鋰離子電池的結(jié)構(gòu)及材料發(fā)展文獻(xiàn)綜述1.1鋰離子電池發(fā)展歷程鋰離子電池最早是在1976年由ExxonMobil公司的Whittingham提出來，Whittingham發(fā)現(xiàn)在室溫下，層狀的TiS2可以與金屬鋰產(chǎn)生電化學(xué)反應(yīng)，并且首次把能量存儲和插入反應(yīng)有機(jī)結(jié)合在一起。二十世紀(jì)七十年代末期，Armand進(jìn)一步全面地討論了插層材料的機(jī)理，并提出了一種新穎的可充電電池設(shè)計(jì)，即“搖椅電池”，它建立在兩個(gè)具有不同電勢的插層電極上，Li+可逆地從一側(cè)到另一側(cè)。隨后Armand等人在1978年申請的專利中確定了石墨適合作為插層式負(fù)極的適用性。二十世紀(jì)八十年代年后，鋰離子電池的研究取得了突破性的進(jìn)展。1980年，Goodenough課題組制成了LiCoO2正極材料，其電位是TiS2的兩倍，并且具有良好的電化學(xué)可逆性，正是由于這一優(yōu)點(diǎn)，LiCoO2在接下來的30年中成為了幾乎無與倫比的商業(yè)化正極材料ADDINEN.CITE<EndNote><Cite><Author>Mizushima</Author><Year>1980</Year><RecNum>11</RecNum><DisplayText><styleface="superscript">[7]</style></DisplayText><record><rec-number>11</rec-number><foreign-keys><keyapp="EN"db-id="d9d5tw0e70fsw9edt5s590ftwxtvx9tz5vxw"timestamp="1620875534">11</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Mizushima,K.</author><author>Jones,P.C.</author><author>Wiseman,P.J.</author><author>Goodenough,J.B.</author></authors></contributors><titles><title>LixCoO2(0<x<-1):Anewcathodematerialforbatteriesofhighenergydensity</title><secondary-title>MaterialsResearchBulletin</secondary-title></titles><periodical><full-title>MaterialsResearchBulletin</full-title></periodical><pages>783-789</pages><volume>15</volume><number>6</number><dates><year>1980</year><pub-dates><date>1980/06/01/</date></pub-dates></dates><isbn>0025-5408</isbn><urls><related-urls><url>/science/article/pii/0025540880900124</url></related-urls></urls><electronic-resource-num>/10.1016/0025-5408(80)90012-4</electronic-resource-num></record></Cite></EndNote>[7]；1983年，Goodenough課題組制成正極材料LiMn2O4ADDINEN.CITE<EndNote><Cite><Author>Thackeray</Author><Year>1983</Year><RecNum>12</RecNum><DisplayText><styleface="superscript">[8]</style></DisplayText><record><rec-number>12</rec-number><foreign-keys><keyapp="EN"db-id="d9d5tw0e70fsw9edt5s590ftwxtvx9tz5vxw"timestamp="1620875655">12</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Thackeray,M.M.</author><author>David,W.I.F.</author><author>Bruce,P.G.</author><author>Goodenough,J.B.</author></authors></contributors><titles><title>Lithiuminsertionintomanganesespinels</title><secondary-title>MaterialsResearchBulletin</secondary-title></titles><periodical><full-title>MaterialsResearchBulletin</full-title></periodical><pages>461-472</pages><volume>18</volume><number>4</number><dates><year>1983</year><pub-dates><date>1983/04/01/</date></pub-dates></dates><isbn>0025-5408</isbn><urls><related-urls><url>/science/article/pii/0025540883901381</url></related-urls></urls><electronic-resource-num>/10.1016/0025-5408(83)90138-1</electronic-resource-num></record></Cite></EndNote>[8]；吉野章于1983年組裝了首個(gè)商用鋰離子電池，該產(chǎn)品將Goodenough的LiCoO2材料作為正極材料與熱處理的石油焦基碳負(fù)極相結(jié)合；1991年，Sony公司的商品化鋰離子二次電池(LiCoO2/C)成為真正意義上的鋰離子電池。