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(xiu)生，薛梅(mei)，楊清欣，汪(wang)繼強(qiang)（信息產業部電(dian)(dian)子第十八研(yan)究所，天津300381）（LiNi0.8Co0.2O2）為(wei)正極(ji)，中間相炭微珠（MCMB）為(wei)負極(ji)的(de)(de)18650型鋰(li)離(li)子蓄電(dian)(dian)池(chi)。電(dian)(dian)池(chi)的(de)(de)放電(dian)(dian)容量(liang)(liang)分(fen)別(bie)大于(yu)1 700mAh電(dian)(dian)池(chi)比能量(liang)(liang)達到了130Wh/kg和350Wh/L.在室溫(wen)條件(jian)下，0.5C電(dian)(dian)池(chi)的(de)(de)循環壽(shou)命1000次時，其容量(liang)(liang)仍為(wei)初始容量(liang)(liang)的(de)(de)60%.70%.以氧化鈷鋰(li)為(wei)正極(ji)的(de)(de)電(dian)(dian)池(chi)在一40°C.0.2C速率(lv)。終(zhong)止電(dian)(dian)壓2.5V的(de)(de)條件(jian)下，放電(dian)(dian)容量(liang)(liang)為(wei)室溫(wen)容量(liang)(liang)的(de)(de)60%.實驗結果表明，電(dian)(dian)池(chi)安全可靠。

　　鋰離子蓄電(dian)(dian)池自1991年商品化以來發展迅(xun)速。目前它不但廣泛用于攝象機、筆(bi)記(ji)本電(dian)(dian)腦(nao)、蜂窩電(dian)(dian)話等便(bian)攜式電(dian)(dian)子(zi)設施(shi)，而(er)且(qie)正在成為(wei)(wei)電(dian)(dian)動車(che)、軍事(shi)通(tong)訊、航天、航空(kong)領域電(dian)(dian)子(zi)設施(shi)的候(hou)選電(dian)(dian)源111.這就要求(qiu)電(dian)(dian)池具(ju)有更(geng)高(gao)的比(bi)能(neng)量、更(geng)長的工(gong)(gong)作壽命及(ji)良(liang)好的高(gao)、低溫放電(dian)(dian)特性(xing)。為(wei)(wei)此我們試(shi)驗了高(gao)性(xing)能(neng)的正極(ji)材(cai)料(liao)氧(yang)化鈷(gu)鋰、氧(yang)化鎳鈷(gu)鋰和(he)負極(ji)碳材(cai)料(liao)一(yi)中間相炭微珠，對電(dian)(dian)池設計進(jin)行優化改進(jin)電(dian)(dian)極(ji)成型工(gong)(gong)藝，篩選不同組分和(he)配比(bi)的電(dian)(dian)液(ye)體系，研制出具(ju)有高(gao)性(xing)能(neng)的18650型鋰離子(zi)蓄電(dian)(dian)池。

　　以金屬鋰(li)為負(fu)極，采用扣式電(dian)(dian)池試驗了正極材料LiCo2和LiNi0.8Co0.O2的(de)充(chong)(chong)放電(dian)(dian)特性。充(chong)(chong)放電(dian)(dian)壓范(fan)圍3.充(chong)(chong)放電(dian)(dian)流密度0.2mA/cm2.研究了負(fu)極炭粉MCMB顆粒度及(ji)其分布(bu)與電(dian)(dian)池容量及(ji)充(chong)(chong)放電(dian)(dian)效率(lv)的(de)關系，并(bing)試驗了負(fu)電(dian)(dian)極成型工藝(yi)條(tiao)件。

　　電液體系的(de)篩選對(dui)電解質為1mol/LLiPFf以(yi)碳(tan)酸乙(yi)烯酯(zhi)(zhi)(zhi)（EC）為主體的(de)不(bu)同(tong)組(zu)分〔包括碳(tan)酸二(er)乙(yi)酯(zhi)(zhi)(zhi)（DEC）碳(tan)酸二(er)甲酯(zhi)(zhi)(zhi)（DMC）碳(tan)酸乙(yi)甲酯(zhi)(zhi)(zhi)（EMC）碳(tan)酸丙(bing)烯酯(zhi)(zhi)(zhi)（PC）等〕和比例(li)的(de)多元電液體系進(jin)行試(shi)驗。研究(jiu)了其與(yu)電極材料的(de)相容(rong)性(xing)和對(dui)電池容(rong)量。充放效率(lv)(lv)、盾環壽命。倍率(lv)(lv)特性(xing)。溫度特性(xing)的(de)影響(xiang)。

