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(qing)欣，汪繼(ji)強（信息(xi)產業部電(dian)子第十八(ba)研究(jiu)所，天津300381）（LiNi0.8Co0.2O2）為(wei)(wei)正極(ji)，中(zhong)間相炭微珠（MCMB）為(wei)(wei)負極(ji)的(de)(de)(de)18650型鋰離子蓄電(dian)池(chi)。電(dian)池(chi)的(de)(de)(de)放電(dian)容量(liang)(liang)分別(bie)大于1 700mAh電(dian)池(chi)比能量(liang)(liang)達到了130Wh/kg和350Wh/L.在室溫條件(jian)下，0.5C電(dian)池(chi)的(de)(de)(de)循環壽命1000次時，其容量(liang)(liang)仍為(wei)(wei)初始容量(liang)(liang)的(de)(de)(de)60%.70%.以氧化鈷鋰為(wei)(wei)正極(ji)的(de)(de)(de)電(dian)池(chi)在一(yi)40°C.0.2C速(su)率(lv)。終(zhong)止電(dian)壓2.5V的(de)(de)(de)條件(jian)下，放電(dian)容量(liang)(liang)為(wei)(wei)室溫容量(liang)(liang)的(de)(de)(de)60%.實驗結果表明，電(dian)池(chi)安(an)全可靠。

　　鋰離子蓄(xu)電(dian)(dian)(dian)(dian)池(chi)自1991年(nian)商品化(hua)(hua)以來發(fa)展迅(xun)速。目前它(ta)不但廣泛用(yong)于(yu)攝象機、筆記(ji)本(ben)電(dian)(dian)(dian)(dian)腦、蜂窩電(dian)(dian)(dian)(dian)話等便(bian)攜式電(dian)(dian)(dian)(dian)子設(she)(she)施，而且正(zheng)在成(cheng)為(wei)電(dian)(dian)(dian)(dian)動車、軍(jun)事通訊、航(hang)天、航(hang)空領域(yu)電(dian)(dian)(dian)(dian)子設(she)(she)施的(de)候(hou)選(xuan)(xuan)電(dian)(dian)(dian)(dian)源(yuan)111.這(zhe)就(jiu)要求電(dian)(dian)(dian)(dian)池(chi)具有(you)更高(gao)的(de)比(bi)能量(liang)、更長的(de)工作(zuo)壽(shou)命及良(liang)好的(de)高(gao)、低(di)溫(wen)放電(dian)(dian)(dian)(dian)特性。為(wei)此我們試驗了高(gao)性能的(de)正(zheng)極(ji)材(cai)料(liao)氧化(hua)(hua)鈷鋰(li)(li)、氧化(hua)(hua)鎳(nie)鈷鋰(li)(li)和負極(ji)碳(tan)材(cai)料(liao)一中間相炭微珠，對電(dian)(dian)(dian)(dian)池(chi)設(she)(she)計進(jin)行優(you)化(hua)(hua)改(gai)進(jin)電(dian)(dian)(dian)(dian)極(ji)成(cheng)型(xing)工藝，篩選(xuan)(xuan)不同組分和配比(bi)的(de)電(dian)(dian)(dian)(dian)液體系，研制出(chu)具有(you)高(gao)性能的(de)18650型(xing)鋰(li)(li)離(li)子蓄(xu)電(dian)(dian)(dian)(dian)池(chi)。

　　以金(jin)屬鋰為負極，采用(yong)扣式電(dian)(dian)池(chi)試(shi)驗了正極材料LiCo2和LiNi0.8Co0.O2的充放電(dian)(dian)特性。充放電(dian)(dian)壓范圍3.充放電(dian)(dian)流密度0.2mA/cm2.研究(jiu)了負極炭粉MCMB顆粒度及(ji)其分布與電(dian)(dian)池(chi)容量及(ji)充放電(dian)(dian)效率的關系，并試(shi)驗了負電(dian)(dian)極成型工藝條件。

