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Article(id=1241081035262317204, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241081025531540408, articleNumber=null, orderNo=null, doi=10.3969/j.issn.0253-6099.2024.04.007, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1715097600000, receivedDateStr=2024-05-08, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1773826376976, onlineDateStr=2026-03-18, pubDate=1722441600000, pubDateStr=2024-08-01, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1773826376976, onlineIssueDateStr=2026-03-18, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1773826376976, creator=13701087609, updateTime=1773826376976, updator=13701087609, issue=Issue{id=1241081025531540408, tenantId=1146029695717560320, journalId=1235980550691926019, year='2024', volume='44', issue='4', pageStart='1', pageEnd='258', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1773826374657, creator=13701087609, updateTime=1773827517159, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1241085817590960730, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241081025531540408, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1241085817590960731, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241081025531540408, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=36, endPage=41, ext={EN=ArticleExt(id=1241081035581084321, articleId=1241081035262317204, tenantId=1146029695717560320, journalId=1235980550691926019, language=EN, title=Improvement of Cyclic Stability of Cathode Material LiNi0.8Co0.1Mn0.1O2 by Dual SiO2@Li2SiO3 Coating, columnId=1241081026567533498, journalTitle=Mining and Metallurgical Engineering, columnName=SPECIAL ISSUE: BATTERY MATERIALS, runingTitle=null, highlight=null, articleAbstract=

With an increase in Ni content, the capacity of high-nickel layered metal oxides (LiNixMnyCo1-x-yO2 (0.8≤x<1, NCM) greatly decreases. In view of such problem, it is proposed that singly-crystal NCM cathode material be modified by dual SiO2@Li2SiO3 coating to improve its electrochemical performance. During the synthesis process, the reaction of can consume the residue lithium on the material surface, thus improving diffusion kinetics of interface lithium ions and inhibiting side reaction at the interface. It is shown that the modified cathode material delivers a specific discharge capacity of 156.88 mAh/g after 120 cycles, with capacity retention rate of 70.52%.

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针对高镍层状金属氧化物（LiNixMnyCo1-x-yO2，0.8≤x<1，NCM）随着Ni摩尔分数增大而容量严重衰退问题，提出了利用SiO2@Li2SiO3双包覆层改性单晶NCM正极材料、提高其电化学性能的策略。合成过程中，通过反应消耗材料表面残锂，改善界面锂离子扩散动力学，抑制界面副反应。SiO2@Li2SiO3双包覆层改性正极材料在120次循环后放电比容量为156.88 mAh/g，容量保持率为70.52%。

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陈奎元（1995—），男，河南郑州人，硕士，讲师，研究方向为轨道交通新能源电池。E-mail：

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陈奎元（1995—），男，河南郑州人，硕士，讲师，研究方向为轨道交通新能源电池。E-mail：

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陈奎元（1995—），男，河南郑州人，硕士，讲师，研究方向为轨道交通新能源电池。E-mail：

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Journal of The Electrochemical Society, 2014, 161: A920-A926., articleTitle=Effect of residual lithium compounds on layer Ni-rich Li[Ni0.7Mn0.3]O2, refAbstract=null)], funds=[Fund(id=1241081050152096402, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241081035262317204, awardId=242102210171, language=CN, fundingSource=河南省科技攻关资助项目(242102210171), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1241081041344058364, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241081035262317204, xref=1., ext=[AuthorCompanyExt(id=1241081041348252669, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241081035262317204, companyId=1241081041344058364, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1.Zhengzhou Railway Vocational & Technical College, Zhengzhou 450018, Henan, China), AuthorCompanyExt(id=1241081041356641278, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241081035262317204, companyId=1241081041344058364, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1.郑州铁路职业技术学院，河南 郑州 450018)]), AuthorCompany(id=1241081041507635214, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241081035262317204, xref=2., ext=[AuthorCompanyExt(id=1241081041549578261, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241081035262317204, companyId=1241081041507635214, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=2.Luoyang Railway Information Engineering School, Luoyang 471000, Henan, China), AuthorCompanyExt(id=1241081041566355480, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241081035262317204, companyId=1241081041507635214, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=2.洛阳铁路信息工程学校，河南 洛阳 471000)]), AuthorCompany(id=1241081041738321953, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241081035262317204, xref=3., ext=[AuthorCompanyExt(id=1241081041750904867, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241081035262317204, companyId=1241081041738321953, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=3.Guizhou Minzu University, Guiyang 550025, Guizhou, China), AuthorCompanyExt(id=1241081041776070694, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241081035262317204, companyId=1241081041738321953, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=3.贵州民族大学，贵州 贵阳 550025)])], figs=[ArticleFig(id=1241081046473691567, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241081035262317204, language=EN, label=null, caption=null, figureFileSmall=aF1ynJfC6NHjm7frHw09TQ==, figureFileBig=bmG0iXDY4KwjdhTli5sRTw==, tableContent=null), ArticleFig(id=1241081046603715000, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241081035262317204, language=CN, label=图1, caption=材料的SEM图

