Bridget Jones Never Gets Old

Bridget Jones, as a character, has always hovered uncomfortably between ==the hard light of reality and the rosy glow of romance== . When she first appeared, in newspaper columns written by the British journalist Helen Fielding during the mid-1990s, the 30- something Bridget was claimed as a ==totem== of woman ==hood== at the time: a calorie-counting, self-improvement-obsessed, chain-smoking, ==wine-guzzling singleton== (a ==neologism== Fielding ==immortalized== ); an ==earnest== ==vassal== of Cosmo culture and the embodiment of ==fearmongering== Newsweek coverage about the plight of unmarried career girls. With Bridget, Fielding “articulated the traumas of a generation,” the writer Alain de Botton observed.

But when Bridget’s diary ==entries== were published in book form, in 1996, her true narrative ==arc== was revealed. It didn’t chart a postmodern Gen X nightmare. It was lovingly ==cribbed== from Pride and Prejudice. The most notorious single woman of an era, as her fans learned in the book and its 1999 ==sequel== , and from the movies they inspired in 2001 and 2004, would be largely protected by the ==tired== old ==trappings== of the marriage plot: She would ==bag== her Mr. Darcy and live happily ever after—with a few ==detours== —in his ==dreamy== ==detached== house in Holland Park.

Her ==trajectory== over the next decade-plus (in another round of newspaper columns; another book; and a third movie, Bridget Jones’s Baby, in 2016, not based on a book) certainly had its ==requisite== ==stumbles== . But the character was ==steadied== throughout by the ==Texan== actor Renée Zellweger as the very English Bridget, an unpredictably brilliant piece of ==casting== that just works.

On paper, Bridget can be ==compellingly== hard to ==pin down== , ==inconstant== and ==ironic== , ==messily self-aware== , undeniably human. Early on, she ==cops== to highly compromised feminist principles: She will not “ ==sulk== about having no boyfriend, but develop inner ==poise== and authority and sense of self as woman of substance, complete without boyfriend, as best way to obtain boyfriend.” On-screen, though, Zellweger makes her all heart, ==guileless== as a ==toddler== , impossibly hopeful and ==lovably== absurd. Whatever cards she’s dealt—not least professional ==humiliation== and an accidental pregnancy (paternity unclear, thanks to separate one-night stands and a box of expired ==eco-friendly condoms== )—she ==muddles== through with ==gusto== . We know that Bridget will get her happy ending; this is just about the last romantic-comedy ==franchise== standing. But Zellweger makes us also deeply want her to win, formulaic predictability be damned.

Bridget Jones: Mad About the Boy, an adaptation of the ==slapdash== third novel that starts ==streaming== on Peacock on February 13, keeps the ==trope-laden structure== , but finds surprising depth in a devastating plot twist. Bridget, now in her 50s, is single once again: Her beloved husband, Mark Darcy (played in grand ==metafictional== form by an actor who played the other Mr. Darcy, Colin Firth), has died while on a ==humanitarian== mission in Sudan, leaving Bridget to raise their two children alone. The book uses Mark’s death mostly as a narrative device to launch Bridget, with her typically obsessive energy, into ==cougardom== : She starts dating a ==hunky== man in his late 20s named— ==inanely== —Roxster, which exposes Bridget to a whole new range of body-image issues, and exposes Roxster to her children’s head ==lice== .

The movie, though, is more interested in documenting Bridget’s loss, and in the process, it presents a more honest and moving version of her than we’ve seen before. How will the last cockeyed optimist in popular culture deal with such desolation? ==Widowhood== is no laughing matter, parenting alone even less so—though we have to laugh at Bridget burying her face in the ==fridge== to curse, and being surprised by her son’s ==uptight== science teacher while buying an astonishing variety of ==contraceptives== . ==Pathos== ==underpins== the plot. “Do you miss Dada sometimes?” Mabel, Bridget’s daughter, asks her in the movie. “I miss him all of the times,” Bridget replies.

==Grief== is a tough sell for a ==rom-com== , which is maybe why the movie has marketed itself as something more timely, once again positioning Bridget as representative of her moment. Cinema lately has been consumed with what viewers call the “ ==age-gap romance== ,” or, less ==decorously== , the “MILF setup.” In 2024’s The Idea of You, Anne Hathaway plays a divorcée not unlike Bridget in her ==ditziness== , who ==careens== her way into a love affair with a handsome British ==boy-bander== . In two separate movie projects within the space of a year, A Family Affair and Babygirl, Nicole Kidman ==parses== the power differentials at play when older women find ==fulfillment== with younger men.

Bridget’s adventures with the age gap are characteristically sweet and ==laced== with ==goofiness== : When she meets Roxster, she’s shinnying up a tree that both of her children have managed to get stuck in. When he later messages her on Tinder, it’s via an account that her friends have set up: “Tragic Widow Seeks Sexual Awakening.” ==Mortification== , for Bridget, is only ever a degree or two removed from triumph.

Yet Mad About the Boy, for all its familiar, delightful notes, is also ==wincingly== ==astute== regarding modernday dynamics, good and bad, for women of Bridget’s age. When her friends encourage her to pursue Roxster, the idea is plausible not just because Zellweger is still ==luminously== ==endearing== in ==midlife== , but because the world really has changed: Women can date men a decade or more younger ==without inciting mass hysteria== . But they’ve remained undesirable in other ways: Bridget works as a producer for a daytime TV show where formerly ==hard-hitting== female news reporters now ==gush== their way through ==cooking segments== and ==softball interviews== . For female journalists over a certain age, “HDTV was an ==extinction-level== event,” Bridget’s friend Talitha ==mutters== .

The tension between sharp contemporary ==verisimilitude== and ==age-old romantic archetype== helps explain why Bridget ==potters== on while so many other ’90s heroines have fallen by the wayside. (Remember Ally McBeal? She of the ==miniskirts== and the ==catfights== and the ==ludicrous== workplace dilemmas?) The book version of Bridget has come in for ==derision== as an embarrassing relic of ==postfeminism== , screwing up even the most basic personal and professional tasks, and fixated on her thigh ==circumference== and her office crushes. In 2023, a New York Times retrospective finally declared her “ ==nuttiness== and ==self-loathing== ” to be well past its expiration date for modern readers. Yet her movie comebacks continue to be irresistible, in part because no one is more aware of her failings than Bridget herself.

