電源技術研究與設計高性能18650型鋰離子蓄電池張澤波，劉秀生，薛梅，楊清欣，汪繼(ji)強（信息(xi)產業部電(dian)子第(di)十八研究所，天津300381）（LiNi0.8Co0.2O2）為(wei)正(zheng)極(ji)，中間(jian)相(xiang)炭(tan)微珠（MCMB）為(wei)負(fu)極(ji)的(de)(de)(de)18650型鋰(li)離子蓄電(dian)池(chi)。電(dian)池(chi)的(de)(de)(de)放電(dian)容量分別大于(yu)1 700mAh電(dian)池(chi)比能(neng)量達到了130Wh/kg和350Wh/L.在(zai)室溫條(tiao)件下，0.5C電(dian)池(chi)的(de)(de)(de)循(xun)環壽(shou)命1000次(ci)時(shi)，其容量仍為(wei)初始容量的(de)(de)(de)60%.70%.以氧(yang)化鈷鋰(li)為(wei)正(zheng)極(ji)的(de)(de)(de)電(dian)池(chi)在(zai)一40°C.0.2C速率。終(zhong)止電(dian)壓2.5V的(de)(de)(de)條(tiao)件下，放電(dian)容量為(wei)室溫容量的(de)(de)(de)60%.實驗結果(guo)表(biao)明，電(dian)池(chi)安全可靠。

　　鋰離子蓄電(dian)池(chi)自1991年商(shang)品化(hua)(hua)(hua)以來發展迅速。目前它不(bu)但廣泛(fan)用(yong)于攝象機(ji)、筆記本電(dian)腦、蜂窩(wo)電(dian)話(hua)等便攜式(shi)電(dian)子(zi)設(she)施(shi)，而(er)且(qie)正在成為(wei)(wei)電(dian)動車、軍事通訊、航(hang)天、航(hang)空領域電(dian)子(zi)設(she)施(shi)的(de)(de)候選電(dian)源111.這就要求電(dian)池(chi)具有更(geng)高的(de)(de)比能量(liang)、更(geng)長的(de)(de)工(gong)作壽(shou)命及良好的(de)(de)高、低溫放(fang)電(dian)特性。為(wei)(wei)此我(wo)們試(shi)驗了(le)高性能的(de)(de)正極(ji)(ji)材料氧化(hua)(hua)(hua)鈷鋰、氧化(hua)(hua)(hua)鎳鈷鋰和(he)負(fu)極(ji)(ji)碳材料一中間相炭(tan)微珠，對(dui)電(dian)池(chi)設(she)計進行優(you)化(hua)(hua)(hua)改(gai)進電(dian)極(ji)(ji)成型工(gong)藝，篩選不(bu)同組分和(he)配比的(de)(de)電(dian)液體系，研制出具有高性能的(de)(de)18650型鋰離子(zi)蓄電(dian)池(chi)。

　　以金屬鋰(li)為負極，采用扣式電池試驗了(le)正極材(cai)料LiCo2和LiNi0.8Co0.O2的充(chong)放(fang)電特性。充(chong)放(fang)電壓范圍(wei)3.充(chong)放(fang)電流密度0.2mA/cm2.研究了(le)負極炭(tan)粉MCMB顆粒(li)度及(ji)(ji)其分布與電池容(rong)量及(ji)(ji)充(chong)放(fang)電效(xiao)率的關(guan)系，并試驗了(le)負電極成(cheng)型工藝條件。

　　電(dian)(dian)(dian)液(ye)體(ti)系(xi)(xi)的(de)(de)(de)篩選對電(dian)(dian)(dian)解(jie)質為1mol/LLiPFf以碳(tan)酸(suan)(suan)乙烯酯(zhi)(zhi)（EC）為主(zhu)體(ti)的(de)(de)(de)不同(tong)組分(fen)〔包括碳(tan)酸(suan)(suan)二乙酯(zhi)(zhi)（DEC）碳(tan)酸(suan)(suan)二甲酯(zhi)(zhi)（DMC）碳(tan)酸(suan)(suan)乙甲酯(zhi)(zhi)（EMC）碳(tan)酸(suan)(suan)丙烯酯(zhi)(zhi)（PC）等〕和(he)比例的(de)(de)(de)多元電(dian)(dian)(dian)液(ye)體(ti)系(xi)(xi)進行試驗。研(yan)究了其與電(dian)(dian)(dian)極材料的(de)(de)(de)相容性(xing)和(he)對電(dian)(dian)(dian)池容量。充放效率(lv)、盾環壽命。倍(bei)率(lv)特性(xing)。溫度特性(xing)的(de)(de)(de)影響。

