電源技術研究與設計高性能18650型鋰離子蓄電池張(zhang)澤(ze)波(bo)，劉(liu)秀生(sheng)，薛梅，楊清欣，汪繼強（信息產業部電子第十八研究所，天津300381）（LiNi0.8Co0.2O2）為(wei)(wei)正極，中間相炭(tan)微珠（MCMB）為(wei)(wei)負極的(de)18650型鋰離子蓄電池(chi)(chi)。電池(chi)(chi)的(de)放電容(rong)(rong)量(liang)分別大于1 700mAh電池(chi)(chi)比能量(liang)達到了130Wh/kg和350Wh/L.在(zai)室溫條(tiao)件下，0.5C電池(chi)(chi)的(de)循環壽命1000次時(shi)，其(qi)容(rong)(rong)量(liang)仍為(wei)(wei)初始容(rong)(rong)量(liang)的(de)60%.70%.以氧化(hua)鈷鋰為(wei)(wei)正極的(de)電池(chi)(chi)在(zai)一(yi)40°C.0.2C速率。終止(zhi)電壓2.5V的(de)條(tiao)件下，放電容(rong)(rong)量(liang)為(wei)(wei)室溫容(rong)(rong)量(liang)的(de)60%.實驗結果表明，電池(chi)(chi)安全可靠(kao)。

　　鋰離子蓄(xu)電池(chi)自1991年商品化(hua)(hua)(hua)以來發展(zhan)迅(xun)速。目前它不但廣(guang)泛用(yong)于(yu)攝(she)象機、筆記本電腦、蜂窩電話等便攜(xie)式電子設(she)施，而且正在成為(wei)(wei)電動車、軍事通訊、航天、航空領域電子設(she)施的(de)候選電源(yuan)111.這(zhe)就要求電池(chi)具有更(geng)高(gao)(gao)的(de)比(bi)能量、更(geng)長的(de)工作壽命及良好的(de)高(gao)(gao)、低溫放電特(te)性。為(wei)(wei)此我們試驗了高(gao)(gao)性能的(de)正極(ji)材料氧化(hua)(hua)(hua)鈷鋰(li)(li)、氧化(hua)(hua)(hua)鎳鈷鋰(li)(li)和負極(ji)碳材料一(yi)中間(jian)相炭微珠，對(dui)電池(chi)設(she)計進(jin)行優化(hua)(hua)(hua)改進(jin)電極(ji)成型(xing)工藝，篩選不同組分和配比(bi)的(de)電液(ye)體系，研制出具有高(gao)(gao)性能的(de)18650型(xing)鋰(li)(li)離子蓄(xu)電池(chi)。

　　以金(jin)屬鋰為負極，采用扣(kou)式電(dian)(dian)池試(shi)驗了正極材料(liao)LiCo2和LiNi0.8Co0.O2的(de)充放電(dian)(dian)特(te)性。充放電(dian)(dian)壓范圍(wei)3.充放電(dian)(dian)流密度0.2mA/cm2.研究了負極炭粉MCMB顆粒度及其分布與電(dian)(dian)池容量(liang)及充放電(dian)(dian)效(xiao)率(lv)的(de)關(guan)系(xi)，并(bing)試(shi)驗了負電(dian)(dian)極成型(xing)工藝條(tiao)件。

　　電液體系(xi)的篩(shai)選(xuan)對電解(jie)質為1mol/LLiPFf以碳(tan)酸(suan)乙烯酯(zhi)(zhi)（EC）為主體的不同組分〔包括碳(tan)酸(suan)二(er)乙酯(zhi)(zhi)（DEC）碳(tan)酸(suan)二(er)甲酯(zhi)(zhi)（DMC）碳(tan)酸(suan)乙甲酯(zhi)(zhi)（EMC）碳(tan)酸(suan)丙烯酯(zhi)(zhi)（PC）等〕和比例的多元(yuan)電液體系(xi)進(jin)行試驗(yan)。研(yan)究了其與電極材(cai)料的相容性(xing)(xing)(xing)和對電池(chi)容量。充(chong)放效率(lv)、盾(dun)環壽(shou)命。倍(bei)率(lv)特性(xing)(xing)(xing)。溫度特性(xing)(xing)(xing)的影響。

　　電(dian)(dian)(dian)池工(gong)藝(yi)參數(shu)的(de)(de)設(she)計(ji)和(he)電(dian)(dian)(dian)極的(de)(de)制作根據材料的(de)(de)試驗結果，設(she)計(ji)了(le)電(dian)(dian)(dian)池正負極活(huo)性物質(zhi)(zhi)的(de)(de)配比(bi)及電(dian)(dian)(dian)極的(de)(de)工(gong)藝(yi)參數(shu)。將正極活(huo)性物質(zhi)(zhi)與一定比(bi)例的(de)(de)添(tian)加劑均勻混和(he)，加到聚偏(pian)二氟乙烯/N甲基吡(bi)咯烷酮（PVDF/NMP）粘(zhan)結液中，攪(jiao)拌均勻，制成(cheng)(cheng)正極漿(jiang)料，均勻涂于鋁箔基體上。經過(guo)烘干。壓片。裁片等工(gong)藝(yi)制成(cheng)(cheng)正電(dian)(dian)(dian)極。按(an)同(tong)樣方法制成(cheng)(cheng)負電(dian)(dian)(dian)極。