　　電(dian)液(ye)(ye)體(ti)系(xi)的(de)篩選對(dui)電(dian)解(jie)質為(wei)(wei)1mol/LLiPFf以碳(tan)酸乙(yi)烯酯(zhi)(zhi)（EC）為(wei)(wei)主體(ti)的(de)不(bu)同(tong)組分(fen)〔包括碳(tan)酸二乙(yi)酯(zhi)(zhi)（DEC）碳(tan)酸二甲酯(zhi)(zhi)（DMC）碳(tan)酸乙(yi)甲酯(zhi)(zhi)（EMC）碳(tan)酸丙烯酯(zhi)(zhi)（PC）等〕和(he)比例的(de)多元電(dian)液(ye)(ye)體(ti)系(xi)進行試(shi)驗。研究了其(qi)與電(dian)極(ji)材料的(de)相容性(xing)和(he)對(dui)電(dian)池容量。充(chong)放效率、盾環壽命(ming)。倍率特性(xing)。溫度特性(xing)的(de)影響。

　　電(dian)(dian)池(chi)(chi)工藝參數的(de)(de)設(she)計和電(dian)(dian)極(ji)的(de)(de)制(zhi)作根(gen)據材(cai)料(liao)的(de)(de)試驗結(jie)果，設(she)計了電(dian)(dian)池(chi)(chi)正(zheng)負(fu)極(ji)活性物(wu)質(zhi)的(de)(de)配比及電(dian)(dian)極(ji)的(de)(de)工藝參數。將(jiang)正(zheng)極(ji)活性物(wu)質(zhi)與一定(ding)比例的(de)(de)添加劑(ji)均(jun)勻(yun)混和，加到聚(ju)偏二氟乙(yi)烯/N甲基(ji)吡咯烷酮（PVDF/NMP）粘結(jie)液中，攪(jiao)拌均(jun)勻(yun)，制(zhi)成(cheng)正(zheng)極(ji)漿料(liao)，均(jun)勻(yun)涂于鋁箔基(ji)體上。經過烘干。壓片。裁片等工藝制(zhi)成(cheng)正(zheng)電(dian)(dian)極(ji)。按(an)同(tong)樣方(fang)法(fa)制(zhi)成(cheng)負(fu)電(dian)(dian)極(ji)。

　　負電(dian)極(ji)基(ji)體(ti)為(wei)銅(tong)箔。

　　電池的(de)制作及(ji)實驗(yan)(yan)(yan)合(he)隔膜卷繞成極芯，電(dian)(dian)(dian)液(ye)為(wei)1mol/LLiPFf/EC+DEC+DMC，制成18650型(xing)電(dian)(dian)(dian)池(chi)。電(dian)(dian)(dian)池(chi)采用恒流(liu)限(xian)壓(ya)、直壓(ya)限(xian)流(liu)的(de)充電(dian)(dian)(dian)機(ji)電(dian)(dian)(dian)源技(ji)(ji)術制，充放(fang)電(dian)(dian)(dian)壓(ya)范(fan)圍為(wei)2.75~4. 1V.電(dian)(dian)(dian)池(chi)化成電(dian)(dian)(dian)流(liu)為(wei)0.2C，循(xun)環(huan)壽命試驗(yan)(yan)(yan)的(de)電(dian)(dian)(dian)流(liu)為(wei)1A.按(an)ICR18650電(dian)(dian)(dian)池(chi)的(de)技(ji)(ji)術條件(jian)，進(jin)行了(le)電(dian)(dian)(dian)池(chi)的(de)倍率（1 C）、低溫(wen)（一(yi)(yi)20C、一(yi)(yi)30C、一(yi)(yi)40C）、循(xun)環(huan)壽命試驗(yan)(yan)(yan)及(ji)安全特(te)性(xing)試驗(yan)(yan)(yan)。其中安全特(te)性(xing)試驗(yan)(yan)(yan)包括(kuo)過(guo)充（3C充電(dian)(dian)(dian)、限(xian)壓(ya)10V）、短路(lu)（電(dian)(dian)(dian)阻小于50線路(lu)內短接）、沖擊（10kg重物、2/3m 5mm尖(jian)針刺透）、熱箱（150°C環(huan)境(jing)下放(fang)置）等。所有試驗(yan)(yan)(yan)數據由計算機(ji)自動采集，試驗(yan)(yan)(yan)現象遠程可視化監控(kong)記錄。電(dian)(dian)(dian)池(chi)的(de)電(dian)(dian)(dian)性(xing)能(neng)試驗(yan)(yan)(yan)在ArbinBT-2401自動充放(fang)電(dian)(dian)(dian)儀(yi)上(shang)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(zai)其表面生成(cheng)一(yi)層固(gu)體電(dian)解質(zhi)(zhi)保護膜(mo)，消(xiao)耗(hao)一(yi)定量(liang)的正(zheng)極活性物質(zhi)(zhi)成(cheng)為不可逆容量(liang)。米用LiNi0.Co0.O2作正(zheng)極時，電(dian)池設計不必考慮過多(duo)增(zeng)加正(zheng)極活性物質(zhi)(zhi)量(liang)。