Crucially, she never lets her ==self-critique== shake a confidence lodged someplace inside her (even if she’s not quite sure where). The academic Kelly A. Marsh has argued that despite her ==ongoing== preoccupation with becoming better, Bridget at her core represents, through all her phases, the victory of self-acceptance. She flourishes not just because of the love stories that the novels’ framing forces on her, but thanks to the faithful love of her friends and her own ==stouthearted== spirit.

There’s something ==poignant== , too, about seeing Zellweger in the role, despite all the ==indignities== the actor has suffered along the way—the 2000 cover shoot for Harper’s Bazaar, rudely shelved because Zellweger had gained weight for the role and was deemed too fat for a fashion magazine; the ==tabloid== coverage declaring her “ ==scary skinny== ” when she then duly dieted; the discourse about her changing face, so rabid and intrusive that she had to strike it down in a personal essay for HuffPost. At 55, Zellweger is in what Germaine ==Greer== once cited as a decade of new “invisibility” for women—a phenomenon that Bridget herself analyzes in her diary. And yet here they both are: ==undaunted== , blond, adorable, enduring, changing the world by refusing to ==shrink away from it== . That, as Bridget might say, is v.v. good to see.

Vocabulary, Phrases and Sentences

Words Chinese Definition Phonetic Symbol
the hard light of reality and the rosy glow of romance 现实的刺眼光芒与浪漫的 rosy 光辉 /ðə hɑːd laɪt ɒv riˈæləti ænd ðə ˈrəʊzi ɡləʊ ɒv ˈrəʊmæns/
totem 图腾 /ˈtəʊtəm/
hood 风帽;兜帽;(汽车发动机的)罩;(非法团伙成员常戴的)头罩 /hʊd/
wine-guzzling singleton 酗酒的单身人士 /ˈwaɪn ˈɡʌzlɪŋ ˈsɪŋɡltən/
neologism 新造词;新词 /niːˈɒlədʒɪzəm/
immortalize 使不朽;使永存;纪念 /ɪˈmɔːtəlaɪz/
earnest 认真的;诚挚的;热切的 /ˈɜːnɪst/
vassal 附庸;臣属;诸侯 /ˈvæsl/
fearmonger 散布恐惧者;制造恐慌者 /ˈfɪəmʌŋɡə(r)/
entry 进入;入口;参赛作品;条目 /ˈentri/
arc 弧;弧形(物);电弧;弧光 /ɑːk/
crib 婴儿床;抄袭;剽窃 /krɪb/
sequel 续集;续篇;后续的事 /ˈsiːkwəl/
tired 疲倦的;累的;厌烦的 /ˈtaɪəd/
trapping (动物的)皮毛;陷阱;圈套;伏击 /ˈtræpɪŋ/
detour 绕道;弯路;迂回路 /ˈdiːtʊə(r)/
dreamy 梦幻般的;轻柔的;恍惚的;心不在焉的 /ˈdriːmi/
detached 分开的;分离的;超然的;冷漠的 /dɪˈtætʃt/
trajectory 轨道;轨迹;弹道 /trəˈdʒektəri/
requisite 必要的;必不可少的;必需品 /ˈrekwɪzɪt/
stumble 绊脚;跌跌撞撞地走;蹒跚;犯错;失足 /ˈstʌmbl/
steady 稳定的;平稳的;持续的;坚定的;使稳定 /ˈstedi/
texan 得克萨斯州的;得克萨斯州人 /ˈteksən/
casting 铸造;铸件;投;掷;选派角色 /ˈkɑːstɪŋ/
compellingly 引人注目地;令人信服地 /kəmˈpelɪŋli/
pin down 确定;查明;准确描述;迫使明确表态 /ˈpɪn daʊn/
inconstant 无常的;多变的;反复无常的 /ɪnˈkɒnstənt/
ironic 具有讽刺意味的;反讽的 /aɪˈrɒnɪk/
messily self-aware 凌乱地自我意识 /ˈmesəli ˈself əˈweə(r)/
cop 警察;抓住;逮捕 /ˈkɒp/
sulk 生闷气;愠怒 /ˈsʌlk/
poise 沉着;镇定;泰然自若;姿势;姿态 /ˈpɔɪz/
guileless 诚实的;坦率的;不狡诈的 /ˈɡaɪlləs/
toddler 学步的幼儿 /ˈtɒdlə(r)/
lovably 可爱地 /ˈlʌvəbli/
humiliation 羞辱;耻辱;蒙羞 /hjuːˌmɪliˈeɪʃn/

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19日晚第一次进实验室,师姐带我合成一种固态电解质,参考文献有Angew. Chem. Int. Ed. 2019, 58, 8681 –8686等。由于电池是锂电池,需要隔绝$\rm{H_2O}$$\rm{O_2}$,所有电解质原料的称量操作需要在手套箱中进行,手套箱中的称量算是对新人的第一大挑战吧哈哈~

手套箱之前也用过,今晚顺便复习了一下

手套箱

稍微总结了一下步骤:

  • 紧闭内舱门,打开 过渡舱外舱门
  • 放入货物并关闭外舱门
  • 进行三次充放气操作(先抽后充),然后停止充放气
  • 打开内舱门取出货物

手套箱内的神器—— 镊子

我在手套箱内主要是称量,如下试剂:

试剂 性状 备注 质量 摩尔质量
$\rm{Li_2S}$ 白色晶体,反萤石结构 有点粘,难称 0.3446g(0.0074995 mol) 45.942
$\rm{P_2S_5}$ 黄色片层状晶体 易水解 0.4168g(0.001875 mol) 222.248
$\rm{LiCl}$ 白色晶体,易潮解 有点像白糖 0.2384g(0.005624 mol) 42.394
$\rm{LiBr}$ 白色晶体,易潮解 有点像白糖 86.845

$$ \rm{Li:P:S:Cl}=0.020623:0.00375:0.0168745:0.005624=\approx5.5:1:4.5:1.5 $$

x=0.5(本次实验)

全固态锂电池的发展依赖于高性能固态电解质,需具备高离子电导率和良好延展性等特性。锂硫银锗矿($\rm{Li_6PS_5X}$)虽有潜力,但此前室温离子电导率等性能有待提升,本次实验尝试复现文献提高电解质的离子电导率。

