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Article(id=1241081037959254839, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241081025531540408, articleNumber=null, orderNo=null, doi=10.3969/j.issn.0253-6099.2024.04.004, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1717689600000, receivedDateStr=2024-06-07, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1773826377619, onlineDateStr=2026-03-18, pubDate=1722441600000, pubDateStr=2024-08-01, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1773826377619, onlineIssueDateStr=2026-03-18, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1773826377619, creator=13701087609, updateTime=1773826377619, 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=18, endPage=23, ext={EN=ArticleExt(id=1241081042220666979, articleId=1241081037959254839, tenantId=1146029695717560320, journalId=1235980550691926019, language=EN, title=Effect of Surface Treatment with Titanate Coupling Agent on Structure and Performance of LiMn2O4, columnId=1241081026567533498, journalTitle=Mining and Metallurgical Engineering, columnName=SPECIAL ISSUE: BATTERY MATERIALS, runingTitle=null, highlight=null, articleAbstract=

TiO2 was coated on the surface of LiMn2O4 by thermal decomposition of titanate coupling agent, and the effects of coating treatment on the structure and electrochemical performance of LiMn2O4, as well as material structure in the cycling were all explored. The results show that TiO2 can be uniformly coated on the surface of the LiMn2O4 by thermal decomposition of titanate coupling agent at 550 ℃. Surface coating does not change the crystal structure of LiMn2O4, but obviously improves its electrochemical performance, especially high temperature rate performance and cycle performance. At 55 ℃, LiMn2O4 with TiO2 coating delivers a specific capacity of 75.34 mAh/g at 5C, which is higher than that without coating (43.05 mAh/g). After 150 cycles, the capacity retention rate of the material with TiO2 coating and without coating is 77.27% and 62.85%, respectively. The improvement of electrochemical performance is attributed to reduction of Mn dissolution in the cathode material by TiO2 coating, which thus inhibits the change of crystal structure during cycling process, reduces the electrode polarization and charge transfer impedance, as well as improves the charge-discharge reversibility of the material and the Li+ diffusion.

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通过加热分解钛酸酯偶联剂在LiMn2O4表面包覆TiO2，研究包覆处理对LiMn2O4材料结构、电化学性能及在循环过程中材料结构的影响。结果表明：550 ℃下加热分解钛酸酯偶联剂，可使TiO2均匀包覆在材料表面；表面包覆不改变LiMn2O4的晶体结构，但能明显提升其电化学性能，特别是高温倍率性能和循环性能；包覆TiO2后的LiMn2O4材料在55 ℃、5C下比容量为75.34 mAh/g，高于原始材料的比容量（43.05 mAh/g）；经150次循环后，未包覆TiO2的材料容量保持率为62.85%，包覆TiO2后的材料容量保持率提高至77.27%。表面处理后LiMn2O4电化学性能提升的原因是TiO2包覆层减少了正极材料中Mn的溶解，抑制了循环过程中的晶体结构变化，降低了电极极化和电荷转移阻抗，提高了材料的充放电可逆性及Li+的扩散能力。

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范广新（1970—），男，河南洛阳人，副教授，主要研究方向为功能材料、晶体结构等。E-mail：
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蔡海洋（1998—），男，河南郑州人，硕士，主要研究方向为锂离子电池正极材料。E-mail：

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蔡海洋（1998—），男，河南郑州人，硕士，主要研究方向为锂离子电池正极材料。E-mail：

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蔡海洋（1998—），男，河南郑州人，硕士，主要研究方向为锂离子电池正极材料。E-mail：

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（a）TG-DSC曲线；（b）分解产物XRD

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（a）XRD；（b）局部放大图

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（a），（b）LMO-0，SEM；（c），（d）LMO-2，SEM；（e）LMO-2，EDS