　　負電極基體為(wei)銅箔。

　　電池的(de)制作及(ji)實驗合隔膜卷繞成極(ji)芯，電(dian)(dian)(dian)(dian)液(ye)為1mol/LLiPFf/EC+DEC+DMC，制成18650型電(dian)(dian)(dian)(dian)池(chi)(chi)。電(dian)(dian)(dian)(dian)池(chi)(chi)采用恒(heng)流(liu)限(xian)壓、直(zhi)壓限(xian)流(liu)的(de)充電(dian)(dian)(dian)(dian)機電(dian)(dian)(dian)(dian)源技術制，充放電(dian)(dian)(dian)(dian)壓范圍為2.75~4. 1V.電(dian)(dian)(dian)(dian)池(chi)(chi)化成電(dian)(dian)(dian)(dian)流(liu)為0.2C，循環壽命(ming)試(shi)(shi)驗的(de)電(dian)(dian)(dian)(dian)流(liu)為1A.按ICR18650電(dian)(dian)(dian)(dian)池(chi)(chi)的(de)技術條件，進行了電(dian)(dian)(dian)(dian)池(chi)(chi)的(de)倍率（1 C）、低溫（一20C、一30C、一40C）、循環壽命(ming)試(shi)(shi)驗及(ji)安(an)(an)全特性試(shi)(shi)驗。其中安(an)(an)全特性試(shi)(shi)驗包括(kuo)過充（3C充電(dian)(dian)(dian)(dian)、限(xian)壓10V）、短路（電(dian)(dian)(dian)(dian)阻小于50線路內短接）、沖擊(ji)（10kg重物、2/3m 5mm尖(jian)針刺(ci)透(tou)）、熱箱（150°C環境下放置）等(deng)。所有試(shi)(shi)驗數據由計算機自動采集，試(shi)(shi)驗現象遠程可(ke)視化監控(kong)記(ji)錄。電(dian)(dian)(dian)(dian)池(chi)(chi)的(de)電(dian)(dian)(dian)(dian)性能試(shi)(shi)驗在ArbinBT-2401自動充放電(dian)(dian)(dian)(dian)儀(yi)上(shang)進行。

　　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，要在其表面生成(cheng)一(yi)層固體電(dian)解質(zhi)保(bao)護膜，消耗一(yi)定量的正極(ji)活(huo)性物質(zhi)成(cheng)為不可逆容量。米(mi)用(yong)LiNi0.Co0.O2作正極(ji)時，電(dian)池設計(ji)不必(bi)考慮過多增(zeng)加(jia)正極(ji)活(huo)性物質(zhi)量。

　　平均每次(ci)循環容降0.04%.電(dian)(dian)(dian)(dian)池以1C、2C速率(lv)(lv)放(fang)(fang)電(dian)(dian)(dian)(dian)容量(liang)分別(bie)為初(chu)始(shi)(shi)容量(liang)的(de)99.4%和98. 9%.電(dian)(dian)(dian)(dian)池具有良(liang)好的(de)低(di)溫放(fang)(fang)電(dian)(dian)(dian)(dian)特(te)(te)性，在(zai)一(yi)MCMLiCoO2電(dian)(dian)(dian)(dian)池倍率(lv)(lv)放(fang)(fang)電(dian)(dian)(dian)(dian)曲(qu)線(xian)°以0. 30時，以率(lv)(lv)放(fang)(fang)電(dian)(dian)(dian)(dian)容量(liang)達到了(le)初(chu)始(shi)(shi)容量(liang)的(de)80%；在(zai)一(yi)40時以0.2C速率(lv)(lv)放(fang)(fang)電(dian)(dian)(dian)(dian)達到了(le)初(chu)始(shi)(shi)容量(liang)的(de)60%.電(dian)(dian)(dian)(dian)池良(liang)好的(de)低(di)溫放(fang)(fang)電(dian)(dian)(dian)(dian)特(te)(te)性主(zhu)要是電(dian)(dian)(dian)(dian)極(ji)(ji)材料和電(dian)(dian)(dian)(dian)MCMLiCoO2電(dian)(dian)(dian)(dian)池低(di)溫放(fang)(fang)電(dian)(dian)(dian)(dian)峨液(ye)共同作用的(de)結果(guo)。尤負極(ji)(ji)的(de)18650型鋰離子(zi)蓄電(dian)(dian)(dian)(dian)池放(fang)(fang)電(dian)(dian)(dian)(dian)特(te)(te)性曲(qu)線(xian)。電(dian)(dian)(dian)(dian)池的(de)放(fang)(fang)電(dian)(dian)(dian)(dian)容量(liang)大于1700mAh，電(dian)(dian)(dian)(dian)池在(zai)室溫、充放(fang)(fang)電(dian)(dian)(dian)(dian)壓2.75放(fang)(fang)電(dian)(dian)(dian)(dian)效率(lv)(lv)由(you)87%提(ti)(ti)高(gao)到90.6%.并且在(zai)優化的(de)電(dian)(dian)(dian)(dian)液(ye)體系中，電(dian)(dian)(dian)(dian)池的(de)充放(fang)(fang)電(dian)(dian)(dian)(dian)效率(lv)(lv)可提(ti)(ti)高(gao)到近92%.通過(guo)改(gai)進電(dian)(dian)(dian)(dian)極(ji)(ji)成型加工工藝，提(ti)(ti)高(gao)了(le)電(dian)(dian)(dian)(dian)池循環的(de)穩定性。