LPSX (X=Cl,Br,I),硫银锗矿型,名称来源于硫银锗矿$\rm{Ag_8GeS_6}$

  • $\rm{Li_{6 - x}PS_{5 - x}Cl_{1 + x}}$固溶体相,发现增加$\rm{\dfrac{Cl^-}{S^{2-}}}$比例可系统且显著地影响晶格中锂离子扩散性,提升电导率。如$\rm{Li_{5.5}PS_{4.5}Cl_{1.5}}$在 298K 时冷压电导率达$\rm{9.4\pm 0.1 mS/cm}$,烧结后为$\rm{12.0\pm 0.2 mS/cm}$,几乎是相同条件下$\rm{Li_{6}PS_{5}Cl}$的四倍
  • 发现卤化物取代降低了锂离子与周围框架阴离子的相互作用,增加了位点无序度和锂空位数量,进而提升锂离子扩散性,明确了离子传输机制

在手套箱内将三种试剂称量后放入研磨罐内,和离心机类似,球磨机的研磨罐也需要配平(最好先用转子球配平再称量药品),配平后放入机器内设置参数

BM20行星式球磨机

工作原理:当仪器启动时,电机带动公共的太阳轮转动,而位于太阳轮上的研磨罐则围绕自身的轴作自转运动,研磨罐自转的方向与太阳轮的方向相反。研磨球与研磨罐一起运转时,受到自转偏向力的叠加影响,在这种影响下,研磨球释放出大量的动能,样品不断受到研磨球的撞击,同时与研磨罐内壁产生大量摩擦,从而被高度粉碎。

参数设置

从上到下球磨机的参数设置分别为:

  • 转速
  • 研磨时间
  • 休息冷却时间
  • 循环次数

本次的研磨时间设置为10min,休息时间设置为5min,循环次数为60,那么总时间就是15h

(机械研磨引发固相反应)

20日上午11点,将研磨罐从球磨机上卸下来(和水热合成反应釜有点像哈哈~),忘了压住研磨罐盖子,大力出奇迹把盖子拔出来了,电解质接触到空气了😇,就当成对照组吧(本次合成了两组相同的,姑且认为盖上盖子就是与外界气体相隔绝哈哈)

将两个罐子转移到手套箱内,首先转移到称量纸上,然后转移到小离心管内,这一步巨难操作,研磨后的电解质有些结块了,需要扣下来,最主要是研磨罐比较重,我给不小心弄撒了一点😑,转移到两个小离心管后把两个研磨罐从手套箱内拿出来,开始洗刷刷,硫化物用水冲几遍、乙醇冲几遍就溶解掉、洗干净了,最后放入80摄氏度烘箱就吃饭去咯~(烘干即可,不可久置,否则==研磨罐胶圈会老化,密封性就不好了==)下午还有仪器分析实验课呢

20日晚上19点,开始隔绝氧气烧结样品。在手套箱内将离心管中的试剂用长颈漏斗分别转移到两个长玻璃管里,然后怼上阀门,用封口胶密封上,然后去一楼首先将气阀门接入压缩机,将长玻璃管内的气体尽可能抽出,接着用$\rm{CH_4+O_2}$的混合气体灼烧长玻璃管使其密封(和大一时无机化学的一次实验有点像,自己烧胶头滴管哈哈哈😳),烧完后就变成了两个完全密封的玻璃管啦,然后把它们放入电炉烧结即可。

冷却后,将玻封转移至手套箱中,打碎玻璃管将药品取出并组装到固态电池模具中,拿出来加压。用Zplot测一下阻抗,结果不理想,准备烧另一组样品,然后电炉给我玩坏了😂

节能箱式电炉

请教维修师傅,好在不是大问题,很快修好了,大哥还贴心的给了我一份食用指南,这下不怕忘记步骤了😀

程序设定步骤

  1. 按一下向左键,C01为初始温度,设置成PV开机数值(室温);
  2. 然后按一下循环键,T01为时间,默认分钟,设定想要的升温时间(自行换算,升温速率不要太快≤10℃/min,一般5-10℃/min最好);
  3. 然后按一下循环键,切换到C02为下一个温度点,设定温度;
  4. 以此类推…
  5. 到T0几上设定为-121是结束指令代码(切记是-的121,两个-121)
  6. 完成后,停滞几秒中回到基础界面,长按RUN键1-2秒钟别抬手,待仪表黄色数字显示一下RUN后,立刻抬手,再按绿色启动键。
  7. 电炉开始加热,注意观察电流表指针是否摆动,有摆动为正常。

范例:以每分钟10度的升温速率升温到1200度,在1200度保温3个小时,再每分钟5度降到1000度后自然降温的程序设置如下

  • C01设置成PV显示值(一般在50-60度之间);
  • T01设置成120;
  • C02设置成1200;
  • T02设置成180;
  • C03设置成1200;
  • T03设置成40;
  • C04设置成1000;
  • T04设置成-121

胡思乱想乱入

Li-Argyrodite的结构晶胞化学式——$\rm{Li_6PS_5Cl}$Li(I):

Li:12(6个面2)+12=24(体内)

P(VI):$12\dfrac{1}{4}$(棱心)+1=4(体心)

S(II):$\rm{\dfrac{1}{4}*4*12}$(棱心)+8=20(体内)

Cl(I):$8*\dfrac{1}{8}+6*\dfrac{1}{2}$=4(立方最密堆积)

假设分别合成$\rm{Li_{5.5}PS_{4.5}Cl(SCN)_{0.5}}$$\rm{Li_{5.5}PS_{4.5}Cl_{0.5}(SCN)}$ 0.003 mol

$\rm{Li_6PS_5Cl}$中的锂有5种配位环境,两种Wackyhoff位置

Li的五种配位环境
Agents $\rm{Li_{5.5}PS_{4.5}Cl(SCN)_{0.5}}$ $\rm{Li_{5.5}PS_{4.5}Cl_{0.5}(SCN)}$
$\rm{Li_2S}$ 0.2757 g 0.2757 g
$\rm{P_2S_5}$ 0.3334 g 0.3334 g
$\rm{LiCl}$ 0.1272 g 0.0636 g
$\rm{LiSCN}$ 0.0975 g 0.1951 g

VASP 通过密度泛函理论(DFT)计算材料的电子结构和原子间相互作用,最终目标是预测锂离子在材料中的迁移能力,具体包括:

  1. 活化能:Li⁺迁移的能量势垒(直接影响传导率)。
  2. 扩散系数:通过分子动力学(MD)模拟计算 Li⁺的扩散速率。
  3. 结构稳定性:掺杂或缺陷对晶格结构的影响。

