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Article(id=1241081029709067247, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241081025531540408, articleNumber=null, orderNo=null, doi=10.3969/j.issn.0253-6099.2024.04.005, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1714233600000, receivedDateStr=2024-04-28, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1773826375652, onlineDateStr=2026-03-18, pubDate=1722441600000, pubDateStr=2024-08-01, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1773826375652, onlineIssueDateStr=2026-03-18, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1773826375652, creator=13701087609, updateTime=1773826375652, 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=24, endPage=30, ext={EN=ArticleExt(id=1241081030241742849, articleId=1241081029709067247, tenantId=1146029695717560320, journalId=1235980550691926019, language=EN, title=Synthesis and Electrochemical Performance of LiMn0.6Fe0.4PO4/C Cathode Materials, columnId=1241081026567533498, journalTitle=Mining and Metallurgical Engineering, columnName=SPECIAL ISSUE: BATTERY MATERIALS, runingTitle=null, highlight=null, articleAbstract=

LiMn0.6Fe0.4PO4/C (LMFP) composite synthesized by a combined process of co-precipitation and solid-phase sintering not only has low impurity content, uniform phase distribution, but also exhibits excellent electrochemical performance. It is shown that such process can inhibit the formation of Mn2P2O7 phase and improve the lithium ion diffusion rate of LMFP, while removing NH4+ and H2O. The Li-ion batteries assembled with LiMn0.6Fe0.4PO4/C exhibit excellent electrochemical performance, showing initial specific discharge capacity of 145.5 mAh/g at 1C and 111.9 mAh/g at 5C. It is concluded that this process, being simple and cost-effective, is suitable for industrial production. Such study provides a feasible scheme in designing cathode materials for commercialized high-performance Li-ion batteries.

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采用共沉淀法和固相烧结法制备了一种杂质少、物相分布均匀、电化学性能优良的LiMn0.6Fe0.4PO4/C（LMFP）复合材料。结果表明，该方法在脱去NH4+和H2O的同时，抑制了Mn2P2O7物相的产生，提高了LMFP的锂离子扩散速率。由LiMn0.6Fe0.4PO4/C组装的锂离子电池展示了优异的电化学性能，1C下首次放电比容量145.5 mAh/g；5C下首次放电比容量111.9 mAh/g。该工艺简单、成本低，适合工业化生产，为设计高性能的商业化锂离子电池正极材料提供了可行性方案。

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周友元（1970—），男，湖南新宁人，博士，教授级高级工程师，主要从事新能源材料研究。E-mail：
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丁伦涛（2000—），男，湖南长沙人，硕士研究生，主要研究方向为锂离子电池正极材料性能研究。E-mail：

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丁伦涛（2000—），男，湖南长沙人，硕士研究生，主要研究方向为锂离子电池正极材料性能研究。E-mail：

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丁伦涛（2000—），男，湖南长沙人，硕士研究生，主要研究方向为锂离子电池正极材料性能研究。E-mail：