　　電(dian)(dian)池工(gong)藝(yi)參(can)數(shu)的(de)(de)(de)設計和(he)電(dian)(dian)極(ji)的(de)(de)(de)制(zhi)作根(gen)據材料(liao)(liao)的(de)(de)(de)試驗結果，設計了電(dian)(dian)池正負極(ji)活性(xing)物(wu)質的(de)(de)(de)配比(bi)及電(dian)(dian)極(ji)的(de)(de)(de)工(gong)藝(yi)參(can)數(shu)。將正極(ji)活性(xing)物(wu)質與一(yi)定比(bi)例(li)的(de)(de)(de)添加劑(ji)均(jun)勻(yun)混和(he)，加到聚偏二氟(fu)乙烯/N甲基吡(bi)咯烷酮（PVDF/NMP）粘(zhan)結液中，攪(jiao)拌均(jun)勻(yun)，制(zhi)成(cheng)(cheng)正極(ji)漿料(liao)(liao)，均(jun)勻(yun)涂于鋁箔基體上(shang)。經過(guo)烘(hong)干。壓片(pian)。裁片(pian)等工(gong)藝(yi)制(zhi)成(cheng)(cheng)正電(dian)(dian)極(ji)。按同樣方(fang)法(fa)制(zhi)成(cheng)(cheng)負電(dian)(dian)極(ji)。

　　負電極基(ji)體為銅箔。

　　電池的制(zhi)作(zuo)及實驗(yan)(yan)(yan)合(he)隔膜卷(juan)繞成(cheng)極(ji)芯，電(dian)(dian)液為1mol/LLiPFf/EC+DEC+DMC，制(zhi)成(cheng)18650型(xing)電(dian)(dian)池。電(dian)(dian)池采(cai)用(yong)恒流(liu)(liu)限壓(ya)、直壓(ya)限流(liu)(liu)的充(chong)(chong)電(dian)(dian)機電(dian)(dian)源技術(shu)制(zhi)，充(chong)(chong)放(fang)(fang)電(dian)(dian)壓(ya)范圍為2.75~4. 1V.電(dian)(dian)池化成(cheng)電(dian)(dian)流(liu)(liu)為0.2C，循(xun)環壽命試(shi)驗(yan)(yan)(yan)的電(dian)(dian)流(liu)(liu)為1A.按ICR18650電(dian)(dian)池的技術(shu)條件(jian)，進(jin)行了電(dian)(dian)池的倍率（1 C）、低(di)溫（一(yi)(yi)20C、一(yi)(yi)30C、一(yi)(yi)40C）、循(xun)環壽命試(shi)驗(yan)(yan)(yan)及安全(quan)特性試(shi)驗(yan)(yan)(yan)。其中安全(quan)特性試(shi)驗(yan)(yan)(yan)包括過充(chong)(chong)（3C充(chong)(chong)電(dian)(dian)、限壓(ya)10V）、短(duan)路（電(dian)(dian)阻(zu)小于50線路內短(duan)接(jie)）、沖擊（10kg重物、2/3m 5mm尖(jian)針刺透）、熱箱（150°C環境下放(fang)(fang)置）等。所有試(shi)驗(yan)(yan)(yan)數(shu)據由計(ji)算機自(zi)動采(cai)集(ji)，試(shi)驗(yan)(yan)(yan)現象遠程可視化監控記錄。電(dian)(dian)池的電(dian)(dian)性能試(shi)驗(yan)(yan)(yan)在ArbinBT-2401自(zi)動充(chong)(chong)放(fang)(fang)電(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(sheng)成一(yi)層固(gu)體電解質保護(hu)膜，消耗一(yi)定量(liang)的正(zheng)(zheng)極活(huo)性物質成為不可逆容量(liang)。米用LiNi0.Co0.O2作正(zheng)(zheng)極時，電池設計不必考慮過(guo)多增加(jia)正(zheng)(zheng)極活(huo)性物質量(liang)。

