電源技術研究與設計高性能18650型鋰離子蓄電池張(zhang)澤波(bo)，劉(liu)秀(xiu)生，薛梅，楊清欣(xin)，汪繼強(qiang)（信(xin)息產業部電(dian)子(zi)第十八研究所，天津300381）（LiNi0.8Co0.2O2）為正(zheng)極，中間相炭微(wei)珠（MCMB）為負(fu)極的(de)(de)18650型(xing)鋰離子(zi)蓄電(dian)池(chi)。電(dian)池(chi)的(de)(de)放電(dian)容(rong)(rong)量分別大于1 700mAh電(dian)池(chi)比能量達到(dao)了130Wh/kg和350Wh/L.在(zai)室溫(wen)條件下，0.5C電(dian)池(chi)的(de)(de)循(xun)環壽命(ming)1000次(ci)時(shi)，其容(rong)(rong)量仍為初(chu)始(shi)容(rong)(rong)量的(de)(de)60%.70%.以氧化鈷(gu)鋰為正(zheng)極的(de)(de)電(dian)池(chi)在(zai)一(yi)40°C.0.2C速率。終(zhong)止(zhi)電(dian)壓2.5V的(de)(de)條件下，放電(dian)容(rong)(rong)量為室溫(wen)容(rong)(rong)量的(de)(de)60%.實驗結果(guo)表明(ming)，電(dian)池(chi)安全(quan)可靠。

　　鋰離子蓄電(dian)(dian)(dian)(dian)(dian)池自(zi)1991年商(shang)品化以來發展迅速。目前它不(bu)但廣泛用于攝(she)象(xiang)機、筆記(ji)本電(dian)(dian)(dian)(dian)(dian)腦、蜂窩電(dian)(dian)(dian)(dian)(dian)話等便攜式電(dian)(dian)(dian)(dian)(dian)子(zi)設(she)施(shi)(shi)，而且正(zheng)在成(cheng)為電(dian)(dian)(dian)(dian)(dian)動車、軍事(shi)通訊、航(hang)天、航(hang)空領域電(dian)(dian)(dian)(dian)(dian)子(zi)設(she)施(shi)(shi)的(de)候(hou)選電(dian)(dian)(dian)(dian)(dian)源111.這就要求電(dian)(dian)(dian)(dian)(dian)池具有更高的(de)比能量、更長的(de)工作壽命及(ji)良(liang)好的(de)高、低溫放電(dian)(dian)(dian)(dian)(dian)特性(xing)。為此我(wo)們試驗了高性(xing)能的(de)正(zheng)極材(cai)(cai)料氧化鈷(gu)鋰、氧化鎳鈷(gu)鋰和負極碳材(cai)(cai)料一中(zhong)間相炭微珠，對電(dian)(dian)(dian)(dian)(dian)池設(she)計進(jin)行優化改進(jin)電(dian)(dian)(dian)(dian)(dian)極成(cheng)型(xing)工藝，篩(shai)選不(bu)同組分和配(pei)比的(de)電(dian)(dian)(dian)(dian)(dian)液體系，研制出具有高性(xing)能的(de)18650型(xing)鋰離子(zi)蓄電(dian)(dian)(dian)(dian)(dian)池。

　　以金屬(shu)鋰為負極(ji)，采用扣式電(dian)池試驗了(le)正極(ji)材料LiCo2和(he)LiNi0.8Co0.O2的充放(fang)電(dian)特性。充放(fang)電(dian)壓(ya)范圍(wei)3.充放(fang)電(dian)流密度0.2mA/cm2.研(yan)究(jiu)了(le)負極(ji)炭粉MCMB顆粒度及(ji)其分(fen)布與電(dian)池容(rong)量(liang)及(ji)充放(fang)電(dian)效率的關系，并試驗了(le)負電(dian)極(ji)成型工藝(yi)條件。

　　電液(ye)體系的(de)篩選對電解(jie)質為(wei)1mol/LLiPFf以(yi)碳酸(suan)乙烯酯(zhi)（EC）為(wei)主體的(de)不同(tong)組分(fen)〔包括碳酸(suan)二乙酯(zhi)（DEC）碳酸(suan)二甲酯(zhi)（DMC）碳酸(suan)乙甲酯(zhi)（EMC）碳酸(suan)丙烯酯(zhi)（PC）等〕和比例(li)的(de)多元電液(ye)體系進行(xing)試(shi)驗。研究了其(qi)與電極材料的(de)相容性(xing)和對電池容量。充(chong)放效(xiao)率、盾環壽(shou)命。倍率特性(xing)。溫(wen)度特性(xing)的(de)影響。

