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物理所等在钠离子电池层状氧化物研究中取得进展

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发布时间：2021-08-25

来源：酯香香化学采购网

【化工仪器网科技前沿】中国科学院物理研究所/北京凝聚态物理国家研究中心博士赵成龙、副研究员陆雅翔、研究员胡勇胜团队与荷兰代尔夫特理工大学Prof. Marnix Wagemaker、法国波尔多大学Prof. Claude Delmas等合作，提出一种预测钠离子层状氧化物构型的方法，并在实验上证实该方法的有效性，为低成本、高性能钠离子电池层状氧化物正极材料的设计制备提供理论指导。11月6日，相关研究成果以《钠离子电池层状氧化物材料的合理设计》(Rational design of layered oxide materials for sodium-ion batteries)为题，在线发表在《科学》(Science)上。

　　层状氧化物具有周期性层状结构和二维离子传输通道，是一类研究较早的嵌入型化合物。自1980年以来，锂离子层状氧化物(LiMO2，M为一种或多种过渡金属元素或其他掺杂元素)一直是锂离子电池的主要正极材料，其通过共边的MO6八面体形成重复的层结构，在这些层间锂离子位于氧的八面体配位环境中，形成O型(Octahedral，八面体)堆积构型。在探索钠离子电池电极材料的过程中，钠离子层状氧化物(NaxMO2)成为研究对象。然而，与LiMO2倾向于形成O型结构不同，钠离子在MO6多面体形成的层间与氧具有两种配位环境，分为O和P(Prismatic，三棱柱)两种构型，其中，O3和P2是钠离子电池层状正极材料中较常见的两种结构(数字代表氧少重复单元的堆垛层数，如2对应ABBA…，3对应ABCABC…)(图1A)。这两种结构的层状氧化物作为钠离子电池的正极材料时各有优势：O3相正极材料具有较高的初始Na含量，能够脱出更多的钠离子，具有较高的容量；P2相正极材料具有较大的Na层间距，可提升钠离子的传输速率和保持层状结构的完整性，具有较好的倍率性能和循环性能。为了寻找具有良好储钠性能的正极材料，研究人员合成大量的O3和P2材料，并发现在材料制备过程中，不同的钠含量，不同的过渡金属元素种类、价态及组成均可能导致不同结构的层状材料，进而影响正极材料的电化学性能。然而，除了通过对合成的材料进行物理表征以确定其具体构型外，目前尚未有方法可直接预测层状材料的堆叠结构，指导层状氧化物正极材料的设计制备。

　　探寻钠离子层状氧化物两种构型形成的影响因素是一个重要的研究方向。1976年，Delmas等(Materials Research Bulletin, 1976, 11, 1483-1488)就提出用Rouxel图(Journal of Solid State Chemistry, 1976, 17, 223-229)区分NaxMO2的堆叠结构，说明钠含量和阴阳离子间键的性质(离子性与共价性)都是决定层状堆叠结构的重要因素。然而，该方法只考虑了鲍林电负性的差异，对于具有相同过渡金属元素但不同价态的层状结构(如Na0.7MnO2中同时含有Mn4+和Mn3+)或含有多种过渡金属元素和掺杂元素的层状结构则难以准确预测。

　　该问题同样引起胡勇胜带领的钠离子电池研究团队的关注。他们发现，在材料制备过程中用相同价态的不同过渡金属元素取代时会获得不同的结构，推测或许能够利用过渡金属的离子半径预测堆叠结构，因此引入等效半径的概念(等效半径即加权半径，是将过渡金属的半径乘以该过渡金属的含量)。通过对已报道的材料进行分析，发现等效半径越大越容易形成O3相，反之越容易形成P2相(戚兴国，钠离子电池层状氧化物材料研究及其产业化探索[D].北京：中国科学院物理研究所，2018)。然而，对于不同系列的层状氧化物，等效半径的临界值不完全一样，只能通过等效半径的变化趋势判断易形成哪种堆叠结构。在总结不同系列层状氧化物结构参数的过程中，研究团队发现O3和P2两种结构材料的Na层间距(d(O-Na-O))和M层间距(d(O-M-O))的比值有一个临界值1.62，比值高于1.62通常形成P2相，低于1.62易形成O3相。层间距的变化从本质上说是由NaO2层和MO2层之间的静电吸引力和静电排斥力相互作用的结果，提高钠含量可增强Na层间的静电吸引力，使d(O-Na-O)变小，从而获得O3相；反之，P2相中静电排斥力起主要作用(Chenglong Zhao, et al., Angewandte Chemie International Edition, 2018, 57, 7056-7060)。该研究进一步认清O3和P2构型形成的本质，但是只能通过结构表征后计算层间距比值以确认材料的构型，而不能直接指导和预测层状材料的堆叠结构。