　　平(ping)均每次循(xun)環(huan)容(rong)(rong)(rong)降0.04%.電(dian)(dian)(dian)(dian)池(chi)(chi)以1C、2C速(su)率放(fang)(fang)電(dian)(dian)(dian)(dian)容(rong)(rong)(rong)量(liang)分別為初始容(rong)(rong)(rong)量(liang)的(de)99.4%和(he)98. 9%.電(dian)(dian)(dian)(dian)池(chi)(chi)具有良好的(de)低(di)溫(wen)放(fang)(fang)電(dian)(dian)(dian)(dian)特性，在一(yi)MCMLiCoO2電(dian)(dian)(dian)(dian)池(chi)(chi)倍率放(fang)(fang)電(dian)(dian)(dian)(dian)曲線°以0. 30時(shi)，以率放(fang)(fang)電(dian)(dian)(dian)(dian)容(rong)(rong)(rong)量(liang)達(da)到(dao)(dao)(dao)了(le)初始容(rong)(rong)(rong)量(liang)的(de)80%；在一(yi)40時(shi)以0.2C速(su)率放(fang)(fang)電(dian)(dian)(dian)(dian)達(da)到(dao)(dao)(dao)了(le)初始容(rong)(rong)(rong)量(liang)的(de)60%.電(dian)(dian)(dian)(dian)池(chi)(chi)良好的(de)低(di)溫(wen)放(fang)(fang)電(dian)(dian)(dian)(dian)特性主要是電(dian)(dian)(dian)(dian)極材料(liao)和(he)電(dian)(dian)(dian)(dian)MCMLiCoO2電(dian)(dian)(dian)(dian)池(chi)(chi)低(di)溫(wen)放(fang)(fang)電(dian)(dian)(dian)(dian)峨液(ye)共同作用(yong)的(de)結(jie)果。尤負極的(de)18650型鋰離子(zi)蓄電(dian)(dian)(dian)(dian)池(chi)(chi)放(fang)(fang)電(dian)(dian)(dian)(dian)特性曲線。電(dian)(dian)(dian)(dian)池(chi)(chi)的(de)放(fang)(fang)電(dian)(dian)(dian)(dian)容(rong)(rong)(rong)量(liang)大(da)于1700mAh，電(dian)(dian)(dian)(dian)池(chi)(chi)在室溫(wen)、充放(fang)(fang)電(dian)(dian)(dian)(dian)壓2.75放(fang)(fang)電(dian)(dian)(dian)(dian)效(xiao)率由87%提高到(dao)(dao)(dao)90.6%.并且在優化的(de)電(dian)(dian)(dian)(dian)液(ye)體(ti)系中，電(dian)(dian)(dian)(dian)池(chi)(chi)的(de)充放(fang)(fang)電(dian)(dian)(dian)(dian)效(xiao)率可提高到(dao)(dao)(dao)近92%.通(tong)過(guo)改進(jin)電(dian)(dian)(dian)(dian)極成(cheng)型加工工藝，提高了(le)電(dian)(dian)(dian)(dian)池(chi)(chi)循(xun)環(huan)的(de)穩定(ding)性。

　　~是以Li-CoO2為(wei)正極、MCMB為(wei)負極的18650型鋰離子蓄(xu)電池的放電特性曲(qu)線。

　　41V、1A放電電流、100%DOD條(tiao)件下(xia)，循環壽命超過(guo)1000次(ci)(ci)，平均每次(ci)(ci)循環容(rong)(rong)降0.04%.電池(chi)(chi)良好的(de)循環壽命主(zhu)要(yao)得益于電極在電解(jie)液中的(de)穩定(ding)性(xing)31.電池(chi)(chi)以(yi)1C、2C速率放(fang)(fang)電容(rong)(rong)量(liang)(liang)(liang)分(fen)別為(wei)初(chu)始容(rong)(rong)量(liang)(liang)(liang)的(de)945%和89.8%.電池(chi)(chi)在一由圖可(ke)知，放(fang)(fang)電容(rong)(rong)量(liang)(liang)(liang)大于1550mAh，電池(chi)(chi)在室(shi)溫、充放(fang)(fang)電壓2.75~41V、1A放(fang)(fang)電電流、100%DOD條(tiao)件下(xia)，循環壽命超過(guo)1000次(ci)(ci)，C時以(yi)0.2C速率放(fang)(fang)電容(rong)(rong)量(liang)(liang)(liang)為(wei)初(chu)始容(rong)(rong)量(liang)(liang)(liang)的(de)80. 5%，一30C時放(fang)(fang)電容(rong)(rong)量(liang)(liang)(liang)為(wei)初(chu)始容(rong)(rong)量(liang)(liang)(liang)的(de)57.1%. ~2為(wei)電池(chi)(chi)的(de)安全特性(xing)試驗(yan)曲線。

　　電池低溫放電曲線過充、短路、沖擊等(deng)項試lowtemperature驗(yan)中，電池的取溫度(du)低于120C無起火、爆炸研究與設計現象(xiang)發生，安全(quan)可(ke)靠。這是(shi)因為在電池的設計及制(zhi)作中，從(cong)材料、結構、安全(quan)裝置等(deng)多方(fang)面采取了安全(quan)保護措(cuo)施。

　　3結(jie)論(lun)通過(guo)試驗(yan)和選擇電(dian)(dian)(dian)極材料(liao)，改進電(dian)(dian)(dian)極成(cheng)(cheng)型工(gong)(gong)藝，篩選電(dian)(dian)(dian)液體系，優化電(dian)(dian)(dian)池設(she)計和安全設(she)計，研(yan)制成(cheng)(cheng)了為(wei)正極、MCMB為(wei)負極的(de)18650型鋰(li)離子蓄(xu)電(dian)(dian)(dian)池。電(dian)(dian)(dian)池具有較高(gao)的(de)放(fang)電(dian)(dian)(dian)容量(liang)(liang)和1700mAh）高(gao)的(de)比能(neng)量(liang)(liang)（130Wh/kg和350Wh/L）長(chang)的(de)工(gong)(gong)作(zuo)壽(shou)命（1 000次）和良好(hao)的(de)低溫放(fang)電(dian)(dian)(dian)性能(neng)（一40°C）。電(dian)(dian)(dian)池工(gong)(gong)作(zuo)安全可靠，能(neng)滿(man)足(zu)不同領域對電(dian)(dian)(dian)池的(de)特殊要求。

                                                                                                                                  本(ben)文(wen)摘自(zi)于中國鋰(li)電網(wang)