實(shí)現(xiàn)了以石墨化碳材料為負(fù)極的鋰二次電池，其組成為：鈷酸鋰/電解質(zhì)/石墨化碳材料；Guyomard和Tarascon在1993年提出了一種在碳酸乙烯酯和碳酸二甲酯(DMC)中基于LiPF6的電解質(zhì)，該電解質(zhì)后來成為當(dāng)今鋰離子電池的標(biāo)準(zhǔn)電解質(zhì)配方ADDINEN.CITE<EndNote><Cite><Author>Guyomard</Author><Year>1993</Year><RecNum>13</RecNum><DisplayText><styleface="superscript">[9]</style></DisplayText><record><rec-number>13</rec-number><foreign-keys><keyapp="EN"db-id="d9d5tw0e70fsw9edt5s590ftwxtvx9tz5vxw"timestamp="1620875914">13</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Guyomard,D.</author><author>Tarascon,J.M.</author></authors></contributors><titles><title>RechargeableLi1?+?xMn2?O?4?/?CarbonCellswithaNewElectrolyteComposition:PotentiostaticStudiesandApplicationtoPracticalCells</title><secondary-title>JournalofTheElectrochemicalSociety</secondary-title></titles><periodical><full-title>JournalofTheElectrochemicalSociety</full-title></periodical><pages>3071-3081</pages><volume>140</volume><number>11</number><dates><year>1993</year><pub-dates><date>1993/11/01</date></pub-dates></dates><publisher>TheElectrochemicalSociety</publisher><isbn>0013-4651 1945-7111</isbn><urls><related-urls><url>/10.1149/1.2220987</url></related-urls></urls><electronic-resource-num>10.1149/1.2220987</electronic-resource-num></record></Cite></EndNote>[9]；1997年，Goodenough報(bào)道了一種正極材料LiFePO4ADDINEN.CITE<EndNote><Cite><Author>Padhi</Author><Year>1997</Year><RecNum>14</RecNum><DisplayText><styleface="superscript">[10]</style></DisplayText><record><rec-number>14</rec-number><foreign-keys><keyapp="EN"db-id="d9d5tw0e70fsw9edt5s590ftwxtvx9tz5vxw"timestamp="1620876019">14</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Padhi,A.K.</author><author>Nanjundaswamy,K.S.</author><author>Goodenough,J.B.</author></authors></contributors><titles><title>Phospho‐olivinesasPositive‐ElectrodeMaterialsforRechargeableLithiumBatteries</title><secondary-title>JournalofTheElectrochemicalSociety</secondary-title></titles><periodical><full-title>JournalofTheElectrochemicalSociety</full-title></periodical><pages>1188-1194</pages><volume>144</volume><number>4</number><dates><year>1997</year><pub-dates><date>1997/04/01</date></pub-dates></dates><publisher>TheElectrochemicalSociety</publisher><isbn>0013-4651 1945-7111</isbn><urls><related-urls><url>/10.1149/1.1837571</url></related-urls></urls><electronic-resource-num>10.1149/1.1837571</electronic-resource-num></record></Cite></EndNote>[10]；2000年，Thackeray等人報(bào)道了鋰鎳鈷錳氧化物(NCM)材料，大大減少了鈷的含量。由于Goodenough，Whittingham以及吉野章三人在鋰離子電池方面所做出的突出貢獻(xiàn)，三人共同獲得了2019年諾貝爾化學(xué)獎。圖1-1過去40年來鋰離子電池的關(guān)鍵發(fā)現(xiàn)ADDINEN.CITEADDINEN.CITE.DATA[11]。Figure1-1Keyfindingsoflithium-ionbatteriesinthepast40years1.2鋰離子電池的結(jié)構(gòu)和工作原理鋰離子電池主要由正極材料，負(fù)極材料，隔膜，電解液四部分構(gòu)成。正極材料是鋰離子電池最重要的組成部分，一般為含Li的過渡金屬化合物，包括LiCoO2，LiFePO4，LiNixCoyMn1-x-yO2以及LiNixCoyAl1-x-yO2等材料。正極材料在鋰離子電池的充放電過程中要完成Li+的反復(fù)脫嵌，同時(shí)自身發(fā)生氧化還原反應(yīng)。負(fù)極材料同樣要求具備Li+的脫嵌能力，一般為石墨等碳材料。隔膜的作用是將正負(fù)極隔開以防止電池短路，同時(shí)能允許Li+通過，隔膜一般為多孔高分子聚合物，目前商業(yè)化的隔膜材質(zhì)主要是聚乙烯和聚丙烯等材料，隔膜的性能決定了電池的界面結(jié)構(gòu)、內(nèi)阻等，直接影響電池的容量、循環(huán)以及安全性能等特性。電解液一般是鋰鹽溶解于有機(jī)溶劑中，目前廣泛應(yīng)用的電解液鋰鹽為LiPF6，有機(jī)溶劑為碳酸乙烯酯(EC)和碳酸二甲酯(DMC)。鋰離子電池與其他二次電池一樣，在充放電過程中完成化學(xué)能與電能的轉(zhuǎn)換。