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Advanced Energy Materials, 2019, 9(11): 1802847., articleTitle=In situ synthesis of hierarchical core double-shell Ti-Doped LiMnPO4@NaTi2(PO4)3@C/3D graphene cathode with high-rate capability and long cycle life for lithium-ion batteries, refAbstract=null), Reference(id=1241081045517398909, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241081029709067247, doi=null, pmid=null, pmcid=null, year=2022, volume=42, issue=5, pageStart=137, pageEnd=142, url=null, language=null, rfNumber=[6], rfOrder=5, authorNames=石杰, 杨乐之, 李贺, journalName=矿冶工程, refType=null, unstructuredReference=石杰, 杨乐之, 李贺, 等. 石墨烯导电剂片径对LiFePO4正极中电荷传输的影响[J]. 矿冶工程, 2022, 42(5): 137-142., articleTitle=石墨烯导电剂片径对LiFePO4正极中电荷传输的影响, refAbstract=null), Reference(id=1241081045639033738, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241081029709067247, doi=null, pmid=null, pmcid=null, year=2022, volume=104, issue=null, pageStart=null, pageEnd=null, url=null, language=null, rfNumber=[7], rfOrder=6, authorNames=HU Q, LIAO J, XIAO X, journalName=Nano Energy, refType=null, unstructuredReference=HU Q, LIAO J, XIAO X, et al. 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Nonaqueous synthesis of nano-sized LiMnPO4@C as a cathode material for high performance lithium ion batteries[J]. Electrochimica Acta, 2016, 194: 52-58., articleTitle=Nonaqueous synthesis of nano-sized LiMnPO4@C as a cathode material for high performance lithium ion batteries, refAbstract=null), Reference(id=1241081046024909741, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241081029709067247, doi=null, pmid=null, pmcid=null, year=2023, volume=10, issue=4, pageStart=1164, pageEnd=1175, url=null, language=null, rfNumber=[10], rfOrder=9, authorNames=ZENG T, LIU D, FAN C, journalName=Inorganic Chemistry Frontiers, refType=null, unstructuredReference=ZENG T, LIU D, FAN C, et al. LiMn0.8Fe0.2PO4@C cathode prepared via a novel hydrated MnHPO4 intermediate for high performance lithium-ion batteries[J]. 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Journal of Power Sources, 2012, 218: 56-64., articleTitle=Synthesis and characterization of Ti-Mn and Ti-Fe co doped Li3V2(PO4)3 as cathode material for lithium ion batteries, refAbstract=null), Reference(id=1241081046490477527, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241081029709067247, doi=null, pmid=null, pmcid=null, year=2021, volume=null, issue=9, pageStart=9147, pageEnd=9157, url=null, language=null, rfNumber=[13], rfOrder=12, authorNames=ZHANG J, ZHANG J, LIU J, journalName=Journal of Materials Chemistry C, refType=null, unstructuredReference=ZHANG J, ZHANG J, LIU J, et al. Environmentally phase-controlled stratagem for open framework pyrophosphate anode materials in battery energy storage[J]. Journal of Materials Chemistry C, 2021(9): 9147-9157., articleTitle=Environmentally phase-controlled stratagem for open framework pyrophosphate anode materials in battery energy storage, refAbstract=null), Reference(id=1241081046595335137, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241081029709067247, doi=null, pmid=null, pmcid=null, year=2024, volume=43, issue=1, pageStart=302, pageEnd=309, url=null, language=null, rfNumber=[14], rfOrder=13, authorNames=于松民, 金洪波, 杨明虎, journalName=化工进展, refType=null, unstructuredReference=于松民, 金洪波, 杨明虎, 等. 氟掺杂改性LiMn0.5Fe0.5PO4正极材料及其电化学性能[J]. 化工进展, 2024, 43(1): 302-309., articleTitle=氟掺杂改性LiMn0.5Fe0.5PO4正极材料及其电化学性能, refAbstract=null), Reference(id=1241081046708581355, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241081029709067247, doi=null, pmid=null, pmcid=null, year=2018, volume=276, issue=null, pageStart=134, pageEnd=141, url=null, language=null, rfNumber=[15], rfOrder=14, authorNames=WEN F, LV T, GAO P, journalName=Electrochimica Acta, refType=null, unstructuredReference=WEN F, LV T, GAO P, et al. 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（a）XRD图谱；（b）TG-DSC曲线

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（a）MFP-4、MFP-5、MFP-6样品XRD图谱；（b）前驱体高温原位XRD图谱

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（a）XRD图谱；（b）局部放大图

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（a）NH4Mn0.6Fe0.4PO4·H2O前驱体水合物；（b）脱水脱氨样品MFP-5；（c）喷雾造粒后样品LMFP-5；（d）400 ℃烧结样品，未粉碎；（e）500 ℃烧结样品，未粉碎；（f）600 ℃烧结样品，未粉碎

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（a）LMFP-4，SEM图；（b）LMFP-5，SEM图；（c）LMFP-6，SEM图；（d）～（f）LMFP-5的TEM、HRTEM图像

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（a）扫描速度0.1 mV/s时样品的CV曲线；（b）LMFP电池示意图；（c）LiMn0.6Fe0.4PO4/C在0.1C时的初始充放电曲线；（d）LMFP-5不同倍率下的初始放电曲线；（e）样品倍率性能；（f）1C下样品的循环性能

, figureFileSmall=6AuSljEA4zx1yR8QXaj1pA==, figureFileBig=dp+GRqAtYPFkHBibhiY8Fw==, tableContent=null), ArticleFig(id=1241081044380742426, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241081029709067247, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
w（Mn）/%w（Fe）/%n（Mn）∶n（Fe）
理论值测试值
22.3915.051.5∶11.512∶1
), ArticleFig(id=1241081044502377256, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241081029709067247, language=CN, label=表1, caption=