（a）NCM；（b）0.5%SO@NCM；（c）1.0%SO@NCM；（d）1.5%SO@NCM

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（a）XRD图谱；（b）（003）峰放大图；（c）（006）/（012）峰放大图；（d）（018）/（110）峰放大图

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（a）1.0%SO@NCM；（b）NCM（101）区域放大图；（c）SiO2（102）区域放大图；（d）Li2SiO3（111）区域放大图

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（a）NCM；（b）1.0%SO@NCM

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（a）放电比容量；（b）容量保持率；（c）放电中压；（d）能量密度

, figureFileSmall=UKVHPBoWQ6meY0wFpZ+1Dg==, figureFileBig=FISVjb2dQKmvYYjy7y63hw==, tableContent=null), ArticleFig(id=1241081049422287434, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241081035262317204, language=EN, label=null, caption=null, figureFileSmall=xuohuQwRULlsEtwuCIAmZA==, figureFileBig=CzaNf2KStgFFj8X1KEhdjw==, tableContent=null), ArticleFig(id=1241081049556505171, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241081035262317204, language=CN, label=图6, caption=样品微分容量曲线

（a）NCM；（b）1.0%SO@NCM

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（a）NCM；（b）1.0%SO@NCM

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材料名称a/nmc/nmc/a值V/nm3混排程度/%
NCM0.287 51.426 74.9620.102 5424.71
0.5%SO@NCM0.286 81.426 34.9730.102 4224.63
1.0%SO@NCM0.287 21.427 14.9690.102 4314.42
1.5%SO@NCM0.287 11.426 84.9700.102 4734.56
), ArticleFig(id=1241081049996907139, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241081035262317204, language=CN, label=表1, caption=

材料精修参数

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材料名称a/nmc/nmc/a值V/nm3混排程度/%
NCM0.287 51.426 74.9620.102 5424.71
0.5%SO@NCM0.286 81.426 34.9730.102 4224.63
1.0%SO@NCM0.287 21.427 14.9690.102 4314.42
1.5%SO@NCM0.287 11.426 84.9700.102 4734.56
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SiO2@Li2SiO3双包覆层策略改善正极材料LiNi0.8Co0.1Mn0.1O2循环稳定性
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陈奎元 1 , 李凯强 2 , 李岩璞 3
矿冶工程杂志 | 电池材料专题 2024,44(4): 36-41
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矿冶工程杂志 | 电池材料专题 2024, 44(4): 36-41
SiO2@Li2SiO3双包覆层策略改善正极材料LiNi0.8Co0.1Mn0.1O2循环稳定性
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陈奎元1 , 李凯强2, 李岩璞3
作者信息
  • 1.郑州铁路职业技术学院，河南 郑州 450018
  • 2.洛阳铁路信息工程学校，河南 洛阳 471000
  • 3.贵州民族大学，贵州 贵阳 550025