　　平均每次循環容(rong)降0.04%.電(dian)(dian)(dian)(dian)(dian)池以(yi)1C、2C速率(lv)(lv)(lv)放電(dian)(dian)(dian)(dian)(dian)容(rong)量(liang)分別為(wei)初始(shi)(shi)(shi)容(rong)量(liang)的(de)(de)(de)99.4%和98. 9%.電(dian)(dian)(dian)(dian)(dian)池具(ju)有良好的(de)(de)(de)低溫(wen)放電(dian)(dian)(dian)(dian)(dian)特(te)性(xing)(xing)，在(zai)一MCMLiCoO2電(dian)(dian)(dian)(dian)(dian)池倍率(lv)(lv)(lv)放電(dian)(dian)(dian)(dian)(dian)曲線(xian)°以(yi)0. 30時，以(yi)率(lv)(lv)(lv)放電(dian)(dian)(dian)(dian)(dian)容(rong)量(liang)達(da)到(dao)了(le)(le)初始(shi)(shi)(shi)容(rong)量(liang)的(de)(de)(de)80%；在(zai)一40時以(yi)0.2C速率(lv)(lv)(lv)放電(dian)(dian)(dian)(dian)(dian)達(da)到(dao)了(le)(le)初始(shi)(shi)(shi)容(rong)量(liang)的(de)(de)(de)60%.電(dian)(dian)(dian)(dian)(dian)池良好的(de)(de)(de)低溫(wen)放電(dian)(dian)(dian)(dian)(dian)特(te)性(xing)(xing)主要是電(dian)(dian)(dian)(dian)(dian)極(ji)材料和電(dian)(dian)(dian)(dian)(dian)MCMLiCoO2電(dian)(dian)(dian)(dian)(dian)池低溫(wen)放電(dian)(dian)(dian)(dian)(dian)峨液共同作用的(de)(de)(de)結(jie)果。尤負極(ji)的(de)(de)(de)18650型(xing)鋰離子蓄(xu)電(dian)(dian)(dian)(dian)(dian)池放電(dian)(dian)(dian)(dian)(dian)特(te)性(xing)(xing)曲線(xian)。電(dian)(dian)(dian)(dian)(dian)池的(de)(de)(de)放電(dian)(dian)(dian)(dian)(dian)容(rong)量(liang)大于1700mAh，電(dian)(dian)(dian)(dian)(dian)池在(zai)室溫(wen)、充放電(dian)(dian)(dian)(dian)(dian)壓(ya)2.75放電(dian)(dian)(dian)(dian)(dian)效(xiao)率(lv)(lv)(lv)由(you)87%提(ti)高到(dao)90.6%.并且在(zai)優化的(de)(de)(de)電(dian)(dian)(dian)(dian)(dian)液體系中(zhong)，電(dian)(dian)(dian)(dian)(dian)池的(de)(de)(de)充放電(dian)(dian)(dian)(dian)(dian)效(xiao)率(lv)(lv)(lv)可提(ti)高到(dao)近92%.通過(guo)改進電(dian)(dian)(dian)(dian)(dian)極(ji)成型(xing)加工(gong)(gong)工(gong)(gong)藝，提(ti)高了(le)(le)電(dian)(dian)(dian)(dian)(dian)池循環的(de)(de)(de)穩定性(xing)(xing)。