NH4Mn0.6Fe0.4PO4·H2O材料中Mn和Fe含量（ICP）

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w（Mn）/%w（Fe）/%n（Mn）∶n（Fe）
理论值测试值
22.3915.051.5∶11.512∶1
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LiMn0.6Fe0.4PO4/C正极材料的制备与电化学性能研究
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丁伦涛 1 , 赵鹏 2 , 周春仙 2 , 王德志 1 , 吴壮志 1 , 李雪豹 1 , 周友元 2
矿冶工程杂志 | 电池材料专题 2024,44(4): 24-30
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矿冶工程杂志 | 电池材料专题 2024, 44(4): 24-30
LiMn0.6Fe0.4PO4/C正极材料的制备与电化学性能研究
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丁伦涛1 , 赵鹏2, 周春仙2, 王德志1, 吴壮志1, 李雪豹1, 周友元2
作者信息
  • 1.中南大学 材料科学与工程学院，湖南 长沙 410083
  • 2.湖南长远锂科股份有限公司，湖南 长沙 410221

    • 丁伦涛（2000—），男，湖南长沙人，硕士研究生，主要研究方向为锂离子电池正极材料性能研究。E-mail：

通讯作者:

周友元（1970—），男，湖南新宁人，博士，教授级高级工程师，主要从事新能源材料研究。E-mail：
Synthesis and Electrochemical Performance of LiMn0.6Fe0.4PO4/C Cathode Materials
Luntao DING1 , Peng ZHAO2, Chunxian ZHOU2, Dezhi WANG1, Zhuangzhi WU1, Xuebao LI1, Youyuan ZHOU2
Affiliations
  • 1.School of Materials Science and Engineering, Central South University, Changsha 410083, Hunan, China
  • 2.Hunan Changyuan Lico Co., Ltd., Changsha 410221, Hunan, China
出版时间: 2024-08-01 doi: 10.3969/j.issn.0253-6099.2024.04.005
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摘要
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采用共沉淀法和固相烧结法制备了一种杂质少、物相分布均匀、电化学性能优良的LiMn0.6Fe0.4PO4/C（LMFP）复合材料。结果表明，该方法在脱去NH4+和H2O的同时，抑制了Mn2P2O7物相的产生，提高了LMFP的锂离子扩散速率。由LiMn0.6Fe0.4PO4/C组装的锂离子电池展示了优异的电化学性能，1C下首次放电比容量145.5 mAh/g；5C下首次放电比容量111.9 mAh/g。该工艺简单、成本低，适合工业化生产，为设计高性能的商业化锂离子电池正极材料提供了可行性方案。

锂离子电池  /  磷酸铁锂  /  磷酸锰铁锂  /  正极材料  /  LiMn0.6Fe0.4PO4  /  前驱体  /  煅烧  /  碳包覆  /  工业化

LiMn0.6Fe0.4PO4/C (LMFP) composite synthesized by a combined process of co-precipitation and solid-phase sintering not only has low impurity content, uniform phase distribution, but also exhibits excellent electrochemical performance. It is shown that such process can inhibit the formation of Mn2P2O7 phase and improve the lithium ion diffusion rate of LMFP, while removing NH4+ and H2O. The Li-ion batteries assembled with LiMn0.6Fe0.4PO4/C exhibit excellent electrochemical performance, showing initial specific discharge capacity of 145.5 mAh/g at 1C and 111.9 mAh/g at 5C. It is concluded that this process, being simple and cost-effective, is suitable for industrial production. Such study provides a feasible scheme in designing cathode materials for commercialized high-performance Li-ion batteries.