　　基于此，该研究引入“阳离子势(Φcation)”这一变量参数，通过将NaxMO2中过渡金属或其他掺杂元素的加权平均离子势和钠的加权平均离子势对氧阴离子势进行归一化，描述阳离子的电子云密度和极化程度，反映层状氧化物中碱金属层(O-Na-O)和过渡金属层(O-M-O)之间的相互作用，以指示O3型结构和P2型结构之间的竞争关系。为了较直观的区分O3和P2结构，将大量已得到实验验证的O3和P2材料分布在以Φcation为横坐标，

　　为纵坐标的直角坐标系中，发现可以用拟合出的“分界线”区分O3和P2两种构型，从而得到O3和P2结构的“相图”(图1B)。利用该相图可指导层状氧化物材料的设计，例如，对于具备特定Na含量的层状材料，要获得P2结构，可以通过增加阳离子势进行调控；阳离子势的增加意味着M-O相互作用增强，从而导致d(O-M-O)间距的减小和d(O-Na-O)间距的增加，有利于获得P2构型。如果增加钠层中钠离子的含量将会增加Na-O的静电吸引力，进而增强对过渡金属排斥力的屏蔽能力，导致结构由P2相变为O3相。由于过渡金属层中的元素选择空间较大，合理地进行过渡金属离子的组合能在一定程度上减弱钠离子含量的影响。因此，阳离子势使得预测钠离子层状氧化物的P2相和O3相成为可能。为进一步验证该方法在材料合成中的实际指导作用，以Na[Li1/3Mn2/3]O2为初始组成，通过调控阳离子势合成富钠O3-Na[Li1/3Ti1/6Mn1/2]O2(图2)和高钠P2-Na5/6[Li5/18Mn13/18]O2(图3)两种纯相层状氧化物正极材料，并显示出较高的储钠容量。后，发现用阳离子势调控钠基层状氧化物结构的方法在锂和钾的层状氧化物中也同样适用(图4)。

　　该研究为层状氧化物结构的设计提供新方法，并用实验确认了该方法的有效性，为低成本、高性能钠离子电池层状氧化物正极材料的设计制备打下科学基础。研究工作得到国家杰出青年科学基金、国家重点研发计划项目、中科院战略性先导科技专项(A类)、北京市科学技术委员会项目、北京市自然科学基金-海淀原始创新联合基金项目和中科院青年创新促进会等项目的支持。

　　论文链接

图1.阳离子势及其在钠离子层状氧化物中的应用。(A)典型P2型和O3型钠离子层状氧化物晶体结构示意图；(B)具有不同钠含量、不同过渡金属氧化态和组成的P2型和O3型钠离子层状氧化物在以阳离子势Φcation为横坐标，钠的加权平均离子势为纵坐标的直角坐标系中的分布图

　　图2.根据阳离子势设计富钠O3材料。(A)Na-Li-Mn(Ti)-O的阳离子势分析；(B)初始组成Na[Li1/3Mn2/3]O2的XRD图谱和相关标准图谱；(C)O3-Na[Li1/3Ti1/6Mn1/2]O2的结构精修XRD图谱；(D)[Li1/3Ti1/6Mn1/2]O2层中Li/Mn(Ti)有序排布的结构示意图