　　電(dian)(dian)池工(gong)藝(yi)參數的(de)設計和電(dian)(dian)極的(de)制(zhi)作根據(ju)材料(liao)的(de)試驗結果(guo)，設計了電(dian)(dian)池正(zheng)(zheng)負極活性物(wu)質的(de)配比(bi)及電(dian)(dian)極的(de)工(gong)藝(yi)參數。將正(zheng)(zheng)極活性物(wu)質與一定(ding)比(bi)例的(de)添加(jia)劑均(jun)(jun)勻(yun)混和，加(jia)到聚偏二氟乙烯/N甲基吡咯烷酮（PVDF/NMP）粘結液中，攪拌(ban)均(jun)(jun)勻(yun)，制(zhi)成正(zheng)(zheng)極漿料(liao)，均(jun)(jun)勻(yun)涂于鋁箔基體(ti)上。經過烘干(gan)。壓片。裁片等工(gong)藝(yi)制(zhi)成正(zheng)(zheng)電(dian)(dian)極。按同樣方法制(zhi)成負電(dian)(dian)極。

　　負電極(ji)基體為銅箔。

　　電池的(de)制作及實驗合(he)隔膜卷繞(rao)成極芯(xin)，電(dian)(dian)(dian)(dian)(dian)液為1mol/LLiPFf/EC+DEC+DMC，制成18650型電(dian)(dian)(dian)(dian)(dian)池。電(dian)(dian)(dian)(dian)(dian)池采用恒流限壓、直壓限流的(de)充(chong)(chong)電(dian)(dian)(dian)(dian)(dian)機電(dian)(dian)(dian)(dian)(dian)源技術(shu)(shu)制，充(chong)(chong)放電(dian)(dian)(dian)(dian)(dian)壓范(fan)圍(wei)為2.75~4. 1V.電(dian)(dian)(dian)(dian)(dian)池化(hua)成電(dian)(dian)(dian)(dian)(dian)流為0.2C，循環壽命試驗的(de)電(dian)(dian)(dian)(dian)(dian)流為1A.按ICR18650電(dian)(dian)(dian)(dian)(dian)池的(de)技術(shu)(shu)條(tiao)件，進(jin)行了(le)電(dian)(dian)(dian)(dian)(dian)池的(de)倍率（1 C）、低(di)溫（一20C、一30C、一40C）、循環壽命試驗及安全(quan)特性(xing)(xing)試驗。其中(zhong)安全(quan)特性(xing)(xing)試驗包括過充(chong)(chong)（3C充(chong)(chong)電(dian)(dian)(dian)(dian)(dian)、限壓10V）、短路(lu)（電(dian)(dian)(dian)(dian)(dian)阻小于50線路(lu)內短接(jie)）、沖擊(ji)（10kg重物(wu)、2/3m 5mm尖針刺透）、熱箱（150°C環境下(xia)放置(zhi)）等。所有試驗數據由(you)計算機自動采集，試驗現象遠程可視化(hua)監控記(ji)錄。電(dian)(dian)(dian)(dian)(dian)池的(de)電(dian)(dian)(dian)(dian)(dian)性(xing)(xing)能試驗在ArbinBT-2401自動充(chong)(chong)放電(dian)(dian)(dian)(dian)(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(qi)表(biao)面生(sheng)成(cheng)一層固體電解質保護(hu)膜，消耗(hao)一定量的(de)正極活性物質成(cheng)為不可逆(ni)容量。米用LiNi0.Co0.O2作正極時，電池(chi)設(she)計不必考慮過多增(zeng)加正極活性物質量。

　　平(ping)均每次循環容(rong)降0.04%.電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)(chi)(chi)以1C、2C速(su)(su)率(lv)(lv)放(fang)(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)容(rong)量(liang)(liang)分(fen)別為初始(shi)(shi)容(rong)量(liang)(liang)的(de)(de)(de)(de)99.4%和98. 9%.電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)(chi)(chi)具有良(liang)好的(de)(de)(de)(de)低(di)溫(wen)放(fang)(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)特性，在一(yi)MCMLiCoO2電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)(chi)(chi)倍率(lv)(lv)放(fang)(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)曲線°以0. 30時，以率(lv)(lv)放(fang)(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)容(rong)量(liang)(liang)達(da)到了(le)初始(shi)(shi)容(rong)量(liang)(liang)的(de)(de)(de)(de)80%；在一(yi)40時以0.2C速(su)(su)率(lv)(lv)放(fang)(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)達(da)到了(le)初始(shi)(shi)容(rong)量(liang)(liang)的(de)(de)(de)(de)60%.電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)(chi)(chi)良(liang)好的(de)(de)(de)(de)低(di)溫(wen)放(fang)(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)特性主要是電(dian)(dian)(dian)(dian)(dian)(dian)極(ji)材料和電(dian)(dian)(dian)(dian)(dian)(dian)MCMLiCoO2電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)(chi)(chi)低(di)溫(wen)放(fang)(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)峨液(ye)共同(tong)作用的(de)(de)(de)(de)結果(guo)。尤負極(ji)的(de)(de)(de)(de)18650型鋰離子蓄電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)(chi)(chi)放(fang)(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)特性曲線。電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)(chi)(chi)的(de)(de)(de)(de)放(fang)(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)容(rong)量(liang)(liang)大于1700mAh，電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)(chi)(chi)在室溫(wen)、充放(fang)(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)壓(ya)2.75放(fang)(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)效(xiao)率(lv)(lv)由(you)87%提(ti)高到90.6%.并且在優化的(de)(de)(de)(de)電(dian)(dian)(dian)(dian)(dian)(dian)液(ye)體系中，電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)(chi)(chi)的(de)(de)(de)(de)充放(fang)(fang)(fang)(fang)電(dian)(dian)(dian)(dian)(dian)(dian)效(xiao)率(lv)(lv)可提(ti)高到近(jin)92%.通(tong)過改進電(dian)(dian)(dian)(dian)(dian)(dian)極(ji)成型加工工藝，提(ti)高了(le)電(dian)(dian)(dian)(dian)(dian)(dian)池(chi)(chi)(chi)循環的(de)(de)(de)(de)穩定性。