Li-ion battery  /  LiFePO4  /  LiMnxFe1-xPO4  /  cathode material  /  LiMn0.6Fe0.4PO4  /  precursor  /  calcination  /  carbon coating  /  industrialization
丁伦涛, 赵鹏, 周春仙, 王德志, 吴壮志, 李雪豹, 周友元. LiMn0.6Fe0.4PO4/C正极材料的制备与电化学性能研究. 矿冶工程杂志, 2024 , 44 (4) : 24 -30 . DOI: 10.3969/j.issn.0253-6099.2024.04.005
Luntao DING, Peng ZHAO, Chunxian ZHOU, Dezhi WANG, Zhuangzhi WU, Xuebao LI, Youyuan ZHOU. Synthesis and Electrochemical Performance of LiMn0.6Fe0.4PO4/C Cathode Materials[J]. Mining and Metallurgical Engineering, 2024 , 44 (4) : 24 -30 . DOI: 10.3969/j.issn.0253-6099.2024.04.005
正文
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锂离子电池被广泛认为是具有高能量和功率密度、长循环寿命和高安全性能的理想储能装置[1-3]。作为电池的关键组成部分，正极材料的发展对提升储能系统的性能至关重要[4]。橄榄石型LiMnPO4因其较高的理论能量密度（701 Wh/kg）、较高电位（4.1 V）及其低成本、环保和良好的热稳定性而备受关注[5-6]，但其电导率和离子扩散系数较低，限制了其应用。以Fe部分替代Mn，可以提高电导率并抑制Mn3+的Jahn-Teller畸变，从而发展出兼具LiMnPO4和LiFePO4优点的LiMn（1-x）FexPO4（简称LMFP）稳定固溶体[7-8]。尽管如此，LMFP仍面临电子电导率低和锂离子扩散速率低的问题。为解决这些问题，采用在材料颗粒表面施加导电碳层的方法，为颗粒表面提供连续的导电网络，同时减少与电解液的副反应，可以增强材料电化学性能。本文采用共沉淀法和固相反应法合成了LiMn0.6Fe0.4PO4/C复合正极材料，并对其电化学性能进行了测试。
1 实验材料和方法
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1.1 LiMn0.6Fe0.4PO4/C材料的制备
首先采用硫酸盐共沉淀法合成前驱体水合物NH4Mn0.6Fe0.4PO4·H2O。按照物质的量比n（Mn）∶n（Fe）=6∶4称取FeSO4·7H2O、MnSO4·H2O，以物质的量比n（Mn+Fe）∶n（P）=0.971加入质量分数85%的H3PO4溶液，同时加入25 g抗坏血酸防止氧化；加纯水至50 L，搅拌120 min，得到1.5 mol/L的Mn、Fe盐混合溶液。随后，在反应釜中加入14 L氨水（浓度为6.5 mol/L）、21 L H2SO4溶液（浓度为2 mol/L）和15 L纯水，并微调pH=4.5。使用蠕动泵将混合盐溶液输送至反应釜，同时以6.5 mol/L氨水控制反应pH值至4.5±0.1。最后，经过纯水洗涤、离心机固液分离和真空干燥，得到棕黄色NH4Mn0.6Fe0.4PO4·H2O前驱体水合物粉末。
在空气气氛下，以升温速率3 ℃/min将NH4Mn0.6-Fe0.4PO4·H2O分别加热到400 ℃、500 ℃和600 ℃，保温4 h，自然降温后得到不同脱水脱氨温度下的前驱体样品，分别命名为MFP-4、MFP-5和MFP-6。
前驱体水合物脱水脱氨后，采用高温固相法制备LiMn0.6Fe0.4PO4/C。首先，在1 L纯水中加入5.5%蔗糖和5.5%聚乙二醇6000得到混合碳源，并搅拌20 min以上至完全溶解。然后将溶液转移至分散罐中，按照n（Li）∶n（Mn+Fe）=1.035加入Li2CO3，补充质量分数85%的H3PO4溶液，以维持n（Mn+Fe）∶n（P）=0.975。接着，将前驱体加入分散罐中高速搅拌3 h。分散完成后，将浆料转移至卧式砂磨机中砂磨1 h。砂磨后的浆料通过喷雾干燥机进行喷雾造粒。经过喷雾干燥后的前驱体在N2气氛下于705 ℃煅烧8 h，随后在气流粉碎机中进行破碎，最终得到LiMn0.6Fe0.4PO4/C材料。将MFP-4、MFP-5和MFP-6前驱体分散煅烧后制备的材料分别命名为LMFP-4、LMFP-5和LMFP-6。