　　图3.根据阳离子势设计高钠P2材料。(A)Na-Li-Mn(Ti)-O的阳离子势分析；(B)O3-Na[Li1/3Ti1/6Mn1/2]O2和P2-Na5/6[Li5/18Mn13/18]O2的XRD图谱；(C)P2-Na5/6[Li5/18Mn13/18]O2的结构精修XRD图谱；(D)[Li5/18Mn13/18]O2层中Li/Mn有序排布的结构示意图

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[ DB ] CONNECT:[ UseTime:0.000293s ] mysql:host=127.0.0.1;port=3306;dbname=yzncms;charset=utf8
[ SQL ] SHOW COLUMNS FROM `yzn_poster` [ RunTime:0.000830s ]
[ SQL ] SELECT * FROM `yzn_poster` WHERE `cate_id` = 99 AND `p_c_id` = 52 AND `status` = 1 LIMIT 1 [ RunTime:0.000380s ]
[ SQL ] SELECT * FROM `yzn_poster` WHERE `cate_id` = 99 AND `p_c_id` = 55 AND `status` = 1 LIMIT 1 [ RunTime:0.000268s ]
[ SQL ] SHOW COLUMNS FROM `yzn_goods_property` [ RunTime:0.000715s ]
[ SQL ] SELECT `g`.`name`,`p`.`price`,`p`.`unit`,`p`.`type`,`p`.`thumb`,p.id as p_id,`p`.`value`,`p`.`is_where`,`p`.`sku_unit`,`p`.`repeat_type`,`p`.`goods_id` FROM `yzn_goods_property` `p` LEFT JOIN `yzn_goods` `g` ON `p`.`goods_id`=`g`.`id` WHERE `p`.`status` = 1 AND `p`.`is_del` = 0 AND `g`.`is_del` = 0 AND `p`.`is_where` LIKE '%1%' AND `p`.`recommend` = 1 GROUP BY `p`.`goods_id`,`p`.`repeat_type` ORDER BY `p`.`sort` DESC,`g`.`id` DESC LIMIT 0,15 [ RunTime:0.000946s ]
[ SQL ] SHOW COLUMNS FROM `yzn_goods_category` [ RunTime:0.000627s ]
[ SQL ] SELECT * FROM `yzn_goods_category` WHERE `hot_search` = 1 AND `status` = 1 ORDER BY `listorder` ASC,`id` DESC [ RunTime:0.000303s ]
[ SQL ] SELECT * FROM `yzn_goods_category` WHERE `is_show` > 0 AND `status` = 1 ORDER BY `listorder` ASC [ RunTime:0.000304s ]
[ SQL ] SELECT * FROM `yzn_goods_category` WHERE `id` IN (1,2,7,16,17,34,92,95,38) [ RunTime:0.000267s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` = 1 AND `status` = 1 ORDER BY `listorder` ASC,`id` DESC [ RunTime:0.000242s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` = 2 AND `status` = 1 ORDER BY `listorder` ASC,`id` DESC [ RunTime:0.000208s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` = 7 AND `status` = 1 ORDER BY `listorder` ASC,`id` DESC [ RunTime:0.000210s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` = 16 AND `status` = 1 ORDER BY `listorder` ASC,`id` DESC [ RunTime:0.000223s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` = 17 AND `status` = 1 ORDER BY `listorder` ASC,`id` DESC [ RunTime:0.000204s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` IN (34,92) AND `status` = 1 ORDER BY `listorder` ASC,`id` DESC [ RunTime:0.000216s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` IN (95,38) AND `status` = 1 ORDER BY `listorder` ASC,`id` DESC [ RunTime:0.000233s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` = 1 AND `status` = 1 [ RunTime:0.000187s ]
[ SQL ] SELECT * FROM `yzn_goods_category` WHERE `status` = 1 AND `id` = 1 [ RunTime:0.000197s ]