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（a）室温（25 ℃）；（b）高温（55 ℃）

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（a）室温（25 ℃）；（b）高温（55 ℃）

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（a）室温（25 ℃）；（b）高温（55 ℃）

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（a）XRD；（b）局部放大图

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（a），（b）LMO-0；（c），（d）LMO-2

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样品名称a/nmV/nm3
LMO-00.823 890.559 25
LMO-10.823 890.559 25
LMO-20.823 910.559 29
LMO-30.823 860.559 19
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LMO-n产品晶胞参数

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样品名称a/nmV/nm3
LMO-00.823 890.559 25
LMO-10.823 890.559 25
LMO-20.823 910.559 29
LMO-30.823 860.559 19
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样品名称Rs/ΩRct/ΩW0/（10-3 Ω）D（Li+）/（10-15 cm2·s-1）
LMO-07.639250.92.00.007
LMO-13.519209.91.41.098
LMO-26.635115.62.10.179
LMO-35.58598.91.90.073
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LMO-n的EIS曲线拟合结果

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样品名称Rs/ΩRct/ΩW0/（10-3 Ω）D（Li+）/（10-15 cm2·s-1）
LMO-07.639250.92.00.007
LMO-13.519209.91.41.098
LMO-26.635115.62.10.179
LMO-35.58598.91.90.073
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样品名称状态a/nmd（111）/nmV/nm3
LMO-0初始0.821 974.742 70.555 35
循环后0.823 354.759 70.558 15
LMO-2初始0.821 934.744 80.555 27
循环后0.822 614.754 50.556 65
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LMO-0和LMO-2高温下循环150次的晶胞参数

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样品名称状态a/nmd（111）/nmV/nm3
LMO-0初始0.821 974.742 70.555 35
循环后0.823 354.759 70.558 15
LMO-2初始0.821 934.744 80.555 27
循环后0.822 614.754 50.556 65
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钛酸酯偶联剂表面处理对LiMn2O4结构及性能的影响
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蔡海洋 1 , 李振京 2 , 范广新 1 , 孟德轩 1 , 刘超帅 1
矿冶工程杂志 | 电池材料专题 2024,44(4): 18-23
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矿冶工程杂志 | 电池材料专题 2024, 44(4): 18-23
钛酸酯偶联剂表面处理对LiMn2O4结构及性能的影响
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蔡海洋1 , 李振京2, 范广新1 , 孟德轩1, 刘超帅1
作者信息
  • 1.河南理工大学 材料科学与工程学院，河南 焦作 454000
  • 2.龙佰集团股份有限公司，河南 焦作 454000

    • 蔡海洋（1998—），男，河南郑州人，硕士，主要研究方向为锂离子电池正极材料。E-mail：

通讯作者:

范广新（1970—），男，河南洛阳人，副教授，主要研究方向为功能材料、晶体结构等。E-mail：
Effect of Surface Treatment with Titanate Coupling Agent on Structure and Performance of LiMn2O4
Haiyang CAI1 , Zhenjing LI2, Guangxin FAN1 , Dexuan MENG1, Chaoshuai LIU1
Affiliations
  • 1.School of Materials Science and Engineering, Henan Polytechnic University, Jiaozuo 454000, Henan, China
  • 2.LongBai Group Co., Ltd., Jiaozuo 454000, Henan, China
出版时间: 2024-08-01 doi: 10.3969/j.issn.0253-6099.2024.04.004
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摘要
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通过加热分解钛酸酯偶联剂在LiMn2O4表面包覆TiO2，研究包覆处理对LiMn2O4材料结构、电化学性能及在循环过程中材料结构的影响。结果表明：550 ℃下加热分解钛酸酯偶联剂，可使TiO2均匀包覆在材料表面；表面包覆不改变LiMn2O4的晶体结构，但能明显提升其电化学性能，特别是高温倍率性能和循环性能；包覆TiO2后的LiMn2O4材料在55 ℃、5C下比容量为75.34 mAh/g，高于原始材料的比容量（43.05 mAh/g）；经150次循环后，未包覆TiO2的材料容量保持率为62.85%，包覆TiO2后的材料容量保持率提高至77.27%。表面处理后LiMn2O4电化学性能提升的原因是TiO2包覆层减少了正极材料中Mn的溶解，抑制了循环过程中的晶体结构变化，降低了电极极化和电荷转移阻抗，提高了材料的充放电可逆性及Li+的扩散能力。