今天又来合另外一种电解质了、、、

改性的argyrodite(Li6PS5X),下面是原料配比,请分析一下使用下面原料合出来的化学式是什么呢?(argyrodite结构没有发生改变)

  • P2S5: 0.4995g (0.001124 mol)
  • $\rm{LiCl}$: 0.2857g (0.006739 mol)
  • $\rm{Sm_2S_3}$: 0.0469g (0.0001181 mol)
  • $\rm{Li_2S}$: 0.4183g (0.009103 mol)

Li: 0.006739+0.009103*2=0.02495

P: 0.001124*2=0.002248

Cl: 0.006739

Sm: 0.0001181*2=0.0002362

S: 0.001124*5+0.0001181*3+0.009103=0.0150773

  • $\rm{Li_6(P_{0.952}Sm_{0.048})S_{4.605}Cl_{1.395}}$(化学式未知)
球磨参数

球磨完之后,在手套箱内将合成的粉末倒入长玻璃管中(将带有勺子的吸管插入玻璃管底部,再舀取药品),将玻璃管插入橡胶管中,不用插得太深,然后关闭阀门,从手套箱内取出来,再缠好封口胶

装好药品密封的玻璃管

接下来去一楼101房间,将阀门接上泵,开启真空泵,缓慢旋转阀门,一定要缓慢,否则就不利于封管

封管的操作暂时学不来,用的是钢瓶中的某种气体,调节大小阀门至淡蓝色的焰心长度约1cm即可,反复灼烧并扭转玻璃管,一段时间后被灼烧处开始变细、拉丝、断开,然后再略微灼烧封号的管的尖端处,应该是去除一些毛刺吧

然后就开始烧,今天(5.17)又复习了一下电炉的使用,龙哥的祖传参数:500摄氏度烧12小时,升温速率5度每分钟

1
2
3
4
Step1:设置C01——一般设置室温
Step2:设置t01——需要计算,目标温度和室温的温差/升温速率
Step3:设置C02——目标温度
Step4:设置t02——保温时间

至此就结束了,下面这张图应该挺形象的,不过我暂时不用这么多梯度升温

梯度升温示意图

4月22日晚,在手套箱内将烧结而成的电解质材料从玻封管内取并研磨,如果烧结后是坚硬的固体则可直接倒出,然后单独用镊子夹到研钵内(如果直接倒可能将碎玻璃渣引入),小TIPS:研磨的时候可以盖一层薄膜再将固体锤碎,将两个样品(6h & 8h)分别装到两个离心管内,放入另一个手套箱,接着师兄带我装全电池,模具如图

中科固态电池模具

全电池

  • 上层一般装负极,锂金属原片(d = 0.6 mm)
  • 中层为固态电解质
  • 下层一般装正极
    • 本次正极部分=正极材料+固态电解质+碳,质量比为70:30:3

对于全电池,需要施加三次压力(对称电池理论上只需要两次

加压过程
  • Step1:先装固态电解质材料,一般称取80-100 mg,本次称取100 mg,装入后振一下,再用上盖旋拧一下,让电解质材料尽量均匀,且上层和下层的豁口尽量对齐
  • Step2:放入压机加压,上旋钮抵住上盖,然后加压至2t,维持2min,加压时豁口不要对着压机地柱子
  • Step3:装正极部分(正极材料+固态电解质+碳),顺便检查一下加压后的固态电解质,一定不能产生裂纹,需要根据正极材料的质量设置测试的电流,将征集部分小心地导入正中央,均匀地覆盖在电解质材料上
  • Step4:放入压机加压,相同操作,加压至4t,维持2-5min左右
  • Step5:装负极材料,负极是一片金属锂(直径0.6cm,先将金属片放在下层盖地柱子上(柱子直径1cm),然后盖上下层,拧紧
  • Step6:放入压机加压,需格外小心,只需施加少许压力即可,指针略微移动即可

OK,装完全电池后放入夹具中,接下来去8楼测试去,将模具连接好电池系统(红正黑负)即可,接下来在计算机上设置参数

使用蓝电电池测试系统

参数设置

目前还看不太懂,待我请教一下做电池的好兄弟后再来更新🤗

5.20下午,龙哥带我测阻抗谱,一些细节我还不太熟练。首先是把烧好的固态电解质材料放到模具中,舀一点材料到模具中,然后“提取模具-放下模具”使得材料做自由落体运动,稍微平整一些,pellet厚度不易过薄或者过厚,我压的pellet1.77mm,显然是过厚了,再拧上旋钮关闭模具。

接着用压机(顺时针锁死即可施加压力,用完需锁死),只需要压到2tons,

压力表

然后上面接负极黑线,下面接正极红线(但其实没有正反),设置好参数就可以开测了,接下来不出意外的话就要出意外了

点击测试

点此图标查看图

看图
局部的阻抗图

如图是我合成的材料的局部的阻抗图,很烂,重新测了几次都不对,晚上测一下XRD看看是怎么回事。

5.21晚上,闯大祸了😢。计划在唐楼测一下XRD(因为物理楼的XRD需要预约),我需要从手套箱内将药品拿出来,但是我发现此时过渡舱是满气状态而非真空状态,我以为是干净的氩气,但其实可能是上一个人用完手套箱忘记了抽真空。我没有多想,直接在手套箱内打开了过渡舱们,氧气含量飙升至90+,害的龙哥搬了一罐氩气来清洗手套箱。I’m sorry😭.The dilemma absolutely, definitely has been caused by myself, which could have been avoided with more patience and careness😭

龙哥给我拿了测XRD的样品槽测试片,我还不小心打碎了一片😭,真是笨手笨脚的🤕。制样方法是将样品均匀地涂在凹槽内即可,不必涂满,尽可能高度平整(否则衍射峰可能出现略微偏移)。涂好样品后需要用密封(暂时还不知道那个黄黄的胶布的学名叫啥),可以用有粘性的“胶布”直接贴上,但是容易黏在手套上,也可以用凡士林+无粘性的胶布(本次采用),4点涂或者8点涂凡士林,然后将凡士林往外刮出去,形成一个密封圈,切忌往内刮否则会出现凡士林的衍射峰

然后去8楼测XRD,切记需要带机器停止工作后才可打开舱门,放置、取下样品时需要双手托住样品!