　　~是(shi)以Li-CoO2為(wei)正極、MCMB為(wei)負極的18650型鋰離子蓄電池的放電特(te)性曲線。

　　41V、1A放電電流、100%DOD條件(jian)下(xia)，循環壽(shou)命(ming)超(chao)(chao)過1000次，平(ping)均每(mei)次循環容(rong)降0.04%.電池(chi)良(liang)好的(de)循環壽(shou)命(ming)主要得益于電極在(zai)電解液中的(de)穩定性31.電池(chi)以(yi)1C、2C速率(lv)放(fang)電容(rong)量(liang)(liang)分別為(wei)(wei)初(chu)始(shi)容(rong)量(liang)(liang)的(de)945%和89.8%.電池(chi)在(zai)一(yi)由圖可知(zhi)，放(fang)電容(rong)量(liang)(liang)大于1550mAh，電池(chi)在(zai)室溫、充放(fang)電壓2.75~41V、1A放(fang)電電流、100%DOD條件(jian)下(xia)，循環壽(shou)命(ming)超(chao)(chao)過1000次，C時以(yi)0.2C速率(lv)放(fang)電容(rong)量(liang)(liang)為(wei)(wei)初(chu)始(shi)容(rong)量(liang)(liang)的(de)80. 5%，一(yi)30C時放(fang)電容(rong)量(liang)(liang)為(wei)(wei)初(chu)始(shi)容(rong)量(liang)(liang)的(de)57.1%. ~2為(wei)(wei)電池(chi)的(de)安(an)全特性試驗曲線。

　　電池低溫放電曲線過充、短路、沖擊等項(xiang)試lowtemperature驗中，電(dian)池(chi)的(de)取溫度低于120C無起(qi)火、爆炸(zha)研(yan)究(jiu)與設計現象(xiang)發生，安(an)(an)全可(ke)靠。這是因為在電(dian)池(chi)的(de)設計及制作中，從材料、結構、安(an)(an)全裝置等多方面(mian)采取了安(an)(an)全保護措施。

　　3結論通過試驗和(he)選擇電(dian)(dian)極材料(liao)，改進電(dian)(dian)極成型工(gong)藝，篩(shai)選電(dian)(dian)液(ye)體系，優化電(dian)(dian)池(chi)設計和(he)安全(quan)設計，研制成了為正極、MCMB為負(fu)極的(de)(de)18650型鋰離子(zi)蓄(xu)電(dian)(dian)池(chi)。電(dian)(dian)池(chi)具有較高的(de)(de)放(fang)(fang)電(dian)(dian)容量(liang)和(he)1700mAh）高的(de)(de)比能(neng)量(liang)（130Wh/kg和(he)350Wh/L）長的(de)(de)工(gong)作壽命（1 000次）和(he)良好的(de)(de)低溫放(fang)(fang)電(dian)(dian)性能(neng)（一40°C）。電(dian)(dian)池(chi)工(gong)作安全(quan)可靠，能(neng)滿足不同領域對電(dian)(dian)池(chi)的(de)(de)特殊要求。

                                                                                                                                  本文摘自(zi)于中國鋰電(dian)網