　　電(dian)池(chi)工藝(yi)參數的(de)設(she)計和(he)電(dian)極的(de)制作根據材料的(de)試驗結果，設(she)計了電(dian)池(chi)正(zheng)負極活性(xing)物質的(de)配比及電(dian)極的(de)工藝(yi)參數。將正(zheng)極活性(xing)物質與一定比例的(de)添加劑(ji)均勻混和(he)，加到聚偏(pian)二(er)氟乙(yi)烯(xi)/N甲基吡(bi)咯烷酮（PVDF/NMP）粘結液中，攪拌均勻，制成(cheng)(cheng)正(zheng)極漿料，均勻涂(tu)于(yu)鋁箔基體上(shang)。經過烘干。壓片。裁片等工藝(yi)制成(cheng)(cheng)正(zheng)電(dian)極。按同樣方法制成(cheng)(cheng)負電(dian)極。

　　負電極基(ji)體為銅箔。

　　電池的(de)(de)制作及實(shi)驗(yan)(yan)合隔膜卷繞成(cheng)極芯(xin)，電(dian)液為(wei)1mol/LLiPFf/EC+DEC+DMC，制成(cheng)18650型電(dian)池(chi)。電(dian)池(chi)采用恒流(liu)(liu)限(xian)壓(ya)、直壓(ya)限(xian)流(liu)(liu)的(de)(de)充電(dian)機電(dian)源技術制，充放電(dian)壓(ya)范(fan)圍為(wei)2.75~4. 1V.電(dian)池(chi)化(hua)成(cheng)電(dian)流(liu)(liu)為(wei)0.2C，循環壽命(ming)(ming)試(shi)驗(yan)(yan)的(de)(de)電(dian)流(liu)(liu)為(wei)1A.按ICR18650電(dian)池(chi)的(de)(de)技術條(tiao)件，進(jin)行了電(dian)池(chi)的(de)(de)倍(bei)率（1 C）、低(di)溫（一(yi)20C、一(yi)30C、一(yi)40C）、循環壽命(ming)(ming)試(shi)驗(yan)(yan)及安(an)全特性(xing)試(shi)驗(yan)(yan)。其(qi)中安(an)全特性(xing)試(shi)驗(yan)(yan)包括過(guo)充（3C充電(dian)、限(xian)壓(ya)10V）、短(duan)(duan)路(lu)（電(dian)阻小于50線路(lu)內短(duan)(duan)接）、沖擊（10kg重物、2/3m 5mm尖(jian)針(zhen)刺透）、熱箱(xiang)（150°C環境下(xia)放置）等。所有試(shi)驗(yan)(yan)數據由計算機自(zi)動(dong)采集(ji)，試(shi)驗(yan)(yan)現象(xiang)遠程可視化(hua)監控記錄。電(dian)池(chi)的(de)(de)電(dian)性(xing)能試(shi)驗(yan)(yan)在ArbinBT-2401自(zi)動(dong)充放電(dian)儀上(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，要在其表面(mian)生(sheng)成一(yi)層(ceng)固體電(dian)解質保(bao)護膜，消耗一(yi)定量的正(zheng)極活性(xing)物質成為不可逆(ni)容量。米用LiNi0.Co0.O2作正(zheng)極時，電(dian)池(chi)設計不必(bi)考(kao)慮(lv)過多增加正(zheng)極活性(xing)物質量。

　　平均每次循環容降0.04%.電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)以(yi)1C、2C速(su)率(lv)(lv)放(fang)電(dian)(dian)(dian)(dian)(dian)容量(liang)(liang)分別為(wei)初(chu)始容量(liang)(liang)的(de)(de)(de)(de)(de)99.4%和(he)98. 9%.電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)具有良(liang)好的(de)(de)(de)(de)(de)低(di)溫放(fang)電(dian)(dian)(dian)(dian)(dian)特(te)性(xing)，在(zai)(zai)一(yi)(yi)MCMLiCoO2電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)倍率(lv)(lv)放(fang)電(dian)(dian)(dian)(dian)(dian)曲(qu)(qu)線°以(yi)0. 30時(shi)，以(yi)率(lv)(lv)放(fang)電(dian)(dian)(dian)(dian)(dian)容量(liang)(liang)達(da)到了初(chu)始容量(liang)(liang)的(de)(de)(de)(de)(de)80%；在(zai)(zai)一(yi)(yi)40時(shi)以(yi)0.2C速(su)率(lv)(lv)放(fang)電(dian)(dian)(dian)(dian)(dian)達(da)到了初(chu)始容量(liang)(liang)的(de)(de)(de)(de)(de)60%.電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)良(liang)好的(de)(de)(de)(de)(de)低(di)溫放(fang)電(dian)(dian)(dian)(dian)(dian)特(te)性(xing)主要是電(dian)(dian)(dian)(dian)(dian)極材料(liao)和(he)電(dian)(dian)(dian)(dian)(dian)MCMLiCoO2電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)低(di)溫放(fang)電(dian)(dian)(dian)(dian)(dian)峨(e)液共同作用的(de)(de)(de)(de)(de)結果。尤負極的(de)(de)(de)(de)(de)18650型(xing)鋰離子蓄電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)放(fang)電(dian)(dian)(dian)(dian)(dian)特(te)性(xing)曲(qu)(qu)線。電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)的(de)(de)(de)(de)(de)放(fang)電(dian)(dian)(dian)(dian)(dian)容量(liang)(liang)大于(yu)1700mAh，電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)在(zai)(zai)室(shi)溫、充放(fang)電(dian)(dian)(dian)(dian)(dian)壓2.75放(fang)電(dian)(dian)(dian)(dian)(dian)效(xiao)率(lv)(lv)由(you)87%提(ti)高到90.6%.并且在(zai)(zai)優化的(de)(de)(de)(de)(de)電(dian)(dian)(dian)(dian)(dian)液體(ti)系中，電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)的(de)(de)(de)(de)(de)充放(fang)電(dian)(dian)(dian)(dian)(dian)效(xiao)率(lv)(lv)可提(ti)高到近92%.通過改進電(dian)(dian)(dian)(dian)(dian)極成型(xing)加(jia)工工藝，提(ti)高了電(dian)(dian)(dian)(dian)(dian)池(chi)(chi)循環的(de)(de)(de)(de)(de)穩定性(xing)。