参数设置

电压和电流分别是40kV和40mA,2theta角度时10~80

XRD衍射图谱

OK,我拿到衍射图谱了,待我进一步分析

分析完毕,样品似乎已经合成出来了,杂峰比较多,但是为啥当天下午没有测出来呢???因为杂峰太多了吗

XRD figure

6.1(六一儿童节快乐🤓),今天大概又看了一下三月份的那篇综述。龙哥装测固态电解质的时候只需压机压倒2Tons了,后面问问它表面积的事,换算成MPa。模具中原盘的面积是0.785 cm2,中科万垣的模具,那么压强是249.68MPa,和文献中所记载的适宜压强一致。

6月5日早上的小组会,杜老师也提了个醒:测定不同类型的电解质时所称量的质量和所选取的压力是不相同的,至于为什么会称量80mg呢?

以下是从网络获取到的模具的资料:

以BM01-10为例

模具拆解图

这个模具和实验室的不太一样哦

内部规格:(连 PPS 套)直径 40mm。腔体直径 10mm。总高度 70mm

整体规格: 装置外直径 90mm,连丝杆总高 130mm

特性

- 稳定性高,密封好;

- 可长期在 可长期在300 Mpa压力下使用;

- 装卸方便,易于操作;

- 可长期在 -40~200℃温度环境下使用;

- 尺寸(mm,BM01-10含不锈钢外架):100 L x 100 W x 130 H

- 重量(kg,BM01-10含不锈钢外架):2kg

受压测试

1、最高压力可至 400 Mpa

2、压机压到 1 吨压力约等于压强 125 Mpa

下图是内部构造示意图:

内部构造图

从上到下依次是:

  • 不锈钢上杆
  • 铜导电极板
  • 聚四氟乙烯捆扎带
  • O形密封圈
  • 聚苯硫醚保护罩
  • 三氧化二铝陶瓷绝缘层
  • 电极和电解质
  • 聚苯硫醚保护罩
  • O形密封圈
  • 聚四氟乙烯捆扎带
  • 铜导电极板
  • 不锈钢下杆

下面的图是一个固态电解质合成制备的流程图,手磨这个步骤不知道是为啥,先挖个坑

固态电解质制备的流程图

注意事项:

  • 固态电池的组装,整个过程需在手套箱中操作
  • 模具保压测试,压力约为 80-150MPa,如果有锂片或者铟片,压力应降低至 80Mpa 以内固态电池绝缘模具说明
  • 模具和粉末压片机配合使用

6月3日下午,刚开完大组会,老师对大家的要求还是蛮高的,虽然我啥都听不懂😂,但还是简单总结了一下可能对自己有帮助的内容,希望以后少犯错甚至不犯错,期待快速成长、入门、甚至成为强者

  • PPT有标签(其实之前科学实践课的时候玛琳老师也提到过了,一直忘了😂)
  • 把结论放在最前面(分情况
  • 做事前三思,想清楚why和how
  • 提出科学问题而非重复造轮子
  • 独立思考
  • 搞清楚各种表征的原理、解释清楚表征结果
  • 以防万一做两个PPT吧(16:9和4:3的),大组会荧幕是4:3的而小组会的屏幕是16:9的

6月3日晚上,拜托奉云师姐帮我封了两个样品管,然后真空烧结12h(500摄氏度),虽然我还没有能力独立封管(安全起见,至少需要2人+),但还是简单总结一下封管步骤吧,省得以后又搞忘了😂(已经忘了,下一次封管再熟悉一下)

  • 关门

  • 先放掉枪中的气体以防发生危险

  • 先开右侧钢瓶总阀,再开小阀门,指示到一格

  • 接着开左侧钢瓶总阀,再开小阀门,忘了几格了

  • 然后开大枪,此时出来甲烷,点燃甲烷

  • 然后开小枪,此时枪头附近氧气浓度增大, 甲烷燃烧剧烈

  • 缓慢增大小枪流速,使得焰心长度约1cm即可

  • 另一人拿稳玻璃管,将待封处对准焰心

  • 灼烧玻璃管至待封处融化,然后两手分别向不同方向旋转至拉丝即可

6月4日晚上,测了一下LPSC(x=0.5)的离子电导率,由于我有些心急,未等模具降至室温就测,所以离子电导率有些偏高,稍大于文献

6月5日晚上,测了一下两个样品的XRD,数据格式保存错了,悲😂

6月6日晚上,测了溴掺杂和氯掺杂的两个样品的阻抗谱,前者偏小,后者偏大,待我稍微分析一下

测完阻抗后的pellet

测试时称取80mg,用压机压到2Tons(249MPa)来减小晶界电阻,降低孔隙率,减小阻抗

简单总结一下最近的工作:

原料原料

首先在手套箱中称量药品并转移至球磨罐中,两罐为不同样品,原料总重均为1.000g,球磨参数为300rpm/min,磨10min休息3min,60cycles,将球磨完的样品转移至玻璃管中,真空玻封。在电炉内以5摄氏度每分钟的升温速率和降温速率在500摄氏度下烧结12个小时,冷却到接近室温(大概65摄氏度左右)取出,破管,称取80mg到模具内,加压到2Tons进行电化学阻抗谱测试,后续又进行了X射线粉末衍射的测试

  • 80mg只是一个经验数值,各大文献的测试细节只提及pellet的厚度和直径而未提及质量,对于F4̅3m空间群的LPSX,80mg在2Tons压力下厚度大约是0.62mm,每次称取80mg进行电化学阻抗测试后就不用再量pellet的厚度了
  • 2Tons是一个适中的压力,能增强 Argyrodite 型硫化物电解质颗粒间的接触,降低孔隙率和晶界电阻,减少离子传输的曲折度,从而提升离子电导率,模具直径为10mm,2Tons的压力大约是249MPa,与文献记载的压力范围一致
image-20250609093142804

对于富氯的样品:

Cl-doping

以上两次测试都是在唐楼进行的

Cl-doping-impedance
六月七日第二次测量富氯电解质的的Nyquist图
image-20250609095524544
  • 受仪器所限制,超高频区域无法测得,观测不到半圆
  • 所测得的阻抗为晶界阻抗与体相阻抗之和

$$ 离子电导率\sigma = \dfrac{L}{S\times R}=\dfrac{0.62 \times 10^{-1} \rm{cm}}{\frac{1}{4}\pi\times1^2 \times 8.5127 \Omega}=9.273 \rm{mS/cm} $$ 与文献报道的$9.4\pm0.1 \rm{mS/cm}$接近

而对于富溴的样品:

$\rm{Li_{5.3}PS_{4.3}Cl_{0.7}Br}$的阻抗谱测试显示其离子电导率较低,大约只有$\rm{3.68 mS/cm}$,与文献差异较大,

Br-doping-impedance

文献中的图

image-20250608202434982

将本次合成的富溴样品与理论计算的S/Br完全有序的$\rm{Li_6PS_5Br}$衍射图谱以及文献图谱对比

左侧为文献中的衍射图谱

我的样品、文献中的衍射图谱、理论模拟的图谱主峰都能对上,但说明都相同形成了特定的晶体结构,但是这三种材料中的阴离子无序度可能不同,导致最终的离子电导率不同,文献的原合成方法比较麻烦就没有采用:称取原料——手磨——球磨(只是为了混合均匀,30min)——300摄氏度真空烧结12小时——再次手磨并压制成==6mm直径==1mm厚的pellet——再次真空烧结,450~460摄氏度,12小时

猜测一:

  • 文献中的合成方法第一次烧结不充分但可以促进晶格部分形成,压片时的高压使颗粒表层晶格畸变,原子间接触更紧密,在第二次烧结时能够形成更加无序的阴离子分布格局

有另一篇合成$\rm{Li_{5.5}PS_{4.5}Br_{1.5}}$的文献Front. Chem. Eng. 4:883502.与本次实验合成时的步骤大致相同但球磨参数为100rpm/min且时间只有2h,离子电导率为5.21 mS/cm,有猜想二:

  • 根据之前看的文献,当掺入更软、半径 更大的阴离子的时候,$\rm{Li_{6-x}PS_xCl_{1+x}}$中的x通常会减小以适应晶格大小变化,那么其实我合成的$\rm{Li_{5.3}PS_{4.3}Cl_{0.7}Br}$其实更稳定一些(但这并不代表阴离子无序度大、离子电导率大)

  • 溴离子与氯离子相比半径大,更软一些,可能需要适当降低球磨强度否则能量过高会导致晶格破碎

能否根据激活能计算大致所需要的临界温度呢?

读一下和球磨相关的文章,球磨的作用究竟是什么?不可能只是简单的混合均匀?

就算球磨强度过高导致晶格无法形成,那为什么后面的高温烧结不可以形成晶相呢?计算一下LPSC和LPSB的晶格能?

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本贴为记录贴,师兄师姐教了我3+次如何设置炉子的程序,然鹅我还是易忘于是就有了本帖😢

程序似乎都是通用的吧,马弗炉、管式炉、电炉……啥时候遇到不一样的了再更新本贴吧

  • 第一步:设置当前温度C1(即待机的PV数值)
  • 第二步:调节最高温度C2
  • 第三步:设置T1,T1=(C2-C1)/升温速率
  • 第四步:设置升温后的保温温度C3
  • 第五步:设置保温时间T2(单位min)
  • 第六步:保持(显示-121)
  • 第七步:长按RUN,启动程序

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Who’s Your Mommy?

In the spring of 2022, I was 36 years old and jumping up and down in my bathroom, trying to ==figure out== my future. I had ordered ==a fertility test== online that said it would provide fast results with just a few drops of blood. The videos on the company’s website featured a smiling blond woman jumping—to stimulate blood flow, naturally—and then ==e­ffortlessly== ==dribbling== blood from her nger tips all over a little strip of test paper. All I had to do was be like her. Joyful. ==Sanguineous== . Fertile.

For years, my husband, Rich, and I had ==gingerly== walked the prime ==meridian== between wanting and not wanting kids, usually leaning toward the “no” side. Having a baby had seemed un a­ ordable and impossible. On days when I nished work at 8 p.m., the thought of ==procreating== made me laugh, then ==shudder== .

Recently, though, I’d begun to reconsider. I was in the midst of an ==admittedly== strange-sounding project: I was spending a year trying to change my personality. According to a scientific personality test I’d taken, I scored sky-high on ==neuroticism== , a trait associated with anxiety and depression, and low on ==agreeable== ==ness== and ==extroversion== . I lived in a constant, ==clenched== state of dread, and it was poisoning my life. My therapist had stopped laughing at my jokes.

But I had read some scientific research suggesting that you can change your personality by behaving like the kind of person you wish you were. Several studies show that people who want to be, say, less isolated or less anxious can make a habit of socializing, meditating, or journaling. Eventually these habits will come naturally, ==knitting== together to form new traits.

I knew that becoming a parent had the potential to change me in even more profound ways. But I had no idea how. My own mother once said to me, “I can’t picture you as a mother.” The truth was, neither could I.

I wasn’t sure I could get pregnant, even if I wanted to. My age put me in a category that was, in a less delicate time, called “ ==geriatric== ” for pregnancy, and one doctor told me my eggs were probably of “poor quality.” The fertility test I’d ordered was meant to determine if those eggs were ==serviceable== . In the bathroom, I unwrapped the ==glossy== white box. The instructions said the test would take 20 minutes and require a pack of ==lancets== . I grabbed one and ==stabbed== it into my geriatric forefinger. Two hours, five lancets, and a ==graveyard== of ==gauze== and alcohol wipes later, I still hadn’t squeezed a single ==droplet== out of my finger. Was I not jumping high enough? Was I already failing as a mother?

I was worried I wouldn’t be able to have a baby. I was also scared to death of having one.

Arguably, many things are wrong with me. I was raised by Russian immigrants who constantly worried that the “ ==dark day== ” was upon us, so hopeful thoughts about the future of humanity don’t come naturally. I’m not a person who is a­ ected by cuteness. I’ve never liked holding—or even really looking at—other people’s babies. I don’t like animals. I couldn’t imagine ==cooing== and smiling at a baby as much as science says you’re supposed to for their brain development.

My neuroticism made it especially hard to decide if I wanted kids, because no process is more ==rife== with uncertainty than parenting, and nothing scares anxious people more than uncertainty. I worried that Rich and I would ght more, and that our relationship would su­ er. I worried about sleep ==deprivation== . I felt ==torn== between my lifelong conviction that people shouldn’t create problems for themselves and my (apparent) desire to do just that.

I would wake up in the middle of the night and Google things like percent ==miscarriage== pregnant while 36?; anxiety pregnancy miscarriage causes; Diet Coke fetal defects; pregnancy brain stops working hands stop working. These searches surfaced ==horrific== ==anecdotes== , but never any conclusive answers about what I should do. One time, I Googled reasons to have kids and found an article that labeled all the reasons I had come up with—like being cared for in old age and having someone who loves me—with the heading “Not-So-Good Reasons to Have Children.”