[ SQL ] SELECT `id` FROM `yzn_goods_category` WHERE `status` = 1 AND ( arrparentid like '0,1,%' ) [ RunTime:0.000258s ]
[ SQL ] SHOW COLUMNS FROM `yzn_goods` [ RunTime:0.000594s ]
[ SQL ] SELECT `g`.`name`,p.id as p_id,`p`.`price`,`p`.`type`,`p`.`thumb`,`p`.`unit`,`p`.`is_where`,`p`.`goods_id`,`p`.`repeat_type` FROM `yzn_goods` `g` LEFT JOIN `yzn_goods_property` `p` ON `p`.`goods_id`=`g`.`id` WHERE `p`.`status` = 1 AND `p`.`is_del` = 0 AND `g`.`is_del` = 0 AND `p`.`is_where` LIKE '%1%' AND `g`.`cate_id` IN (25,26,29,30,48,1) AND `p`.`hot_sale` = '1' GROUP BY `p`.`repeat_type`,`p`.`goods_id` ORDER BY `p`.`sort` DESC,`p`.`id` DESC LIMIT 0,10 [ RunTime:0.000973s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` = 2 AND `status` = 1 [ RunTime:0.000289s ]
[ SQL ] SELECT * FROM `yzn_goods_category` WHERE `status` = 1 AND `id` = 2 [ RunTime:0.000214s ]
[ SQL ] SELECT `id` FROM `yzn_goods_category` WHERE `status` = 1 AND ( arrparentid like '0,2,%' ) [ RunTime:0.000209s ]
[ SQL ] SELECT `g`.`name`,p.id as p_id,`p`.`price`,`p`.`type`,`p`.`thumb`,`p`.`unit`,`p`.`is_where`,`p`.`goods_id`,`p`.`repeat_type` FROM `yzn_goods` `g` LEFT JOIN `yzn_goods_property` `p` ON `p`.`goods_id`=`g`.`id` WHERE `p`.`status` = 1 AND `p`.`is_del` = 0 AND `g`.`is_del` = 0 AND `p`.`is_where` LIKE '%1%' AND `g`.`cate_id` IN (42,43,2) AND `p`.`hot_sale` = '1' GROUP BY `p`.`repeat_type`,`p`.`goods_id` ORDER BY `p`.`sort` DESC,`p`.`id` DESC LIMIT 0,10 [ RunTime:0.000981s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` = 7 AND `status` = 1 [ RunTime:0.000218s ]
[ SQL ] SELECT * FROM `yzn_goods_category` WHERE `status` = 1 AND `id` = 7 [ RunTime:0.000210s ]
[ SQL ] SELECT `id` FROM `yzn_goods_category` WHERE `status` = 1 AND ( arrparentid like '0,7,%' ) [ RunTime:0.000220s ]
[ SQL ] SELECT `g`.`name`,p.id as p_id,`p`.`price`,`p`.`type`,`p`.`thumb`,`p`.`unit`,`p`.`is_where`,`p`.`goods_id`,`p`.`repeat_type` FROM `yzn_goods` `g` LEFT JOIN `yzn_goods_property` `p` ON `p`.`goods_id`=`g`.`id` WHERE `p`.`status` = 1 AND `p`.`is_del` = 0 AND `g`.`is_del` = 0 AND `p`.`is_where` LIKE '%1%' AND `g`.`cate_id` IN (10,14,32,33,49,50,51,52,53,54,55,56,57,58,96,97,7) AND `p`.`hot_sale` = '1' GROUP BY `p`.`repeat_type`,`p`.`goods_id` ORDER BY `p`.`sort` DESC,`p`.`id` DESC LIMIT 0,10 [ RunTime:0.000997s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` = 16 AND `status` = 1 [ RunTime:0.000216s ]
[ SQL ] SELECT * FROM `yzn_goods_category` WHERE `status` = 1 AND `id` = 16 [ RunTime:0.000237s ]
[ SQL ] SELECT `id` FROM `yzn_goods_category` WHERE `status` = 1 AND ( arrparentid like '0,16,%' ) [ RunTime:0.000224s ]