1.2 材料表征
通过X射线衍射仪（XRD，Bruker D8 Advance，Cu-Kα）表征材料的晶体结构。通过扫描电子显微镜（SEM，日立S-4800）观察和分析材料形貌和微观结构。采用电感耦合等离子体发射光谱仪（ICP-OES，SHIMADZU ICPE-9000）分析元素含量。通过同步热分析仪（TG-DSC，耐驰STA449F5）研究材料在加热过程中的质量和热量变化。利用透射电子显微镜（TEM，FEI-Tecnai-F20）观察样品的内部结构和晶格边缘。
1.3 电化学性能测试
采用湿涂法制备铝箔集流器和电极：将活性材料、活性炭和聚偏氟乙烯（PVDF）按质量比90∶5∶5称重，均匀混合，然后均匀分散在N-甲基吡咯烷酮（NMP）中，制备得到正电极浆料。将浆料均匀涂敷在铝箔上，置于120 ℃真空烘箱中烘干8 h，随后，将涂有活性材料的铝箔用卷压机压平，切割成直径1.1 cm的圆盘。在氩气气氛的手套箱内，利用不锈钢电池壳、正极极片、隔膜、电解液、镍网以及作为对电极的锂金属，组装CR2032纽扣电池。随后，将其置于25 ℃的恒温房间静置12 h后备用。其中，电解液为1 mol/L的LiPF6溶于碳酸乙烯酯/碳酸二甲酯/碳酸甲乙酯（体积比为EC∶DMC∶EMC=1∶1∶1）中制备得到；隔膜采用聚丙烯微孔膜（Cellgard 2400）；镍网厚度为5 mm。随后，在LAND CT2001A电池测试仪上进行恒流充电/放电测试，电压窗口为2.0～4.5 V（vs Li/Li+）。在CHI660E电化学工作站上进行循环伏安（CV）测试（扫描速度0.1 mV/s，电压2.0～4.5 V）和电化学阻抗（EIS）测试（频率0.01～100 000 kHz）。
2 实验结果与讨论
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2.1 物相及形貌分析
为了研究不同脱水脱氨温度下NH4Mn0.6Fe0.4PO4·H2O前驱体水合物的物相变化，进行了氧气气氛下的TG-DSC分析，TG-DSC结果和脱水脱氨前前驱体水合物的XRD检测结果如图1所示，其中TG-DSC测试温度范围为25～800 ℃，升温速率为5 ℃/min。
从图1（a）可知，前驱体水合物衍射峰与Pnma橄榄石系磷酸盐结构大致吻合，未发现明显杂质峰，其衍射峰位处于NH4MnPO4·H2O（JDPDS-50-0554）和NH4FePO4·H2O（JDPDS-45-0424）标准卡片之间，ICP测试结果（见表1）表明，NH4Mn0.6Fe0.4PO4·H2O中Mn/Fe物质的量比为1.512，与理论值基本一致。
由图1（b）可知，NH4Mn0.6Fe0.4PO4·H2O的脱水脱氨过程主要集中在2个温度区间。TG曲线上，25～495 ℃之间发生了失重反应（失重19.93%），与NH4Mn0.6Fe0.4PO4·H2O在此温度范围内发生了结晶水和NH4+的脱去有关。DSC曲线上，在196.4 ℃出现放热峰，显示发生了脱水脱氨反应[9]，但脱水和脱氨反应不能很好分离。TG曲线上，在495～620 ℃范围内发生失重现象（失重2.24%），表明前驱体发生了固态相变。DSC曲线上，608.4 ℃的吸热峰也与相变有关。在620 ℃之后，TG曲线下降趋势缓慢，说明相变反应基本完成，前驱体最终由非晶态转化为晶态。推测预烧结过程的反应机理[10]如下：
第一阶段（100～495 ℃，H2O和NH4+共消除）：
第二阶段（495～620 ℃，晶态转变）：
图2（a）展示了不同预烧温度下前驱体的XRD图。经过400 ℃预烧得到的MFP-4材料中显示微弱的XRD衍射峰，结晶度较差，表明此时物相为非晶态Mn0.6Fe0.4HPO4相[11]。500 ℃预烧得到的MFP-5样品的脱水脱氨反应基本完成，XRD图谱中出现Mn2P2O7（JDPDS-29-0891）的特征峰，表明在500 ℃以内开始发生分相反应，MnHPO4相转化为微量Mn2P2O7相。600 ℃预烧得到的MFP-6材料呈现出衍射强度较高的衍射峰，指向FePO4相（JSPDS-50-1635）和Mn2P2O7相，无其他杂质峰，说明在600 ℃脱水脱氨后，NH4Mn0.6Fe0.4PO4·H2O基本转化为FePO4和Mn2P2O7的混合物相。