正极材料  /  LiMn2O4  /  TiO2  /  钛酸酯偶联剂  /  表面包覆  /  改性  /  电化学性能

TiO2 was coated on the surface of LiMn2O4 by thermal decomposition of titanate coupling agent, and the effects of coating treatment on the structure and electrochemical performance of LiMn2O4, as well as material structure in the cycling were all explored. The results show that TiO2 can be uniformly coated on the surface of the LiMn2O4 by thermal decomposition of titanate coupling agent at 550 ℃. Surface coating does not change the crystal structure of LiMn2O4, but obviously improves its electrochemical performance, especially high temperature rate performance and cycle performance. At 55 ℃, LiMn2O4 with TiO2 coating delivers a specific capacity of 75.34 mAh/g at 5C, which is higher than that without coating (43.05 mAh/g). After 150 cycles, the capacity retention rate of the material with TiO2 coating and without coating is 77.27% and 62.85%, respectively. The improvement of electrochemical performance is attributed to reduction of Mn dissolution in the cathode material by TiO2 coating, which thus inhibits the change of crystal structure during cycling process, reduces the electrode polarization and charge transfer impedance, as well as improves the charge-discharge reversibility of the material and the Li+ diffusion.

cathode material  /  LiMn2O4  /  TiO2  /  titanate coupling agent  /  surface coating  /  modification  /  electrochemical performance
蔡海洋, 李振京, 范广新, 孟德轩, 刘超帅. 钛酸酯偶联剂表面处理对LiMn2O4结构及性能的影响. 矿冶工程杂志, 2024 , 44 (4) : 18 -23 . DOI: 10.3969/j.issn.0253-6099.2024.04.004
Haiyang CAI, Zhenjing LI, Guangxin FAN, Dexuan MENG, Chaoshuai LIU. Effect of Surface Treatment with Titanate Coupling Agent on Structure and Performance of LiMn2O4[J]. Mining and Metallurgical Engineering, 2024 , 44 (4) : 18 -23 . DOI: 10.3969/j.issn.0253-6099.2024.04.004
正文