鋰離子電池的工作原理如圖1-2所示，在充放電過程中Li+會在正極和負(fù)極之間來回移動，鋰離子電池的充放電過程，就是鋰離子嵌入和脫嵌的過程。充電時(shí)，Li+從正極材料的晶格中脫嵌進(jìn)入電解質(zhì)中，經(jīng)過電解質(zhì)和隔膜嵌入負(fù)極材料，電子通過外電路由正極移動到負(fù)極；放電時(shí)則相反。圖1-2鋰離子電池的工作原理示意圖ADDINEN.CITE<EndNote><Cite><Author>Zhang</Author><Year>2015</Year><RecNum>15</RecNum><DisplayText><styleface="superscript">[12]</style></DisplayText><record><rec-number>15</rec-number><foreign-keys><keyapp="EN"db-id="d9d5tw0e70fsw9edt5s590ftwxtvx9tz5vxw"timestamp="1620879052">15</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Zhang,YiDi</author><author>Li,Yi</author><author>Xia,XinHui</author><author>Wang,XiuLi</author><author>Gu,ChangDong</author><author>Tu,JiangPing</author></authors></contributors><titles><title>High-energycathodematerialsforLi-ionbatteries:Areviewofrecentdevelopments</title><secondary-title>ScienceChinaTechnologicalSciences</secondary-title></titles><periodical><full-title>ScienceChinaTechnologicalSciences</full-title></periodical><pages>1809-1828</pages><volume>58</volume><number>11</number><dates><year>2015</year><pub-dates><date>2015/11/01</date></pub-dates></dates><isbn>1869-1900</isbn><urls><related-urls><url>/10.1007/s11431-015-5933-x</url></related-urls></urls><electronic-resource-num>10.1007/s11431-015-5933-x</electronic-resource-num></record></Cite></EndNote>[12]Figure1-2Schematicdiagramoftheworkingprincipleoflithium-ionbattery鋰離子電池的電化學(xué)反應(yīng)如下：正極反應(yīng)：LiMO2負(fù)極反應(yīng)：C+電池總反應(yīng)：LiMO21.3鋰離子電池正極材料簡介在鋰離子電池系統(tǒng)中，正極材料是其至關(guān)重要的一部分，相較于負(fù)極材料，正極材料的比容量低，循環(huán)穩(wěn)定性差，制備成本高且工藝較復(fù)雜，是決定鋰離子電池性能最重要的一環(huán)。為了提高鋰離子電池的性能，以滿足日益增長的需求，正極材料需要滿足一下要求：(1)比容量高，正極材料的比容量決定著鋰離子電池的能量密度；（2）循環(huán)性能好，材料在循環(huán)過程中要保持結(jié)構(gòu)穩(wěn)定，有較長的使用壽命；（3）具有較高的電子電導(dǎo)率和離子電導(dǎo)率，要有良好的倍率性能；（4）化學(xué)穩(wěn)定性和熱穩(wěn)定性好，鋰離子電池要具備一定的安全性；（5）低毒，且對環(huán)境友好；（6）成本低，相對較低的價(jià)格能擴(kuò)大鋰離子電池的適用范圍。目前研究最多的正極材料主要有三大類，分別是橄欖石型結(jié)構(gòu)的LiFePO4，尖晶石型的LiMn2O4，層狀結(jié)構(gòu)的LiCoO2以及三元材料LiNixCoyMn1-x-yO2和LiNixCoyAl1-x-yO2。橄欖石型結(jié)構(gòu)的LiFePO4正極材料在1997年由Goodenough課題組首次報(bào)道，由于材料本身的熱穩(wěn)定性好，安全性高，并且價(jià)格低廉而受到廣泛的研究和關(guān)注，已成為電池研究領(lǐng)域中最熱門的正極材料之一ADDINEN.CITE<EndNote><Cite><Author>Wang</Author><Year>2015</Year><RecNum>17</RecNum><DisplayText><styleface="superscript">[13]</style></DisplayText><record><rec-number>17</rec-number><foreign-keys><keyapp="EN"db-id="d9d5tw0e70fsw9edt5s590ftwxtvx9tz5vxw"timestamp="1620880276">17</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Wang,Jiajun</author><author>Sun,Xueliang</author></authors></contributors><titles><title>OlivineLiFePO4:theremainingchallengesforfutureenergystorage</title><secondary-title>Energy&EnvironmentalScience</secondary-title></titles><periodical><full-title>Energy&EnvironmentalScience</full-title></periodical><pages>1110-1138</pages><volume>8</volume><number>4</number><section>1110</section><dates><year>2015</year></dates><isbn>1754-5692 1754-5706</isbn><urls></urls><electronic-resource-num>10.1039/c4ee04016c</electronic-resource-num></record></Cite></EndNote>[13]。