为进一步观察脱水脱氨过程中前驱体晶体结构的变化，对NH4Mn0.6Fe0.4PO4·H2O前驱体水合物在空气气氛中进行了高温原位XRD测试，结果见图2（b）。结果显示，随着温度升高，从室温的NH4Mn0.6Fe0.4PO4·H2O物相开始，材料特征峰强度减弱，逐步转变为无定形结构。400 ℃时，前驱体未完全脱水脱氨，500 ℃时XRD图谱显示微弱的Mn2P2O7特征峰。温度达到600 ℃时，FePO4和Mn2P2O7特征峰明显，峰强随温度升高而增大，表明结晶度和Mn2P2O7含量增多。600 ℃下样品焦磷酸盐物相较500 ℃下有所增加。Mn2P2O7的生成是在高温下破坏2个磷酸基团，约束它们形成一个焦磷酸盐基团。此外，由于不稳定的高温条件，P2O74+会分解形成PO43+，导致高温过程的不稳定现象，使材料中存在P2O74+和PO43+混合相的相杂质。杂质含量增加会阻碍Li+的传输路径，不利于Li+的脱嵌和扩散[12]。Mn2P2O7基团的生成不仅能源成本巨大，产生污染风险，且在晶体结构中增加了金属离子的扩散难度，在电池中表现出明显的电化学衰减[13]。微量P2O74+可通过高温煅烧反应转化为PO43+，MFP-6样品中含有过量Mn2P2O7基团，在煅烧过程中因煅烧时间一定，Mn2P2O7基团没有足够热力学条件转化为PO43+而形成相杂质。结合原位XRD与TG-DSC测试结果，推测在500 ℃下样品相对于其他脱水脱氨温度下样品具有更好的电化学性能。
前驱体烧结后的样品XRD图谱如图3所示。所有样品的衍射峰峰形均能与LiMnPO4（JCPDS-74-0375）标准卡片的Pnma橄榄石结构对应。正交Pnma空间群的特征衍射峰清晰可见，未观察到明显的杂质峰，表明成功合成了纯固溶相的LiMn0.6Fe0.4PO4材料[14]，证实了半液半固法的有效性。特别是没有观察到LiFePO4的衍射峰，表明LiFePO4和LiMnPO4主要存在于固溶体中，而非简单的物理混合物。由于没有观察到碳的衍射峰，材料表面的热解碳呈无定形结构[15]。在600 ℃样品中（131）晶面峰强度最高，显示结晶度最佳。此外与LiMnPO4相比，LMFP/C样品的衍射峰在27°～37°范围内略微向高衍射角方向偏移，如图3（b）所示。布拉格公式2dsinθ=nλ表明，较小的晶格参数d对应较大的衍射角（θ）。因此，这种现象与晶格收缩有关，表现为Fe2+成功掺入LiMnPO4晶格中，因为Fe2+的离子半径（0.92 nm）小于Mn2+的离子半径（0.97 nm）。
不同阶段样品SEM图见图4。从图4（a）可见，NH4Mn0.6Fe0.4PO4·H2O呈纳米插片状，单个纳米片向各方向生长。经脱水脱氨后，插片状结构未大变，但因高温下表面能增大，导致颗粒团聚，单个纳米片减少（图4（b））。图4（c）中，喷雾造粒后的LMFP-5材料形成约10 μm的二次颗粒。图4（d）～（f）显示，400 ℃和500 ℃样品形态稳定，600 ℃样品颗粒团聚严重，烧结过度引起结块。结块和团聚的纳米颗粒不利于电化学性能。随着烧结温度升高，颗粒表面气孔增多，BET结果显示，MFP-4、MFP-5、MFP-6的比表面积依次为2.285、3.080、4.393 m2/g，反映脱水脱氨速率随温度升高而加快。MFP-5表面气孔多且形貌良好，推测500 ℃下的脱水脱氨有利于前驱体的电化学性能。
烧结并喷雾造粒后材料的SEM图像与LMFP-5的TEM和HRTEM图像见图5。
由图5（a）～（c）可见，气流粉碎后的LMFP/C材料粒径均匀，在100～500 nm范围内，显示出优良形貌。如图5（d）所示，由碳层包覆的LMFP-5初级纳米颗粒的晶粒尺寸为400～700 nm，形状尺寸与SEM结果一致。非晶碳和高结晶度晶体的分界可以在图5（e）中清晰显现。图5（f）中可以观察到0.35 nm的晶面间距，对应（111）晶格平面，具有清晰规则的FFT点的晶面。这些结果表明合成的LiMn0.6Fe0.4PO4是一种高度有序的纯相材料，在纳米颗粒表面覆盖了厚度为4 nm的无定形碳层，合适厚度的碳包覆层可以构建优良的导电网络，从而提高电子导电性[16]。这些TG-DSC、XRD、SEM和HRTEM结果共同证明了磷酸铁锰前驱体经过预煅烧已成功转变为具有橄榄石结构的LiMn0.6Fe0.4PO4/C。
2.2 电化学性能分析