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随着便携式移动设备、电动汽车不断普及，锂离子电池的应用越来越广泛[1]。尖晶石型LiMn2O4（LMO）因原料来源丰富、安全性高、工作电压高、环境友好等优点，被视为具有较好前景的正极材料之一，但在实际应用过程中仍存在高温下倍率及循环性能差等问题[2-4]。
在锂离子电池循环过程中，电解液中残留的少量H2O会引起LiPF6的水解，其水解产物HF会造成正极材料LiMn2O4溶解[5-7]。表面包覆是改善LiMn2O4电化学性能的一种常用手段，通过化学或物理方法在材料表面包覆一层具有保护作用的包覆层，可以抑制正极材料与电解液的接触及副反应的发生[8-10]。有研究[11-12]发现，TiO2可以有效中和电解液中的HF，从而抑制电化学反应中副反应的发生，常被用作表面包覆材料。文献[13]利用原位喷雾热解工艺制备出具有TiO2涂层的LiMn2O4，在1C电流密度下经过170次循环，容量保持率为86%，远高于原始材料的69%。文献[14]采用原子层沉积法对LiMn2O4包覆TiO2，在室温和高温条件下材料均表现出较好的循环性能和倍率性能，特别在高温下150次循环，容量保持率从56.1%提升至62.1%；在大倍率（5C）放电条件下比容量由74 mAh/g提高到96.5 mAh/g。可见，包覆TiO2是改善LiMn2O4循环性能和倍率性能的一种有效方法。然而上述改性方法价格较高，实际操作过程较复杂，并不适用于大规模工业化生产。
钛酸酯偶联剂是一种含钛有机物，成本较低，在高温条件下易发生分解，经过热处理后可得到稳定的TiO2。本课题组已通过对铝锆偶联剂简单热处理后实现了在LiMn2O4材料表面包覆Al2O3/ZrO2[15-16]，该方法简单有效，改性后的材料表现出较好的循环性能和倍率性能。本文利用钛酸酯偶联剂在LiMn2O4表面包覆TiO2，系统研究包覆处理对材料结构、电化学性能及在循环过程中材料结构变化的影响。
1 实验
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1.1 LiMn2O4表面处理
用钛酸酯偶联剂处理LiMn2O4表面的过程如下：将钛酸酯偶联剂CS-101（C55H111O9Ti，分解温度260 ℃）0.3 g、0.4 g、0.5 g分别溶解于25 mL无水乙醇中，30 ℃下磁力搅拌30 min，使其充分混合；再分别加入5 g LiMn2O4（焦作伴侣纳米材料公司），继续搅拌2 h；将混合物干燥12 h，然后置于高温管式炉中，550 ℃下保温5 h，得到表面处理后的LiMn2O4。根据钛酸酯偶联剂用量不同，将所得产品分别标记为LMO-n（n=0、1、2、3，代表CS-101相对LiMn2O4的加入量分别为0、6%、8%、10%）。
1.2 材料表征
使用X射线衍射仪（XRD，Smart-Lab型，日本理学）分析材料晶体结构；采用扫描电子显微镜（SEM，德国蔡司Merlin Compact）观察材料形貌及颗粒尺寸，并使用能谱仪（EDS）分析材料表面元素；利用程序控温热焓分析仪对材料进行热分析。
1.3 电化学性能测试
将LMO、聚偏氟乙烯（PVDF）和乙炔黑按照质量比8∶1∶1充分混合，加入N-甲基吡咯烷酮2.5 mL搅拌均匀，制成浆料。把浆料均匀涂敷在铝箔表面，置于90 ℃真空干燥箱中干燥12 h制成正极片。将正极片、负极片（金属锂）、隔膜（美国Celgard2300）和电解液（1 mol/L的LiPF6溶于体积比1∶1的碳酸乙烯酯与碳酸二乙酯混合溶液中）在氩气手套箱中组装成CR-2016型电池。利用电池测试仪（深圳NEWRE CT3008型）测试电池充放电性能，恒流充放电截止电压3.0～4.3 V。使用电化学工作站（武汉Corr Test CS350H）进行循环伏安（CV）和交流阻抗（EIS）测试。
2 实验结果与讨论
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2.1 钛酸酯偶联剂热处理
图1为钛酸酯偶联剂在空气气氛下的TG-DSC曲线及分解产物XRD图谱。DSC曲线显示，加热至473.68 ℃时，出现了一个较强的放热峰，对应钛酸酯偶联剂的氧化；TG曲线显示，随着温度不断升高，样品质量持续减少，加热至475 ℃后，产物质量不再发生变化，表明在475 ℃以上可以保证偶联剂的完全分解。XRD测试结果显示分解产物为TiO2。
2.2 表面包覆对LMO晶体结构的影响