But then I would remember the times we visited Rich’s mom, who had ==dementia== , in her nursing home. ==Her face lit up at the sight of him== . “My son, my son, my only son,” she’d say, grabbing his arm. He was the only person she still recognized. The visits were a reminder that the people who matter most at the end are your children. The readers of your blog posts won’t make the trip.

Heather Rackin, a sociologist at Louisiana State University, found in a study that the death of a mother or sibling increased the likelihood that a woman would give birth within two years. The e proximity of death is, perhaps, ==a wake-up call== . Who will remember us? The study was based on Rackin’s personal experience: When her father died in 2017, she decided not to wait any longer to have kids. His death got her thinking, she told me, about what was important in life: the experience of being loved and the chance to provide that love for someone else. Her rst child was born in 2019.

There are many reasons to postpone or avoid having children— the cost, the responsibility, ==the existence of and use case for the NoseFrida== . But in addition to the practical challenges, a narrative has taken hold: Everything changes when you become a mother.

Once they reach their 30s, many people have carefully cultivated friend groups and ==sourdough== starters and five-year plans. They “really have a good sense of who they are, and then having a baby totally disrupts everything that they thought they knew about themselves,” says Lauren Ratli  , a ==perinatal== therapist in Illinois. Of course, this is where I di  er from the rest of my ==cohort== . By the time I was ready to have a baby, I’d already been trying to disrupt everything about myself.

For my personality-change project, I had experimented with science- backed strategies to turn down my neuroticism and ==amp== up my ==extroversion== and ==agreeableness== . I had spent hundreds of hours trying out different ==iterations== of ==mindfulness== , culminating in a day-long meditation retreat that almost killed me with boredom but somehow ==alleviated== my depression. Among other agreeableness-boosting activities, I traveled to London for a “conversation workshop,” where I learned techniques that can make even British people show an emotion. And to become more extroverted, I went out as much as humanly possible. I played table tennis. I did ==improv== , and survived.

For the most part, my efforts worked: I no longer thought of talking with people as a waste of time. I became less afraid of uncertainty and disappointment. I made one very good new friend. I drank less.

I had been changing, but it was a type of change that I directly determined. I could go to happy hour, or not. I could meditate, or stop. I was aware that ==parenthood== would ==transform me further== , but what I found unsettling was that I couldn’t know exactly how. Bizarrely, for the biggest disruption of your life, study after study shows there’s no “typical” way that becoming a parent changes your personality. Some studies have found tiny average decreases in extroversion or openness among new parents— but even those findings aren’t consistent.

Despite my progress, I was still too ==neurotic== to feel comfortable ==surrendering== control and letting biology ==mold== me into someone I couldn’t predict and might not recognize.

After doctors pronounced me insufficiently fertile, Rich and I decided to just stop being careful one month and see what happened. We figured we would at least have some fun before we ==embarked== on our ==arduous== “fertility journey.”

A short time later, on a ==choppy== boat tour in Europe, I couldn’t stop ==leaning over== the edge of the ==catamaran== and ==hurling== .

“Do you think you might be pregnant?” Rich whispered ==as the boat crew force-fed me pita bread== .

“Don’t be ==insane== ,” I said. Everyone knows that 37-year-olds— especially infertile ones—don’t get pregnant on their first try.

A week after that, I found out that I had indeed gotten pregnant on my first try.

Being pregnant means having your brain replaced with an anxiety T-shirt cannon. I didn’t feel ==glowy== or ==goddessy== ; I felt crazy. None of my friends has kids, and many of them reacted to my news like I’d gotten a face ==tattoo== . One sent me a TikTok of everything that can ==supposedly== go wrong in pregnancy, including the possibility that ==vomit== will come out of your eyes. (It won’t.) I spent more and more time by myself, obsessing over which ==swaddles== were best. (We didn’t end up using any.)

Thanks to ==a king tide of hormones== , ==irritability== ==spikes== during the first and last ==trimesters== of pregnancy. People say your baby will remember the sounds they hear in the ==womb== , but I fear mine detected little in there other than me screaming at his father. Every few weeks, something would ==set me off== , at a deafening volume. If they’d ==overheard== me, those couples therapists who say ==contempt== is the most glaring sign of a failed relationship would probably have advised us to start ==divvying== up our furniture.

Sometimes when I was yelling, being so mean felt amazing— as though I’d finally ==engulfed== Rich in my distress. Obviously you need a travel ==stroller== and a regular stroller! I always apologized, and Rich always accepted my apology. But one time he said, “You know that with a kid, ==that’s not really something you can take back, right?== ” Sometimes, late at night, after yet another argument, I would rotate my ==spheroid== belly toward Rich and ask, “What if I turn out to be a bad mother?”

The rest of the pregnancy was horrible. I didn’t think it was possible to feel so tired and still be technically alive. At my baby shower, when some friends asked me how I was feeling, I quoted the Russian ==dissident== Boris Nadezhdin responding to a question about whether he feared ==imprisonment== or death: “The ==tastiest== and the sweetest years of my life are already in the past.” (This is is the closest Russians get to excited.)

Three weeks before my due date, after a routine ultrasound, my high-risk ob-gyn walked briskly into the room. She looked around for something to sit on and, finding nothing, ==plopped down on top of a closed trash== can. She told me that something was wrong with my ==placenta== , and that the baby was in danger. And that I should now ==walk over to the delivery wing of the hospita== l.

==In the antechamber of the operating room== , I ==hyperventilated== in my paper gown and tapped out emails to all my sources and ==bosses== : I’m having an emergency C-section today, so I won’t be available for the next few months. My last day of caring whether people were mad at me.

Afterward, while ==the medical residents== were rearranging my ==innards== , I thought I heard one of them ask me something.

“I’m sorry, I don’t know what’s going on down there at all,” I said across the blue curtain.

“That’s … probably for the best,” the resident said.

HE CAME OUT with white hair, a perfectly round face, and a ==grumpy== expression, like the leader of a former Yugoslav republic. I called him “Slobodan” a couple of times, until Rich told me to stop.

Because he was early, we panic-picked a name from our shortlist— Evan. The same day he was born, doctors ==whisked== him away to the ==NICU== ; I saw him only a few times before we were all sent home days later. My ==discharge paperwork== said, “Mom is ==breastfeeding== four or five times a day,” which was funny because at that point I had not done it successfully even once. It was also funny because I—quite possibly the least qualified person for the job—was apparently “Mom.”