    • 陈奎元（1995—），男，河南郑州人，硕士，讲师，研究方向为轨道交通新能源电池。E-mail：

Improvement of Cyclic Stability of Cathode Material LiNi0.8Co0.1Mn0.1O2 by Dual SiO2@Li2SiO3 Coating
Kuiyuan CHEN1 , Kaiqiang LI2, Yanpu LI3
Affiliations
  • 1.Zhengzhou Railway Vocational & Technical College, Zhengzhou 450018, Henan, China
  • 2.Luoyang Railway Information Engineering School, Luoyang 471000, Henan, China
  • 3.Guizhou Minzu University, Guiyang 550025, Guizhou, China
出版时间: 2024-08-01 doi: 10.3969/j.issn.0253-6099.2024.04.007
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摘要
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针对高镍层状金属氧化物（LiNixMnyCo1-x-yO2，0.8≤x<1，NCM）随着Ni摩尔分数增大而容量严重衰退问题，提出了利用SiO2@Li2SiO3双包覆层改性单晶NCM正极材料、提高其电化学性能的策略。合成过程中，通过反应消耗材料表面残锂，改善界面锂离子扩散动力学，抑制界面副反应。SiO2@Li2SiO3双包覆层改性正极材料在120次循环后放电比容量为156.88 mAh/g，容量保持率为70.52%。

锂离子电池  /  三元正极材料  /  改性  /  高镍层状金属氧化物  /  表面包覆  /  高能量密度  /  循环稳定性

With an increase in Ni content, the capacity of high-nickel layered metal oxides (LiNixMnyCo1-x-yO2 (0.8≤x<1, NCM) greatly decreases. In view of such problem, it is proposed that singly-crystal NCM cathode material be modified by dual SiO2@Li2SiO3 coating to improve its electrochemical performance. During the synthesis process, the reaction of can consume the residue lithium on the material surface, thus improving diffusion kinetics of interface lithium ions and inhibiting side reaction at the interface. It is shown that the modified cathode material delivers a specific discharge capacity of 156.88 mAh/g after 120 cycles, with capacity retention rate of 70.52%.