　　~是以Li-CoO2為正極、MCMB為負極的18650型(xing)鋰離子蓄(xu)電池(chi)的放電特性曲線(xian)。

　　41V、1A放電電流、100%DOD條件(jian)(jian)下(xia)，循(xun)(xun)環壽命(ming)(ming)超(chao)(chao)過(guo)1000次(ci)，平均每(mei)次(ci)循(xun)(xun)環容(rong)(rong)降0.04%.電(dian)(dian)(dian)(dian)池良好的循(xun)(xun)環壽命(ming)(ming)主要得益于電(dian)(dian)(dian)(dian)極在電(dian)(dian)(dian)(dian)解液中(zhong)的穩定性31.電(dian)(dian)(dian)(dian)池以1C、2C速率放(fang)電(dian)(dian)(dian)(dian)容(rong)(rong)量(liang)分別為初(chu)始(shi)容(rong)(rong)量(liang)的945%和89.8%.電(dian)(dian)(dian)(dian)池在一由圖可知，放(fang)電(dian)(dian)(dian)(dian)容(rong)(rong)量(liang)大于1550mAh，電(dian)(dian)(dian)(dian)池在室溫(wen)、充放(fang)電(dian)(dian)(dian)(dian)壓2.75~41V、1A放(fang)電(dian)(dian)(dian)(dian)電(dian)(dian)(dian)(dian)流、100%DOD條件(jian)(jian)下(xia)，循(xun)(xun)環壽命(ming)(ming)超(chao)(chao)過(guo)1000次(ci)，C時以0.2C速率放(fang)電(dian)(dian)(dian)(dian)容(rong)(rong)量(liang)為初(chu)始(shi)容(rong)(rong)量(liang)的80. 5%，一30C時放(fang)電(dian)(dian)(dian)(dian)容(rong)(rong)量(liang)為初(chu)始(shi)容(rong)(rong)量(liang)的57.1%. ~2為電(dian)(dian)(dian)(dian)池的安全特性試驗曲線。

　　電池低溫放電曲線過充、短路、沖擊等(deng)項試lowtemperature驗中(zhong)，電池的(de)取(qu)溫(wen)度低(di)于(yu)120C無(wu)起火、爆炸研究與(yu)設計(ji)現象發生，安全(quan)可靠。這是因為在電池的(de)設計(ji)及制作中(zhong)，從材料、結(jie)構、安全(quan)裝置等(deng)多方面采(cai)取(qu)了(le)安全(quan)保護措施(shi)。

　　3結論通(tong)過試驗和(he)(he)選擇電(dian)(dian)(dian)(dian)(dian)(dian)極材料，改進電(dian)(dian)(dian)(dian)(dian)(dian)極成型工藝(yi)，篩(shai)選電(dian)(dian)(dian)(dian)(dian)(dian)液體系，優化電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)設(she)(she)計和(he)(he)安全(quan)設(she)(she)計，研制(zhi)成了為正極、MCMB為負極的(de)(de)(de)18650型鋰離子蓄電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)。電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)具(ju)有較高的(de)(de)(de)放(fang)電(dian)(dian)(dian)(dian)(dian)(dian)容量(liang)和(he)(he)1700mAh）高的(de)(de)(de)比能量(liang)（130Wh/kg和(he)(he)350Wh/L）長的(de)(de)(de)工作(zuo)壽命(ming)（1 000次）和(he)(he)良好的(de)(de)(de)低溫放(fang)電(dian)(dian)(dian)(dian)(dian)(dian)性能（一(yi)40°C）。電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)工作(zuo)安全(quan)可靠，能滿足(zu)不同領域對電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)的(de)(de)(de)特殊要(yao)求。

                                                                                                                                  本文摘自于(yu)中國鋰電網