　　~是以Li-CoO2為正極、MCMB為負極的(de)18650型(xing)鋰(li)離子蓄電池的(de)放電特性曲(qu)線(xian)。

　　41V、1A放電電流、100%DOD條(tiao)件下，循環壽命超過(guo)1000次(ci)，平均每(mei)次(ci)循環容(rong)降0.04%.電(dian)(dian)(dian)池(chi)(chi)良好的(de)循環壽命主要(yao)得益于電(dian)(dian)(dian)極(ji)在(zai)電(dian)(dian)(dian)解液中的(de)穩定性31.電(dian)(dian)(dian)池(chi)(chi)以1C、2C速率放(fang)(fang)電(dian)(dian)(dian)容(rong)量(liang)(liang)分別為初始容(rong)量(liang)(liang)的(de)945%和89.8%.電(dian)(dian)(dian)池(chi)(chi)在(zai)一由圖可知，放(fang)(fang)電(dian)(dian)(dian)容(rong)量(liang)(liang)大于1550mAh，電(dian)(dian)(dian)池(chi)(chi)在(zai)室溫、充放(fang)(fang)電(dian)(dian)(dian)壓2.75~41V、1A放(fang)(fang)電(dian)(dian)(dian)電(dian)(dian)(dian)流、100%DOD條(tiao)件下，循環壽命超過(guo)1000次(ci)，C時以0.2C速率放(fang)(fang)電(dian)(dian)(dian)容(rong)量(liang)(liang)為初始容(rong)量(liang)(liang)的(de)80. 5%，一30C時放(fang)(fang)電(dian)(dian)(dian)容(rong)量(liang)(liang)為初始容(rong)量(liang)(liang)的(de)57.1%. ~2為電(dian)(dian)(dian)池(chi)(chi)的(de)安(an)全特性試驗曲(qu)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(de)(de)取(qu)溫度低(di)于(yu)120C無起(qi)火、爆炸研(yan)究與設計現象發(fa)生，安全可靠。這是因為(wei)在電池(chi)的(de)(de)設計及制作(zuo)中，從(cong)材料、結構、安全裝置(zhi)等多方(fang)面采取(qu)了安全保護措施。

　　3結論通過試驗和(he)選擇電(dian)(dian)(dian)(dian)(dian)極(ji)材料，改進(jin)電(dian)(dian)(dian)(dian)(dian)極(ji)成型(xing)工藝，篩(shai)選電(dian)(dian)(dian)(dian)(dian)液(ye)體系，優化電(dian)(dian)(dian)(dian)(dian)池設(she)計(ji)和(he)安全設(she)計(ji)，研制成了為正極(ji)、MCMB為負(fu)極(ji)的(de)18650型(xing)鋰離(li)子蓄電(dian)(dian)(dian)(dian)(dian)池。電(dian)(dian)(dian)(dian)(dian)池具有(you)較(jiao)高(gao)的(de)放電(dian)(dian)(dian)(dian)(dian)容量和(he)1700mAh）高(gao)的(de)比(bi)能(neng)量（130Wh/kg和(he)350Wh/L）長的(de)工作壽命（1 000次(ci)）和(he)良好的(de)低溫(wen)放電(dian)(dian)(dian)(dian)(dian)性(xing)能(neng)（一40°C）。電(dian)(dian)(dian)(dian)(dian)池工作安全可靠，能(neng)滿足(zu)不(bu)同領域對電(dian)(dian)(dian)(dian)(dian)池的(de)特(te)殊要求。

                                                                                                                                  本文摘(zhai)自(zi)于中國鋰電網(wang)