采用恒流充放电法研究了不同电流密度下样品的电化学性能，结果如图6所示。由图6（a）可见，CV曲线显示氧化峰和还原峰，分别对应Mn2+/Mn3+和Fe2+/Fe3+的氧化还原反应，峰形锋利并具有良好的对称性，表明该材料具备出色的电化学可逆性；特别是LMFP-5样品的CV曲线显示出最大的峰电流和最锋利的峰形，氧化还原峰之间的电位差（ΔV1和ΔV2）最小，表明Li+的嵌入/脱出速率最快，表明LMFP-5具有较低的极化现象和更优的电化学可逆性。由图6（c）可见，0.1C条件下样品的初始充放电曲线有2个充放电平台，分别位于4.1 V和3.5 V，LMFP-4、LMFP-5、LMFP-6的放电比容量分别为131.4、151.8、147.4 mAh/g，其中LMFP-5表现最佳。由图6（d）可见，LMFP-5在不同倍率下维持了良好的放电比容量；随着电流密度增大，样品放电比容量逐渐减小，Mn2+/Mn3+的电压平台极化增加，其原因是在大电流下Li+的不可逆脱嵌导致容量退化。由图6（e）可见，尽管电流密度增加导致放电比容量从151.8 mAh/g降至111.9 mAh/g，电压极化增加，但回到0.1C时容量可恢复到初始水平，表明材料具有优异的电化学可逆性。与LMFP-4和LMFP-6相比，LMFP-5在高电流密度下的电压曲线极化最低，高倍率下表现出更稳定的性能。由图6（f）可见，3种材料在1C下的循环性能，电池初期在0.1C～0.5C电流密度下活化后，1C下LMFP-4、LMFP-5、LMFP-6的初始比容量分别为123.9、145.5、133.7 mAh/g，经过100次循环后的容量保持率分别为96.0%、91.8%、97.3%；LMFP-5在循环80次后放电比容量衰减较快，可能是由于长时间循环后出现更大的结构变化或副反应，从而影响其循环稳定性。
总体而言，500 ℃处理前体水合物可转变为无定形Mn0.6Fe0.4HPO4，烧结后样品表面形成的孔洞有利于电解液渗透，提升了Li+的迁移效率，从而增强电池的初始放电比容量和倍率性能。
3 结论
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1）通过500 ℃、4 h的脱水脱氨预煅烧处理，成功制备了杂质含量低、物相单一的Mn0.6Fe0.4HPO4前驱体。这种处理工艺有效抑制了Mn2P2O7相的产生，提升了材料的锂离子扩散速率。
2）通过共沉淀法和固相烧结法合成的LiMn0.6-Fe0.4PO4/C正极材料在1C下的初始比容量达到145.5 mAh/g，经过100次循环后容量保持率为91.8%。
3）本合成工艺简单、成本低，适合工业化生产。
基金
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  • 长沙市科技重大专项(kh2401022)
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doi: 10.3969/j.issn.0253-6099.2024.04.005
  • 接收时间：2024-04-28
  • 首发时间：2026-03-18
  • 出版时间：2024-08-01
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  • 收稿日期：2024-04-28
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长沙市科技重大专项(kh2401022)
作者信息
    1.中南大学 材料科学与工程学院，湖南 长沙 410083
    2.湖南长远锂科股份有限公司，湖南 长沙 410221

通讯作者:

周友元（1970—），男，湖南新宁人，博士，教授级高级工程师，主要从事新能源材料研究。E-mail：
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2种不同金属材料的力学参数
科
Family		 属数
Number of
genus		 种数
Number of
species		 占总种数比例
Percentage of
total species (%)		 属
Genus		 种数
Number of
species		 占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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