橄欖石型LiFePO4為正交晶系，屬于Pnma空間群。如圖1-3所示，氧原子以略微扭曲的六邊形密堆積排列，磷原子占據(jù)四面體位點(diǎn)；鐵和鋰原子分別占據(jù)八面體4a和4c位置。圖1-3沿[001]投影的橄欖石LiFePO4的晶體結(jié)構(gòu)ADDINEN.CITE<EndNote><Cite><Author>Tarascon</Author><Year>2001</Year><RecNum>16</RecNum><DisplayText><styleface="superscript">[14]</style></DisplayText><record><rec-number>16</rec-number><foreign-keys><keyapp="EN"db-id="d9d5tw0e70fsw9edt5s590ftwxtvx9tz5vxw"timestamp="1620880183">16</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Tarascon,J.M.</author><author>Armand,M.</author></authors></contributors><titles><title>Issuesandchallengesfacingrechargeablelithiumbatteries</title><secondary-title>Nature</secondary-title></titles><periodical><full-title>Nature</full-title></periodical><pages>359-367</pages><volume>414</volume><number>6861</number><dates><year>2001</year><pub-dates><date>2001/11/01</date></pub-dates></dates><isbn>1476-4687</isbn><urls><related-urls><url>/10.1038/35104644</url></related-urls></urls><electronic-resource-num>10.1038/35104644</electronic-resource-num></record></Cite></EndNote>[14]。Figure1-3ThecrystalstructureofolivineLiFePO4inprojectionalong[001].橄欖石型LiFePO4被認(rèn)為是用于電動汽車最具競爭力的正極材料，然而，LiFePO4的電子電導(dǎo)率低限制了它的應(yīng)用和發(fā)展，因此，已經(jīng)做出了許多努力來改善LiFePO4的性能ADDINEN.CITE<EndNote><Cite><Author>Wang</Author><Year>2008</Year><RecNum>18</RecNum><DisplayText><styleface="superscript">[15]</style></DisplayText><record><rec-number>18</rec-number><foreign-keys><keyapp="EN"db-id="d9d5tw0e70fsw9edt5s590ftwxtvx9tz5vxw"timestamp="1620880786">18</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Wang,Y.</author><author>Wang,Y.</author><author>Hosono,E.</author><author>Wang,K.</author><author>Zhou,H.</author></authors></contributors><auth-address>InstituteofEnergyTechnology,NationalInstituteofAdvancedIndustrialScienceandTechnology(AIST),Umezono1-1-1,Tsukuba,Japan.</auth-address><titles><title>ThedesignofaLiFePO4/carbonnanocompositewithacore-shellstructureanditssynthesisbyaninsitupolymerizationrestrictionmethod</title><secondary-title>AngewChemIntEdEngl</secondary-title></titles><periodical><full-title>AngewChemIntEdEngl</full-title></periodical><pages>7461-5</pages><volume>47</volume><number>39</number><edition>2008/08/23</edition><dates><year>2008</year></dates><isbn>1521-3773(Electronic) 1433-7851(Linking)</isbn><accession-num>18720357</accession-num><urls><related-urls><url>/pubmed/18720357</url></related-urls></urls><electronic-resource-num>10.1002/anie.200802539</electronic-resource-num></record></Cite></EndNote>[15]。