　　~是以Li-CoO2為正極(ji)、MCMB為負極(ji)的(de)(de)18650型鋰離子蓄電池的(de)(de)放電特性(xing)曲(qu)線。

　　41V、1A放電電流、100%DOD條件下(xia)，循環壽(shou)命超(chao)過1000次，平均(jun)每次循環容(rong)(rong)降0.04%.電(dian)(dian)池良(liang)好(hao)的(de)循環壽(shou)命主要得(de)益于(yu)電(dian)(dian)極(ji)在電(dian)(dian)解液中(zhong)的(de)穩定(ding)性31.電(dian)(dian)池以1C、2C速(su)率放(fang)(fang)電(dian)(dian)容(rong)(rong)量(liang)分別為(wei)初(chu)始容(rong)(rong)量(liang)的(de)945%和(he)89.8%.電(dian)(dian)池在一(yi)由圖可知，放(fang)(fang)電(dian)(dian)容(rong)(rong)量(liang)大于(yu)1550mAh，電(dian)(dian)池在室(shi)溫、充放(fang)(fang)電(dian)(dian)壓2.75~41V、1A放(fang)(fang)電(dian)(dian)電(dian)(dian)流、100%DOD條件下(xia)，循環壽(shou)命超(chao)過1000次，C時(shi)以0.2C速(su)率放(fang)(fang)電(dian)(dian)容(rong)(rong)量(liang)為(wei)初(chu)始容(rong)(rong)量(liang)的(de)80. 5%，一(yi)30C時(shi)放(fang)(fang)電(dian)(dian)容(rong)(rong)量(liang)為(wei)初(chu)始容(rong)(rong)量(liang)的(de)57.1%. ~2為(wei)電(dian)(dian)池的(de)安全特性試驗曲線。

　　電池低溫放電曲線過充、短路、沖擊等項試lowtemperature驗中(zhong)，電池的取溫(wen)度低于120C無起火、爆炸研究(jiu)與(yu)設(she)計(ji)現象發生，安(an)全(quan)可(ke)靠。這(zhe)是因為在電池的設(she)計(ji)及制作(zuo)中(zhong)，從材料、結構(gou)、安(an)全(quan)裝置等多方面采取了安(an)全(quan)保護(hu)措施。

　　3結(jie)論(lun)通過試驗和(he)(he)選(xuan)擇電(dian)極(ji)材料，改(gai)進電(dian)極(ji)成型(xing)工(gong)藝(yi)，篩選(xuan)電(dian)液體系(xi)，優(you)化電(dian)池(chi)(chi)設計和(he)(he)安全設計，研制(zhi)成了為(wei)正(zheng)極(ji)、MCMB為(wei)負(fu)極(ji)的(de)18650型(xing)鋰離子(zi)蓄電(dian)池(chi)(chi)。電(dian)池(chi)(chi)具有較高的(de)放(fang)電(dian)容量(liang)和(he)(he)1700mAh）高的(de)比能量(liang)（130Wh/kg和(he)(he)350Wh/L）長的(de)工(gong)作(zuo)壽命（1 000次）和(he)(he)良好的(de)低溫放(fang)電(dian)性(xing)能（一40°C）。電(dian)池(chi)(chi)工(gong)作(zuo)安全可靠，能滿足不同(tong)領(ling)域對(dui)電(dian)池(chi)(chi)的(de)特殊要(yao)求。

                                                                                                                                  本文摘自(zi)于中(zhong)國(guo)鋰電網