lithium-ion battery  /  ternary cathode material  /  modification  /  high nickel layered metal oxide  /  surface coating  /  high energy density  /  cyclic stability
陈奎元, 李凯强, 李岩璞. SiO2@Li2SiO3双包覆层策略改善正极材料LiNi0.8Co0.1Mn0.1O2循环稳定性. 矿冶工程杂志, 2024 , 44 (4) : 36 -41 . DOI: 10.3969/j.issn.0253-6099.2024.04.007
Kuiyuan CHEN, Kaiqiang LI, Yanpu LI. Improvement of Cyclic Stability of Cathode Material LiNi0.8Co0.1Mn0.1O2 by Dual SiO2@Li2SiO3 Coating[J]. Mining and Metallurgical Engineering, 2024 , 44 (4) : 36 -41 . DOI: 10.3969/j.issn.0253-6099.2024.04.007
正文
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锂离子电池广泛应用于智能手机、移动笔记本、可穿戴便捷设备等电子产品中。电动汽车的快速发展更进一步推动了锂离子电池行业的发展[1-2]。高镍三元正极材料（NCM）可以提供更多的Ni2+/Ni3+和Ni3+/Ni4+氧化还原对，具有更高的理论比容量（270～280 mAh/g）和实际放电比容量（200 mAh/g），因此，近年来研究者非常关注高镍层状氧化物正极材料（LiNixMnyCo1-x-yO2，0.8≤x<1）。然而，当正极材料中镍摩尔分数超过80%时，层状氧化物的结构稳定性随之下降，电池在长循环过程中会出现严重容量衰退[3]。此外，合成NCM正极材料的过程中需要添加过量的锂源来弥补高温煅烧下锂的挥发，导致NCM正极材料表面的残锂积累，残锂与空气中的CO2和H2O反应生成LiHCO3、LiOH和Li2CO3等碱性杂质，使颗粒表面的固有性质发生改变。正极材料中Li+离子半径（0.076 nm）和Ni2+离子半径（0.069 nm）较为接近，可导致不可逆的Li+/Ni2+阳离子混排现象发生[4]。同时，在高温高电压长循环中NCM正极材料会发生严重的伴随着晶格参数变化的H2-H3相变，长期的体积变化带来的应力积累导致二次颗粒微裂纹的形成。颗粒开裂不仅使颗粒界面处接触不良，而且大大增加了颗粒表面积，使正极材料发生严重容量衰退[5-7]。
因此，如何延缓高镍正极材料的容量衰减仍然是一个挑战。针对上述高镍NCM正极材料存在的问题，研究人员提出了表面涂层、元素掺杂和优化材料结构等方法来增强NCM正极材料的结构稳定性以提高它的电化学性能。为了缓解NCM正极材料在长循环中降解的问题，目前科研工作者做了大量研究，比如在正极材料颗粒表面附着一层致密的包覆层，其中包覆材料包括磷酸盐、过渡金属氧化物、金属氟化物和硅碳材料等，例如，Li1.3In0.3Ti1.7（P4O）3[8]，LiTi2（P4O）3[9]，Li4Mn5O12[10]，SiO2[11]，Li3PO4[12]和TiO2[13]都是提高正极材料界面稳定性的候选材料。这些表面改性方法可以提高正极材料与电解质界面的稳定性、减少副反应的发生、提高界面处Li+的扩散效率。然而，涂层与基体材料之间的弱结合可能导致涂层脱落，严重影响材料电化学性能。因此，具有良好的晶格适配的双功能涂层是实现长循环性能的首选[14]。
三元正极材料的颗粒是由一次颗粒团聚而形成的二次颗粒微球，与这种常规的二次球正极相比，准单晶NCM正极材料无随机取向的纳米颗粒（2～5 μm的一次颗粒）具有更强的结构稳定性，防止长循环过程中结构崩塌，并有效抑制副反应。钠超离子导体（NASICON）型结构的Li2SiO3材料具有优异的锂离子扩散系数，可以有效提高单晶NCM正极材料的导电性。鉴于此，本文提出了一种新的协同策略，以SiO2为原材料，通过反应，在消耗NCM正极材料表面残锂的同时在材料表面形成Li2SiO3修饰层，从而在材料表面获得SiO2@Li2SiO3双包覆层。使用XRD、SEM和TEM对材料进行表征，研究SiO2@Li2SiO3双包覆层在正极材料界面的保护作用和促进锂离子传输方面的独特影响。
1 实验部分
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1.1 实验样品制备
通过共沉淀法合成前驱体材料Ni0.8Co0.1Mn0.1（OH）2。
正极材料LiNi0.8Co0.1Mn0.1O2的制备：前驱体与LiOH（阿拉丁，99.9%）按1∶1.05（物质的量比）称量，充分研磨后在纯氧气气氛下500 ℃烧结10 h，随后升温至820 ℃烧结24 h，自然冷却，得到高镍三元正极材料LiNi0.8Co0.1Mn0.1O2。