碳包覆是提高LiFePO4正極材料電導(dǎo)率的一種廣泛接受的方法ADDINEN.CITE<EndNote><Cite><Author>Wang</Author><Year>2018</Year><RecNum>19</RecNum><DisplayText><styleface="superscript">[16]</style></DisplayText><record><rec-number>19</rec-number><foreign-keys><keyapp="EN"db-id="d9d5tw0e70fsw9edt5s590ftwxtvx9tz5vxw"timestamp="1620881137">19</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Wang,Xufeng</author><author>Feng,Zhijun</author><author>Huang,Juntong</author><author>Deng,Wen</author><author>Li,Xibao</author><author>Zhang,Huasen</author><author>Wen,Zhenhai</author></authors></contributors><titles><title>Graphene-decoratedcarbon-coatedLiFePO4nanospheresasahigh-performancecathodematerialforlithium-ionbatteries</title><secondary-title>Carbon</secondary-title></titles><periodical><full-title>Carbon</full-title></periodical><pages>149-157</pages><volume>127</volume><keywords><keyword>Graphene</keyword><keyword>Carbon-coatedLiFePO</keyword><keyword>Cathodematerials</keyword><keyword>Lithium-ionbatteries</keyword></keywords><dates><year>2018</year><pub-dates><date>2018/02/01/</date></pub-dates></dates><isbn>0008-6223</isbn><urls><related-urls><url>/science/article/pii/S0008622317311053</url></related-urls></urls><electronic-resource-num>/10.1016/j.carbon.2017.10.101</electronic-resource-num></record></Cite></EndNote>[16]。通常，碳包覆過程涉及將電池材料與各種碳前體混合，然后進(jìn)行高溫?zé)崽幚怼＿@種方法簡單，可行，適合大規(guī)模工業(yè)生產(chǎn)。然而，控制均勻的包覆層和改善包覆層質(zhì)量仍然是非常具有挑戰(zhàn)性的。碳包覆層太薄將不能均勻地覆蓋活性材料，但是碳包覆層太厚將限制鋰離子擴(kuò)散并降低電池材料的體積能量密度。為了滿足對高性能電池材料的需求，當(dāng)前的碳包覆層技術(shù)仍需要進(jìn)一步改進(jìn)。目前，主要有選擇高質(zhì)量碳源，改善包覆技術(shù)，制備混合涂層等方法來進(jìn)一步改進(jìn)碳包覆LiFePO4正極材料。除了碳包覆改性策略外，摻雜被認(rèn)為是增強(qiáng)LiFePO4固有電子/離子電導(dǎo)率的另一種重要方法，摻雜方法主要有在Li位點(diǎn)，F(xiàn)e位點(diǎn)的陽離子和在O位點(diǎn)處的陰離子摻雜來改善LiFePO4正極材料的電化學(xué)性能，提高材料的循環(huán)和倍率性能ADDINEN.CITEADDINEN.CITE.DATA[17-18]。尖晶石型結(jié)構(gòu)的正極材料LiMn2O4工作電壓較高(4.7V)，理論比容量有148mAhg-1，原料儲量豐富且合成相對容易，是當(dāng)前鋰離子電池中有希望的正極材料之一ADDINEN.CITE<EndNote><Cite><Author>Chen</Author><Year>2021</Year><RecNum>22</RecNum><DisplayText><styleface="superscript">[19]</style></DisplayText><record><rec-number>22</rec-number><foreign-keys><keyapp="EN"db-id="d9d5tw0e70fsw9edt5s590ftwxtvx9tz5vxw"timestamp="1620883286">22</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Chen,Junxin</author><author>Huang,Zhe</author><author>Zeng,Weihao</author><author>Cao,Fei</author><author>Ma,Jingjing</author><author>Tian,Weixi</author><author>Mu,Shichun</author></authors></contributors><titles><title>Synthesis,Modification,andLithium‐StoragePropertiesofSpinelLiNi 0.5 Mn 1.5 O 4</title><secondary-title>ChemElectroChem</secondary-title></titles><periodical><full-title>ChemElectroChem</full-title></periodical><pages>608-624</pages><volume>8</volume><number>4</number><section>608</section><dates><year>2021</year></dates><isbn>2196-0216 2196-0216</isbn><urls></urls><electronic-resource-num>10.1002/celc.202001414</electronic-resource-num></record></Cite></EndNote>[19]。LiMn2O4的結(jié)構(gòu)屬于Fd-3m空間群，晶體結(jié)構(gòu)如圖1-4所示，具有三維的鋰離子擴(kuò)散通道，Li位于四面體8a位點(diǎn)，Mn占八面體16d位點(diǎn)，而O占在32e位點(diǎn)。當(dāng)LiMn2O4充電時(shí)，Li+將從四面體8a位點(diǎn)釋放。充電過程的完成時(shí)，LiMn2O4結(jié)構(gòu)演變?yōu)镸n2O4，其中錳離子的化合價(jià)態(tài)也完全變?yōu)?4。LiMn2O4放電時(shí)，材料會經(jīng)歷單相到兩個(gè)立方相Li0.5Mn2O4和λ-MnO2共存的相轉(zhuǎn)變，與此對應(yīng)的是放電曲線上有兩個(gè)平臺：4.10V和3.95VADDINEN.CITEADDINEN.CITE.DATA[20-21]。LiMn2O4在電化學(xué)循環(huán)過程中會發(fā)生過渡金屬溶解，Jahn-Teller效應(yīng)，巖鹽相變，以及與電解質(zhì)的副反應(yīng)，縮短了材料的循環(huán)壽命，限制了大規(guī)模的商業(yè)應(yīng)用。