(yi)40時以(yi)(yi)0.2C速(su)率(lv)放(fang)(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)達到(dao)(dao)了(le)初(chu)始(shi)容(rong)(rong)(rong)量(liang)(liang)(liang)的(de)(de)(de)60%.電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)池良(liang)好(hao)(hao)的(de)(de)(de)低溫(wen)(wen)放(fang)(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)特性主要是(shi)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)極(ji)材料和電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)MCMLiCoO2電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)池低溫(wen)(wen)放(fang)(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)峨液(ye)共同作用的(de)(de)(de)結果。尤(you)負極(ji)的(de)(de)(de)18650型鋰(li)離子蓄電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)池放(fang)(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)特性曲線。電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)池的(de)(de)(de)放(fang)(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)容(rong)(rong)(rong)量(liang)(liang)(liang)大于1700mAh，電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)池在(zai)室溫(wen)(wen)、充(chong)放(fang)(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)壓2.75放(fang)(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)效率(lv)由87%提(ti)高(gao)到(dao)(dao)90.6%.并且在(zai)優化(hua)的(de)(de)(de)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)液(ye)體系中，電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)池的(de)(de)(de)充(chong)放(fang)(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)效率(lv)可提(ti)高(gao)到(dao)(dao)近92%.通過(guo)改進電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)極(ji)成型加工(gong)工(gong)藝，提(ti)高(gao)了(le)電(dian)(dian)(dian)(dian)(dian)(dian)(dian)(dian)池循環的(de)(de)(de)穩定性。

　　~是以Li-CoO2為正極、MCMB為負極的(de)(de)18650型鋰(li)離(li)子蓄電池的(de)(de)放電特性曲線。

　　41V、1A放電電流、100%DOD條件下，循環(huan)(huan)壽命(ming)超過(guo)1000次(ci)，平均每次(ci)循環(huan)(huan)容(rong)降0.04%.電(dian)池良好的(de)循環(huan)(huan)壽命(ming)主要得(de)益(yi)于電(dian)極在電(dian)解(jie)液中的(de)穩(wen)定性(xing)31.電(dian)池以1C、2C速(su)率放電(dian)容(rong)量(liang)(liang)分別(bie)為(wei)(wei)初始(shi)容(rong)量(liang)(liang)的(de)945%和89.8%.電(dian)池在一(yi)由圖可(ke)知(zhi)，放電(dian)容(rong)量(liang)(liang)大于1550mAh，電(dian)池在室溫、充放電(dian)壓2.75~41V、1A放電(dian)電(dian)流、100%DOD條件下，循環(huan)(huan)壽命(ming)超過(guo)1000次(ci)，C時(shi)以0.2C速(su)率放電(dian)容(rong)量(liang)(liang)為(wei)(wei)初始(shi)容(rong)量(liang)(liang)的(de)80. 5%，一(yi)30C時(shi)放電(dian)容(rong)量(liang)(liang)為(wei)(wei)初始(shi)容(rong)量(liang)(liang)的(de)57.1%. ~2為(wei)(wei)電(dian)池的(de)安全(quan)特性(xing)試驗曲線。

　　電池低溫放電曲線過充、短路、沖擊等(deng)項試lowtemperature驗中，電(dian)池(chi)的(de)取溫度低于120C無(wu)起火、爆炸研究與設計(ji)現象發生，安全可靠。這是(shi)因為在電(dian)池(chi)的(de)設計(ji)及制作中，從材料、結構、安全裝(zhuang)置等(deng)多(duo)方面采(cai)取了安全保護措(cuo)施。

　　3結(jie)論通(tong)過(guo)試驗(yan)和(he)選擇電(dian)(dian)(dian)(dian)(dian)極材料，改進(jin)電(dian)(dian)(dian)(dian)(dian)極成(cheng)型工藝(yi)，篩選電(dian)(dian)(dian)(dian)(dian)液體系，優化電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)設計和(he)安(an)全設計，研(yan)制成(cheng)了為正(zheng)極、MCMB為負極的18650型鋰離子蓄電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)。電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)具有(you)較高的放電(dian)(dian)(dian)(dian)(dian)容(rong)量(liang)和(he)1700mAh）高的比能(neng)量(liang)（130Wh/kg和(he)350Wh/L）長(chang)的工作壽命（1 000次）和(he)良好的低溫放電(dian)(dian)(dian)(dian)(dian)性能(neng)（一40°C）。電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)工作安(an)全可靠，能(neng)滿足不同(tong)領域(yu)對電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)的特殊要求。

                                                                                                                                  本文摘自于中國(guo)鋰電網