[ SQL ] SELECT `g`.`name`,p.id as p_id,`p`.`price`,`p`.`type`,`p`.`thumb`,`p`.`unit`,`p`.`is_where`,`p`.`goods_id`,`p`.`repeat_type` FROM `yzn_goods` `g` LEFT JOIN `yzn_goods_property` `p` ON `p`.`goods_id`=`g`.`id` WHERE `p`.`status` = 1 AND `p`.`is_del` = 0 AND `g`.`is_del` = 0 AND `p`.`is_where` LIKE '%1%' AND `g`.`cate_id` IN (59,60,61,62,63,16) AND `p`.`hot_sale` = '1' GROUP BY `p`.`repeat_type`,`p`.`goods_id` ORDER BY `p`.`sort` DESC,`p`.`id` DESC LIMIT 0,10 [ RunTime:0.000937s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` = 17 AND `status` = 1 [ RunTime:0.000221s ]
[ SQL ] SELECT * FROM `yzn_goods_category` WHERE `status` = 1 AND `id` = 17 [ RunTime:0.000238s ]
[ SQL ] SELECT `id` FROM `yzn_goods_category` WHERE `status` = 1 AND ( arrparentid like '0,17,%' ) [ RunTime:0.000214s ]
[ SQL ] SELECT `g`.`name`,p.id as p_id,`p`.`price`,`p`.`type`,`p`.`thumb`,`p`.`unit`,`p`.`is_where`,`p`.`goods_id`,`p`.`repeat_type` FROM `yzn_goods` `g` LEFT JOIN `yzn_goods_property` `p` ON `p`.`goods_id`=`g`.`id` WHERE `p`.`status` = 1 AND `p`.`is_del` = 0 AND `g`.`is_del` = 0 AND `p`.`is_where` LIKE '%1%' AND `g`.`cate_id` IN (40,64,65,66,67,68,100,17) AND `p`.`hot_sale` = '1' GROUP BY `p`.`repeat_type`,`p`.`goods_id` ORDER BY `p`.`sort` DESC,`p`.`id` DESC LIMIT 0,10 [ RunTime:0.000943s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` = 34 AND `status` = 1 [ RunTime:0.000223s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` = 92 AND `status` = 1 [ RunTime:0.000205s ]
[ SQL ] SELECT * FROM `yzn_goods_category` WHERE `status` = 1 AND `id` IN (34,92) [ RunTime:0.000243s ]
[ SQL ] SELECT `id` FROM `yzn_goods_category` WHERE `status` = 1 AND ( arrparentid like '0,34,%' or arrparentid like '0,92,%' ) [ RunTime:0.000228s ]
[ SQL ] SELECT `g`.`name`,p.id as p_id,`p`.`price`,`p`.`type`,`p`.`thumb`,`p`.`unit`,`p`.`is_where`,`p`.`goods_id`,`p`.`repeat_type` FROM `yzn_goods` `g` LEFT JOIN `yzn_goods_property` `p` ON `p`.`goods_id`=`g`.`id` WHERE `p`.`status` = 1 AND `p`.`is_del` = 0 AND `g`.`is_del` = 0 AND `p`.`is_where` LIKE '%1%' AND `g`.`cate_id` IN (35,70,71,93,94,34,92) AND `p`.`hot_sale` = '1' GROUP BY `p`.`repeat_type`,`p`.`goods_id` ORDER BY `p`.`sort` DESC,`p`.`id` DESC LIMIT 0,10 [ RunTime:0.000922s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` = 95 AND `status` = 1 [ RunTime:0.000222s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` = 38 AND `status` = 1 [ RunTime:0.000202s ]
[ SQL ] SELECT * FROM `yzn_goods_category` WHERE `status` = 1 AND `id` IN (95,38) [ RunTime:0.000272s ]
[ SQL ] SELECT `id` FROM `yzn_goods_category` WHERE `status` = 1 AND ( arrparentid like '0,38,%' or arrparentid like '0,95,%' ) [ RunTime:0.000220s ]