图2为LMO-n产品的XRD图及局部放大图，LMO-n产品晶胞参数见表1。可以看到，所有样品都具有近似的衍射峰，与尖晶石锰酸锂标准PDF卡片（PDF#4-006-9473，空间群）相对应。图中没有TiO2特征峰，这是由于分解后生成的TiO2含量较低，超出了仪器的精度范围。从图2和表1可以看出，各材料晶胞参数相近，晶胞体积没有发生变化。上述结果表明TiO2未进入LMO晶格，没有对晶体结构产生影响。
图3为LMO-0和LMO-2在不同放大倍数下的表面形貌以及LMO-2的EDS能谱图。可以看出，2种材料的二次颗粒均由一次颗粒团聚而成，呈现类球形，尺寸在8 μm左右。然而，处理后的材料表面变得粗糙，可能是TiO2在LMO表面形成了一层包覆层，这与文献[17]报道一致。由LMO-2的EDS能谱扫描结果可知，Mn、O、Ti元素分布均匀，由此推测TiO2已在LMO表面形成了均匀的包覆层。
2.3 表面包覆对LMO电化学性能的影响
图4为0.2C电流密度下LMO-n产品在室温（25 ℃）和高温（55 ℃）条件下的首次充放电曲线。几种材料的充放电曲线基本相似，均出现了两个明显的充/放电电压平台。不同温度下，包覆后材料的首次放电比容量都有所降低，主要是钛酸酯偶联剂分解后的TiO2降低了正极材料中活性物质的比例。从充电曲线看，材料在不同温度下的电压平台无明显差别；但从放电曲线看，包覆后材料在高温下的电压平台（相较于室温）更高，平台电压差更小（充/放电平台间电压差越小，极化越弱[18]）。小的电位差印证了TiO2包覆有助于减小材料在电化学反应中的极化效应。
图5为LMO-n产品在不同温度下的倍率测试曲线。所有材料的放电比容量均随着电流密度增大而降低，但在相同倍率下，包覆后材料在室温和高温条件下放电比容量均有所提升。与LMO-0相比，5C下，LMO-2在室温和高温下比容量分别为49.37 mAh/g和75.34 mAh/g，10C下，包覆后材料室温放电比容量从19.79 mAh/g提升至49.65 mAh/g；10C下，LMO-0在高温下几乎不能放电，而LMO-2的放电比容量为10.00 mAh/g。以上结果证实TiO2包覆可以提升LMO在高倍率下的放电性能，尤其是高温倍率性能。
图6为1C电流密度下LMO-n在室温和高温条件下的循环曲线。包覆后材料在不同温度下的循环性能均有所提高，且高温条件下提升更明显。1C电流密度下，室温、循环200次后LMO-2容量保持率为88.45%；高温、循环150次后LMO-2容量保持率为77.27%，比LMO-0容量保持率（62.85%）提升了14.42个百分点。结果表明，TiO2包覆可以有效提升LMO的循环性能。
图7为材料的循环伏安（CV）曲线。可以看到，所有样品CV曲线均出现了一对明显的氧化还原峰，形状大致对称。有研究[19]发现，氧化还原峰的电势差（ΔEp）越小，说明正极材料的极化效应越弱。其中，LMO-2的氧化还原峰电势差（ΔEp=0.51 V）比LMO-0的氧化还原峰电势差（ΔEp=0.71 V）小。以上结论印证了TiO2包覆能减弱电化学反应过程中的极化效应、提高LMO的充放电可逆性。
图8为LMO的交流阻抗曲线（EIS）及等效电路。材料的EIS曲线由高频区的半圆和低频区的斜线两部分组成，其中高频区半圆代表电荷转移阻抗（Rct），低频区斜线（Warburg阻抗）对应Li+在正极材料中的扩散能力，Rs为电池体电阻[20-21]。EIS曲线拟合结果见表2。由表2可知，表面包覆后正极材料Rct值均有所减小。
为了进一步研究TiO2包覆对锂离子扩散能力的影响，通过式（1）～（2）计算锂离子扩散系数D（Li+）[22]：
式中：Z′为Warburg阻抗，Ω；ω为角频率，ω=2πf；R为气体常数，R=8.314 J/（mol·K）；T为实验中的绝对温度，T=298.15 K；A为电极表面积，A=1.54 cm2；n为电化学反应电子的数量，LiMn2O4的n值为1；F为法拉第常数，F=96 500 C/mol；C为Li+在电极中的浓度，LiMn2O4浓度为0.023 78 mol/cm3；σ为Warburg阻抗因子，σ可由阻抗Z′和角频率ω-0.5拟合获得，如图9所示。
锂离子扩散系数D（Li+）计算结果见表2。经TiO2包覆后Li+扩散系数明显增加。结果表明，TiO2包覆可以有效降低电荷转移阻抗、提高Li+的扩散能力。
2.4 TiO2包覆处理对高温循环中LMO晶体结构和表面形貌的影响