SiO2@Li2SiO3双包覆层正极材料的制备：一定量的SiO2与LiNi0.8Co0.1Mn0.1O2正极材料充分混匀、研磨，得到的黑色粉末在纯氧气气氛下700 ℃烧结12 h，得到SiO2@Li2SiO3包覆的正极材料。将SiO2@Li2SiO3包覆层质量分数0.5%、1.0%和1.5%的样品分别标记为0.5%SO@NCM、1.0%SO@NCM和1.5%SO@NCM。
1.2 样品表征
采用X射线衍射仪（美国布鲁克仪器公司，AXS D8 Advance）分析材料的晶体结构、纯度和相关物质组成。采用扫描电子显微镜（SEM，日本日立公司JSM 6400 JEOL）、透射电子显微镜（TEM，日本日立公司JEOL 2100F JEOL）观察材料表面形貌。
1.3 电化学性能测试
将制备的正极材料、5%Super-P炭黑与聚偏氟乙烯（PVDF）按质量比8∶1∶1混合均匀，磨成黑色粉末，滴加液态N-甲基吡咯烷酮（NMP，99.9%），研磨充分形成黑色的糊状浆料，用涂布机一次性涂抹在铝箔上，最终制备成活性正极片。在惰性气体保护的多功能手套箱中制备CR2032电池，采用深圳市贝特瑞新能源材料股份有限公司的纯锂作为负极的对电极，微孔聚丙烯（Aladdin）为隔膜，将1 mol/L LiPF6溶解于碳酸乙酯（EC）和碳酸二乙酯（DEC）混合溶液（EC/DEC体积比3∶7）中作为电解质溶液。采用新威测试系统对电池进行充放电性能检验，测试温度为室温（25 ℃），电压范围2.75～4.6 V（0.5C）。
2 实验结果与分析
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2.1 材料物理结构表征
NCM正极材料和SiO2@Li2SiO3包覆的正极材料形貌见图1。SiO2@Li2SiO3修饰后，单晶颗粒的微观形貌基本保持不变，平均粒径2～5 μm，表面光滑，说明SiO2@Li2SiO3异质结的引入不会破坏单晶正极形态。
SiO2@Li2SiO3异质结的引入对NCM正极材料相纯度和晶体结构的影响见图2。由图2可知，所有样品的衍射峰均与LiNiO2的标准卡片PDF#89-3601相匹配，材料属于具有R-3m空间群的α-NaFeO2型层状结构[15]。XRD谱图中未观察到其他杂质峰，SiO2@Li2SiO3包覆没有引入新的相，这是由于包覆量太少，与SiO2@Li2SiO3相关的峰不明显，同时，随着SiO2@Li2SiO3包覆量增加，样品（003）峰没有发生明显偏移，说明SiO2@Li2SiO3没有进入三元材料晶体结构中，只是包覆在正极材料的表面。此外，从（006）/（102）和（008）/（110）的分裂峰进一步证明SiO2@Li2SiO3包覆不会破坏材料应有的层状结构[16]。结合Rietveld方法的精修参数（见表1）对各正极材料进行分析，可以看出4个样品的晶格常数a和c变化不明显，但随着SiO2@Li2SiO3包覆量增加，Li+/Ni2+混排程度发生了一定变化，NCM、0.5%SO@NCM、1.0%SO@NCM和1.5% SO@NCM阳离子混排程度分别为4.71%、4.63%、4.42%和4.56%，表明SiO2@Li2SiO3包覆会消耗材料表面的残锂，使Li+/Ni2+混排值相应减小，可以进一步优化材料表面组成。
为了进一步了解SiO2@Li2SiO3包覆对NCM正极材料表面微观结构的影响，采用HRTEM对NCM和1.0%SO@NCM材料进行表征，结果见图3。在高温烧结过程中添加的过量锂源没有充分反应，在NCM正极材料颗粒表面积累，同时过量的锂源与空气中的CO2和H2O反应导致残锂化合物（Li2CO3/LiOH）的形成，该残锂化合物会严重阻碍长循环过程中Li+的嵌入和脱嵌，影响电池的电化学性能[17]。经过SiO2@Li2SiO3包覆后，1.0%SO@NCM材料表面有一层明显异质结层，厚度5～10 nm（图3（a））。颗粒内部经过HRTEM放大后，相应的晶格间距为0.245 nm，对应于NCM正极材料的（101）面（图3（b））。同时，表面晶格间距0.23 nm对应于SiO2的（102）面（图3（c）），另一区域的晶格间距为0.33 nm，对应于Li2SiO3的（111）面（图3（d）），证明了SiO2@Li2SiO3很好地包覆在NCM正极材料颗粒的表面，具有快离子导体性质的Li2SiO3涂层可以显著提高锂离子的传递速率，同时在长循环过程中SiO2@Li2SiO3涂层可以防止电解液中HF对颗粒表面的腐蚀[18]。
2.2 电化学性能测试
25 ℃、2.75～4.6 V条件下，NCM和1.0%SO@NCM的充放电曲线见图4。由图4可知，1.0%SO@NCM充放电曲线重合度较好、化学可逆性强，而NCM充放电曲线重合度差、电化学可逆性差。