[ SQL ] SELECT `g`.`name`,p.id as p_id,`p`.`price`,`p`.`type`,`p`.`thumb`,`p`.`unit`,`p`.`is_where`,`p`.`goods_id`,`p`.`repeat_type` FROM `yzn_goods` `g` LEFT JOIN `yzn_goods_property` `p` ON `p`.`goods_id`=`g`.`id` WHERE `p`.`status` = 1 AND `p`.`is_del` = 0 AND `g`.`is_del` = 0 AND `p`.`is_where` LIKE '%1%' AND `g`.`cate_id` IN (47,74,75,76,77,78,79,80,81,82,83,99,95,38) AND `p`.`hot_sale` = '1' GROUP BY `p`.`repeat_type`,`p`.`goods_id` ORDER BY `p`.`sort` DESC,`p`.`id` DESC LIMIT 0,10 [ RunTime:0.000953s ]
[ SQL ] SHOW COLUMNS FROM `yzn_article` [ RunTime:0.000659s ]
[ SQL ] SELECT `A`.*,`AD`.*,`C`.`catname` FROM `yzn_article` `A` INNER JOIN `yzn_article_data` `AD` ON `A`.`id`=`AD`.`did` INNER JOIN `yzn_category` `C` ON `C`.`id`=`A`.`catid` WHERE `A`.`id` = 5643 AND `A`.`status` = 1 LIMIT 1 [ RunTime:0.001626s ]
[ SQL ] SHOW COLUMNS FROM `yzn_category` [ RunTime:0.000596s ]
[ SQL ] SELECT `id` FROM `yzn_category` WHERE `parentid` = 35 AND `status` = 1 [ RunTime:0.000223s ]
[ SQL ] SELECT `id` FROM `yzn_category` WHERE `parentid` IN (36,37,38,39,40,41,42) AND `status` = 1 [ RunTime:0.000195s ]
[ SQL ] SELECT `id` FROM `yzn_category` WHERE `parentid` = 43 AND `status` = 1 [ RunTime:0.000180s ]
[ SQL ] SELECT `id` FROM `yzn_category` WHERE `parentid` IN (44,45,46,47,48,49,50) AND `status` = 1 [ RunTime:0.000204s ]
[ SQL ] SELECT `id` FROM `yzn_category` WHERE `parentid` = 6 AND `status` = 1 [ RunTime:0.000178s ]
[ DB ] CONNECT:[ UseTime:0.000256s ] mysql:host=127.0.0.1;port=3306;dbname=yzncms;charset=utf8
[ SQL ] SELECT `A`.`id`,`A`.`title` FROM `yzn_article` `A` INNER JOIN `yzn_category` `C` ON `C`.`id`=`A`.`catid` WHERE `A`.`status` = 1 AND `A`.`catid` IN (35,36,37,38,39,40,41,42) ORDER BY `A`.`flag` DESC,`A`.`listorder` ASC,`A`.`updatetime` DESC [ RunTime:0.020732s ]
[ SQL ] UPDATE `yzn_article` SET `hits` = `hits` + 1 WHERE `id` = 5643 [ RunTime:0.000307s ]
[ SQL ] SELECT * FROM `yzn_poster` WHERE `cate_id` = 10 AND `p_c_id` = 41 ORDER BY `listorder` ASC LIMIT 4 [ RunTime:0.000352s ]
[ SQL ] SELECT COUNT(*) AS tp_count FROM `yzn_article` `a` INNER JOIN `yzn_category` `c` ON `a`.`catid`=`c`.`id` WHERE `catid` = 38 AND `a`.`status` = 1 [ RunTime:0.002641s ]
[ SQL ] SELECT `a`.*,`c`.`catname` FROM `yzn_article` `a` INNER JOIN `yzn_category` `c` ON `a`.`catid`=`c`.`id` WHERE `catid` = 38 AND `a`.`status` = 1 ORDER BY `flag` DESC,`listorder` ASC,`updatetime` DESC LIMIT 0,6 [ RunTime:0.004618s ]
[ SQL ] SELECT COUNT(*) AS tp_count FROM `yzn_article` `a` INNER JOIN `yzn_category` `c` ON `a`.`catid`=`c`.`id` WHERE `catid` = 37 AND `a`.`status` = 1 [ RunTime:0.002567s ]
[ SQL ] SELECT `a`.*,`c`.`catname` FROM `yzn_article` `a` INNER JOIN `yzn_category` `c` ON `a`.`catid`=`c`.`id` WHERE `catid` = 37 AND `a`.`status` = 1 ORDER BY `flag` DESC,`listorder` ASC,`updatetime` DESC LIMIT 0,6 [ RunTime:0.004939s ]