通過用Ni取代部分Mn位獲得了的高電壓(5V)正極材料LiNi0.5Mn1.5O4ADDINEN.CITE<EndNote><Cite><Author>Liang</Author><Year>2020</Year><RecNum>25</RecNum><DisplayText><styleface="superscript">[22]</style></DisplayText><record><rec-number>25</rec-number><foreign-keys><keyapp="EN"db-id="d9d5tw0e70fsw9edt5s590ftwxtvx9tz5vxw"timestamp="1620883770">25</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Liang,Gemeng</author><author>Peterson,VanessaK.</author><author>See,KhayWai</author><author>Guo,Zaiping</author><author>Pang,WeiKong</author></authors></contributors><titles><title>Developinghigh-voltagespinelLiNi0.5Mn1.5O4cathodesforhigh-energy-densitylithium-ionbatteries:currentachievementsandfutureprospects</title><secondary-title>JournalofMaterialsChemistryA</secondary-title></titles><periodical><full-title>JournalofMaterialsChemistryA</full-title></periodical><pages>15373-15398</pages><volume>8</volume><number>31</number><dates><year>2020</year></dates><publisher>TheRoyalSocietyofChemistry</publisher><isbn>2050-7488</isbn><work-type>10.1039/D0TA02812F</work-type><urls><related-urls><url>/10.1039/D0TA02812F</url></related-urls></urls><electronic-resource-num>10.1039/D0TA02812F</electronic-resource-num></record></Cite></EndNote>[22]。LiNi0.5Mn1.5O4具有兩個(gè)晶體結(jié)構(gòu)，即P4332（有序）和Fd-3m（無序），其中Fd-3m晶格具有高度對稱性。LiNi0.5Mn1.5O4面臨著與LiMn2O4同樣的問題，依然發(fā)生過渡金屬溶解和Jahn-Teller效應(yīng)，同時(shí)其高工作電壓導(dǎo)致無法與普通電解液相適應(yīng)，也限制了大規(guī)模的使用。許多研究者對LiMn2O4和LiNi0.5Mn1.5O4做了摻雜，包覆等改性，在一定程度上提高了材料的循環(huán)穩(wěn)定性ADDINEN.CITEADDINEN.CITE.DATA[23-24]。圖1-4LiMn2O4尖晶石晶體結(jié)構(gòu)。Figure1-4LiMn2O4spinelcrystalstructure.層狀結(jié)構(gòu)材料LiCoO2是最早商業(yè)化的鋰離子電池正極材料。由于LiCoO2具有高振實(shí)密度，高能量密度，良好的電子/離子電導(dǎo)率，優(yōu)異的循環(huán)壽命和可靠性，使其成為便攜式電子設(shè)備市場中鋰離子電池的主要正極ADDINEN.CITE<EndNote><Cite><Author>Lyu</Author><Year>2020</Year><RecNum>33</RecNum><DisplayText><styleface="superscript">[25]</style></DisplayText><record><rec-number>33</rec-number><foreign-keys><keyapp="EN"db-id="d9d5tw0e70fsw9edt5s590ftwxtvx9tz5vxw"timestamp="1620885459">33</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Lyu,Yingchun</author><author>Wu,Xia</author><author>Wang,Kai</author><author>Feng,Zhijie</author><author>Cheng,Tao</author><author>Liu,Yang</author><author>Wang,Meng</author><author>Chen,Riming</author><author>Xu,Leimin</author><author>Zhou,Jingjing</author><author>Lu,Yuhao</author><author>Guo,Bingkun</author></authors></contributors><titles><title>AnOverviewontheAdvancesofLiCoO 2 CathodesforLithium‐IonBatteries</title><secondary-title>AdvancedEnergyMaterials</secondary-title></titles><periodical><full-title>AdvancedEnergyMaterials</full-title></periodical><volume>11</volume><number>2</number><section>2000982</section><dates><year>2020</year></dates><isbn>1614-6832 1614-6840</isbn><urls></urls><electronic-resource-num>10.1002/aenm.202000982</electronic-resource-num></record></Cite></EndNote>[25]。LiCoO2具有α-NaFeO2型分層結(jié)構(gòu)，屬于R-3m空間群，如圖1-5所示。