各样品循环性能测试结果见图5。NCM、0.5%SO@NCM、1.0%SO@NCM、1.5%SO@NCM正极材料的初始放电比容量分别为225.20、222.60、225.40、222.90 mAh/g，初始放电容量的差距不明显，说明包覆层的存在并不会影响Li+的嵌入/脱嵌过程[19]。此外，随着充电深度增加，SiO2@Li2SiO3修饰的正极材料有更多的活性Li+被释放出来，材料的容量保持率较好，在120次循环后，NCM、1.0%SO@NCM、1.5%SO@NCM正极材料的放电比容量分别为100.10、156.88、142.80 mAh/g，相应的容量保持率分别为45.10%、70.52%、64.06%。此外，1.0%SO@NCM在长循环过程中电压平台明显，放电中压较大，这种现象为材料保持较好的能量密度提供了保证，相应的能量密度数据表明，NCM在120次循环后能量密度仅325.66 Wh/kg，而1.0%SO@NCM的能量密度为549.64 Wh/kg，远高于本体NCM，说明SiO2 @Li2SiO3修饰后在一定程度上提高了电化学反应动力学，电化学可逆性强。
为了研究SiO2@Li2SiO3修饰层对电化学反应可逆性的影响，在2.75～4.6 V、0.5C条件下比较了样品不同循环次数的微分容量曲线dQ/dV，结果见图6。从dQ/dV曲线可以看出，电化学氧化还原过程中峰值位置的差异很明显，表明SiO2@Li2SiO3修饰层对电池的极化有明显抑制作用。正极材料在电化学反应过程中会经历不同程度的相变，从最初的六方相H1到单斜相M、再从M相到第2个六方相H2、最后H2到第3个六方相H3的相变，其中代表H1-M相变的峰最明显，可以通过对比H1-M相变氧化还原峰之间的电压差来判断极化程度[20]。4.2 V时，NCM还原峰强度逐渐减弱甚至消失，表明长循环过程中材料的结构稳定性逐渐变差；而1.0%SO@NCM的H2→H3相变对应的还原峰强度基本不变，极化现象不明显，表明相变的可逆性，材料没有发生明显退化，在长循环过程中有利于Li+的迁移。
2.3 循环后材料表征
为了研究SiO2@Li2SiO3修饰层在长循环过程中对正极材料表面结构和形貌的影响，对NCM与1.0%SO@NCM的循环120次后电极片进行了SEM观察，结果见图7。NCM正极材料表面出现明显破碎的小颗粒，说明材料遭受了强烈的电解液腐蚀和渗透，这种长期腐蚀使材料界面发生改变，造成长循环后颗粒表面微裂痕的形成；纳米级微裂痕会进一步渗透到颗粒内部，使材料结构发生不可逆的改变。1.0%SO@NCM正极材料表面有裂纹，SiO2@Li2SiO3修饰层对正极表面具有一定的保护作用，可以保护正极材料免受HF的侵蚀，并进一步提供快速的Li+导电网络，加快锂离子的传输过程，降低副反应的发生，提高界面稳定性[21]。
3 结论
收起
1）采用高温固相烧结法将SiO2包覆在NCM正极材料表面，同时在烧结过程中，发生反应，在NCM正极材料表面形成SiO2@Li2SiO3双包覆层。SiO2@Li2SiO3改性后增加了材料界面处的传输网络，加速了Li+的传输，提高正极界面的电化学可逆性。
2）SiO2@Li2SiO3双包覆层能抑制界面处副反应的发生，保护正极材料免受HF的侵蚀。
3）SiO2@Li2SiO3改性后样品具有更好的循环性能，1.0%SO@NCM初始放电比容量为225.40 mAh/g，循环120次后比容量为156.88 mAh/g，远高于LiNi0.8Co0.1Mn0.1O2的100.1 mAh/g。
4）该方法可为改善高镍正极材料电化学性能提供一种新颖而有价值的途径。
基金
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  • 河南省科技攻关资助项目(242102210171)
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2024年第44卷第4期
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doi: 10.3969/j.issn.0253-6099.2024.04.007
  • 接收时间：2024-05-08
  • 首发时间：2026-03-18
  • 出版时间：2024-08-01
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  • 收稿日期：2024-05-08
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河南省科技攻关资助项目(242102210171)
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    1.郑州铁路职业技术学院，河南 郑州 450018
    2.洛阳铁路信息工程学校，河南 洛阳 471000
    3.贵州民族大学，贵州 贵阳 550025
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