图10为材料循环前后的XRD图及局部放大图。可以看到，2种样品的衍射峰仍对应尖晶石构型，均未出现新的衍射峰，表明电化学反应没有改变材料的晶型，也没有生成新的物相。从局部放大图中衍射峰均向低角度偏移可知，LMO晶面间距增加，这是循环过程中Li+从LMO中脱出后不能全部重新嵌入晶格内部，致使材料结构发生不可逆改变[23]。LMO-0和LMO-2高温下循环150次的晶胞参数见表3。由表3可知，材料晶胞参数a、V值均有所增大，但包覆后材料晶胞参数变化较小。说明TiO2包覆可以有效抑制材料在循环过程中的晶体结构变化，起到增强其结构稳定性的作用，进而提高LMO循环稳定性。
图11为LMO-0和LMO-2高温循环后的表面形貌。可以观察到，2种材料的二次颗粒均保持明显的类球形特征，经过表面包覆的材料形貌保持完整，表面较为光滑；未经表面包覆的材料一次颗粒发生了明显变化，其表面变得粗糙，颗粒表面出现少量裂纹，这是材料在循环过程中表层Mn受到了HF的侵蚀，造成Mn的溶解，样品表面产生裂纹[24]。由此可见，TiO2包覆可以抑制电解液对LMO的腐蚀、减少Mn的溶解、提高材料循环稳定性。
3 结论
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针对商品化尖晶石LiMn2O4存在的容量衰减问题，本文采用一种简单有效的改性方法对LiMn2O4进行了包覆处理，可以得到以下结论。
1）利用钛酸酯偶联剂在550 ℃下分解得到的TiO2对LiMn2O4进行表面处理，可以实现TiO2的均匀包覆。包覆不改变材料的晶体结构，但能明显改善其电化学性能。
2）经TiO2包覆后，LiMn2O4在高温下的倍率性能和循环性能明显提升。向5 g LiMn2O4中加入0.4 g钛酸酯偶联剂，LiMn2O4材料表现出较好的电化学性能。55 ℃下，材料在5C下的放电比容量为75.34 mAh/g；1C下经过150次循环后容量保持率达到77.27%。
3）表面包覆使LiMn2O4材料电化学性能明显提升归因于TiO2包覆层减少了LMO中Mn的溶解，抑制了材料在循环过程中晶体结构变化，降低了电极极化和电荷转移阻抗，提高了材料充放电可逆性及Li+的扩散能力。
基金
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  • 国家自然科学基金重点项目(U1804135)
  • 国家自然科学基金重点项目(51671080)
  • 河南省科技创新人才计划(194200510019)
文献
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2024年第44卷第4期
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文章信息
doi: 10.3969/j.issn.0253-6099.2024.04.004
  • 接收时间：2024-06-07
  • 首发时间：2026-03-18
  • 出版时间：2024-08-01
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  • 收稿日期：2024-06-07
基金
国家自然科学基金重点项目(U1804135)
国家自然科学基金重点项目(51671080)
河南省科技创新人才计划(194200510019)
作者信息
    1.河南理工大学 材料科学与工程学院，河南 焦作 454000
    2.龙佰集团股份有限公司，河南 焦作 454000

通讯作者:

范广新（1970—），男，河南洛阳人，副教授，主要研究方向为功能材料、晶体结构等。E-mail：
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https://castjournals.cast.org.cn/joweb/kygczz/CN/10.3969/j.issn.0253-6099.2024.04.004
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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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