為了滿足智能手機(jī)和筆記本電腦等便攜式電子設(shè)備不斷增長的能源需求，LiCoO2的電池的截止電壓一直在提高，以實(shí)現(xiàn)更高的能量密度。但是，LiCoO2在高電壓（>4.2Vvs.Li/Li+）時(shí)，就會出現(xiàn)一些有害的問題，包括表面退化，相變引起的晶體損傷，這會導(dǎo)致容量，壽命的迅速下降A(chǔ)DDINEN.CITEADDINEN.CITE.DATA[26-27]。為了克服上述問題并滿足LiCoO2在高壓下的長期循環(huán)穩(wěn)定性，已提出了各種策略，例如元素?fù)诫sADDINEN.CITE<EndNote><Cite><Author>Zhang</Author><Year>2019</Year><RecNum>28</RecNum><DisplayText><styleface="superscript">[28]</style></DisplayText><record><rec-number>28</rec-number><foreign-keys><keyapp="EN"db-id="d9d5tw0e70fsw9edt5s590ftwxtvx9tz5vxw"timestamp="1620884498">28</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Zhang,Jie-Nan</author><author>Li,Qinghao</author><author>Ouyang,Chuying</author><author>Yu,Xiqian</author><author>Ge,Mingyuan</author><author>Huang,Xiaojing</author><author>Hu,Enyuan</author><author>Ma,Chao</author><author>Li,Shaofeng</author><author>Xiao,Ruijuan</author><author>Yang,Wanli</author><author>Chu,Yong</author><author>Liu,Yijin</author><author>Yu,Huigen</author><author>Yang,Xiao-Qing</author><author>Huang,Xuejie</author><author>Chen,Liquan</author><author>Li,Hong</author></authors></contributors><titles><title>TracedopingofmultipleelementsenablesstablebatterycyclingofLiCoO2at4.6?V</title><secondary-title>NatureEnergy</secondary-title></titles><periodical><full-title>NatureEnergy</full-title></periodical><pages>594-603</pages><volume>4</volume><number>7</number><dates><year>2019</year><pub-dates><date>2019/07/01</date></pub-dates></dates><isbn>2058-7546</isbn><urls><related-urls><url>/10.1038/s41560-019-0409-z</url></related-urls></urls><electronic-resource-num>10.1038/s41560-019-0409-z</electronic-resource-num></record></Cite></EndNote>[28]，表面涂層ADDINEN.CITEADDINEN.CITE.DATA[29-30]等方法。經(jīng)過近30年的努力，商用鋰離子電池中LiCoO2的截止電壓已提高至4.5V，實(shí)現(xiàn)了約185mAhg-1的可逆容量，并具有實(shí)用的循環(huán)性能。LiCoO2的層狀結(jié)構(gòu)存在于鋰過渡金屬氧化物的其他類似物中，其通式為LiMO2，其中M=V，Cr，Ni和Fe。LiCoO2的成功應(yīng)用激發(fā)了人們探索鋰離子電池正極材料的興趣，例如，同屬層狀結(jié)構(gòu)的LiNiO2就是廣泛使用的NCM和NCA正極材料的基礎(chǔ)。層狀富鎳的LiNixCoyMn1-x-yO2和LiNixCoyAl1-x-yO2活性材料，由于其高能量密度，高比容量和較低的材料成本引起了人們極大的關(guān)注，成為電動汽車領(lǐng)域最具前景的鋰離子電池正極材料之一ADDINEN.CITEADDINEN.CITE.DATA[31-32]。但是，層狀富鎳材料較低的熱穩(wěn)定性以及對H2O和CO2的較高敏感性使其不易長期保存，并且會導(dǎo)致潛在的性能下降和安全性下降。因此需要繼續(xù)深入研究，提高層狀材料的熱穩(wěn)定性和循環(huán)穩(wěn)定性，使其能夠更好的發(fā)揮其高容量和低成本的優(yōu)勢ADDINEN.CITE<EndNote><Cite><Author>Xu</Author><Year>2017</Year><RecNum>36</RecNum><DisplayText><styleface="superscript">[33-34]</style></DisplayText><record><rec-number>36</rec-number><foreign-keys><keyapp="EN"db-id="d9d5tw0e70fsw9edt5s590ftwxtvx9tz5vxw"timestamp="1620886518">36</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Xu,Jing</author><author>Lin,Feng</author><author>Doeff,MarcaM.</author><author>Tong,Wei</author></authors></contributors><titles><title>AreviewofNi-basedlayeredoxidesforrechargeableLi-ionbatteries</title><secondary-title>JournalofMaterialsChemistryA</secondary-title></titles><periodical><full-title>JournalofMaterialsChemistryA</full-title></periodical><pages>874-901</pages><volume>5</volume><number>3</number><section>874</section><dates><year>2017</year></dates><isbn>2050-7488 2050-7496</isbn><urls></urls><electronic-resource-num>10.1039/c6ta07991a</electronic-resource-num></record></Cite><Cite><Author>Kim</Author><Year>2018</Year><RecNum>37</RecNum><record><rec-number>37</rec-number><foreign-keys><keyapp="EN"db-id="d9d5tw0e70fsw9edt5s590ftwxtvx9tz5vxw"timestamp="1620886552">37</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Kim,Junhyeok</author><author>Lee,Hyomyung</author><author>Cha,Hyungyeon</author><author>Yoon,Moonsu</author><author>Park,Minjoon</author><author>Cho,Jaephil</author></authors></contributors><titles><title>ProspectandRealityofNi-RichCathodeforCommercialization</title><secondary-title>AdvancedEnergyMaterials</secondary-title></titles><periodical><full-title>AdvancedEnergyMaterials</full-title></periodical><volume>8</volume><number>6</number><section>1702028</section><dates><year>2018</year></dates><isbn>16146832</isbn><urls></urls><electronic-resource-num>10.1002/aenm.201702028</electronic-resource-num></record></Cite></EndNote>[33-34]。圖1-5層狀氧化物L(fēng)iCoO2的晶體結(jié)構(gòu)示意圖Figure1-5SchematicdiagramofthecrystalstructureoflayeredoxideLiCoO2參考文獻(xiàn)：[1]王鵬博，鄭俊超.鋰離子電池的發(fā)展現(xiàn)狀及展望[J].自然雜志,2017,39(4):283-289.[2]FanE.,LiL.,WangZ.,etal.SustainableRecyclingTechnologyforLi-IonBatteriesandBeyond:ChallengesandFutureProspects[J].ChemRev,2020,120(14):7020-7063.[3]郭孝東，徐春柳，向偉，吳振國，鐘本和.富鎳三元正極材料的改性研究進(jìn)展[J].工程科學(xué)與技術(shù),2020,52(1):9-17.[4]WangX.,DingY.L.,DengY.P.,etal.Ni‐Rich/Co‐PoorLayeredCathodeforAutomotiveLi‐IonBatteries:PromisesandChallenges[J].AdvancedEnergyMaterials,2020,10(12).[5]WuF.,MaierJ.,YuY.Guidelinesandtrendsfornext-generationrechargeablelithiumandlithium-ionbatteries[J].ChemSocRev,2020,49(5):1569-1614.[6]ArmandM.,TarasconJ.M.Buildingbetterbatteries[J].Nature,2008,451(7179):652-657.[7]MizushimaK.,JonesP.C.,WisemanP.J.,etal.LixCoO2(0<x<-1):Anewcathodematerialforbatteriesofhighenergydensity[J].MaterialsResearchBulletin,1980,15(6):783-789.[8]ThackerayM.M.,DavidW.I.F.,BruceP.G.,etal.Lithiuminsertionintomanganesespinels[J].MaterialsResearchBulletin,1983,18(4):461-472.[9]GuyomardD.,TarasconJ.M.RechargeableLi1?+?xMn2?O?4?/?CarbonCellswithaNewElectrolyteComposition:PotentiostaticStudiesandApplicationtoPracticalCells[J].JournalofTheElectrochemicalSociety,1993,140(11):3071-3081.[10]PadhiA.K.,NanjundaswamyK.S.,GoodenoughJ.B.Phospho‐olivinesasPositive‐ElectrodeMaterialsforRechargeableLithiumBatteries[J].JournalofTheElectrochemicalSociety,1997,144(4):1188-1194.[11]ZhangH.,LiC.,EshetuG.G.,etal.FromSolid-SolutionElectrodesandtheRocking-ChairConcepttoToday'sBatteries[J].AngewChemIntEdEngl,2020,59(2):534-538.[12]ZhangY.,LiY.,XiaX.,etal.High-energycathodematerialsforLi-ionbatteries:Areviewofrecentdevelopments[J].ScienceChinaTechnologicalSciences,2015,58(11):1809-1828.[13]WangJ.,SunX.OlivineLiFePO4:theremainingchallengesforfutureenergystorage[J].Energy&EnvironmentalScience,2015,8(4):1110-113