Once home, we entered the period we now refer to as “Cute Abu Ghraib.” ==Sleep deprivation== ==addled== me to the point that, on a call with the ==pediatrician== , I forgot the baby’s name. When Evan was two weeks old, I ==bit into a piece of chicken== and tasted something ==bloody== and sharp. I had ground my teeth so hard during his NICU stay that I’d ==loosened a crown== .

We ==agonized== over whether the ==gyrations== of the SNOO Smart Sleeper Bassinet would rattle his brain too much, then grew too exhausted to care. I became the CEO of Baby Inc., and Rich was employee No. 1; we communicated only about ==ointments== and ==ounces== . I finally had the big ==boobs== of my dreams, but the only man who saw them was two feet tall and couldn’t read.

But then something interrupted the misery. One night, I was holding Evan while he was sleeping. I had read that singing to your baby was beneficial, so I decided to ==serenade== him with one of the few songs I know by heart: “Forever and Ever, Amen,” by Randy Travis. Except I couldn’t seem to get through the fourth line: “This is love that I feel for you always will be.” I, a bad bitch who has never cried at a wedding, kept choking up.

Rich asked me if I was okay.

“Whatever!” I said, ==tears rolling down my cheeks== . “Shut up!”

I thought ==motherhood== would be a forced march through inert ==babyhood== and ==feral== ==toddler== years before we finally reached the golden time of my imagination: having a talking, ==precocious== elementary schooler. But there I was, flooded with adoration for someone who barely registered my presence. I’d hated being pregnant, so I thought I would hate having a baby, too. But I loved him. I loved this.

Recall the research showing there’s no one way that parenthood tends to change people’s personalities. Anecdotally, researchers told me that they do notice certain patterns among new parents. Most moms worry about their kid, more or less constantly, from the minute they find out they’re pregnant. “ ==Signing up to be a parent is signing up to have a lifetime of some degree of depression and anxiety== ,” Ratliff , the therapist, told me.

New parents’ satisfaction with their romantic relationship goes down, especially for mothers, and especially in the first year. “ ==Guilt is another universal== ,” says Aurélie Athan, a clinical psychologist at Columbia University’s Teachers College, who researches the transition known as “ ==matrescence== .” ==The creeping sense== that you should be with your kid while you’re working and working while you’re with your kid apparently never goes away.

She told me that mothers become more ==attuned== and ==prosocial== — more caring and empathetic toward others. Athan said this is why so many mothers cry when their babies cry and have a hard time watching ==gory== movies. “Moms get a really bad taste in their mouth with violent television or looking at images of war,” she said.

That’s where she lost me. My son had ==colic== ; for the first four months, he screamed like the possessed unless he was within the ==jiggly confines of his SNOO== . The ==doula== we hired referred to him, alternately, as “Mr. Cheeks,” “Mr. Crab,” and, ==sarcastically== , “Mr. Wonderful.” If I had cried every time he cried, I wouldn’t have had time to do anything else.

Eventually, Rich and I grew desensitized, or felt like we had to match his chaotic energy with equally intense ==stimuli== . One night, after Evan ==wailed== in our ears for two hours, we shuffed downstairs and collapsed onto the couch. There was only one thing we could think to watch that would serve as a ==comedown== from what had just happened: Saving Private Ryan.

“Did you remember to ==sterilize== the pump parts?” I asked Rich as the ==entrails== of American soldiers ==spilled out== over the beaches of Normandy.

“The sterilizer thing broke, so I had to reset it,” he said as a man stumbled around ==with his arm blown off== .

Even within these supposedly universal rules of parenthood, that is, there’s a lot of variability. That’s because life events like parenthood seem to change everyone di erently, and how you’ll change is, in part, up to you. For a recent study, Ted Schwaba, a psychologist at Michigan State University, and his co-authors asked thousands of Dutch people about a life event in the past 10 years, such as a divorce or a new job, that they felt had changed who they were as a person. About 7 percent of the participants identified parenthood as the event that changed them, and on average, they felt that it had made them slightly more agreeable and ==conscientious== .

But ==the big takeaway== for Schwaba, from looking at all the data for all the different types of life events, was that there really was no pattern. Some people became more ==extroverted== when they got a new job. Some became less so. Some people actually became less neurotic— that is, less depressed and anxious— after, say, a cancer diagnosis.

To Schwaba, this research suggests that it’s how you experience an event such as parenthood, more than the event itself, that determines how you’ll change. “The same event, like getting divorced, might be someone’s worst thing that’s ever happened to them, and for someone else, it might be the best thing that’s ever happened to them,” he told me.

Or your personality might change not immediately after an event like childbirth, but through a long process that the event sets in motion. It’s not the cry you hear in ==the delivery room== that changes you; it’s the many years of researching child care and ==soothing boo-boos== that gradually turn you into someone new. To change, you have to take steps every day to do so. Having a baby won’t make you a better person. Behaving like a better person for your baby will.

Of all the things I wanted motherhood to change about me, neuroticism was high on the list. Before I had Evan, I felt like I was personally responsible for ==making life unfold perfectly== , and whenever I “failed” to do so, ==I had a meltdown== . One day a few years ago, I got a bad haircut, ==got stuck in traffic== , and had professional photos taken that looked terrible. My response to this—what my new-parent eyes now see as an 8-out-of-10 day—was to ==chug half a bottle of wine== and scream to my husband through sobs, “I hate everyone and everything!”

But now so much goes wrong every single day that there’s no time to get upset about any one thing. I recently took a flight with Evan by myself, an exercise that really underscores the first Noble Truth of Buddhism (life is su­ ering). As I ==hauled== the car seat, the stroller, the baby, the diaper bag, and the ==trendy== , impractical tote from my childless years to the TSA line, an airline attendant took one look at me and said, “I know; it is too much.”

In the middle of the flight, I noticed that the two bottles of formula Evan nervously drank during takeo­ had caught up with him, and that ==he was now soaked with pee== . I grabbed him under the ==armpits== and ==scooted== across the seats to change him in the airplane’s ==postage-stamp-size bathroom== . With one hand, I held him, crying, on the ==changing table== , and with the other, I dug a clean onesie out of the bottom of the diaper bag. I fastened a million tiny onesie buttons. Then I saw that I had ==misaligned== them and fastened them again. Next it was my turn. I couldn’t leave him on the changing table, or put him on the disgusting floor. I ==yanked my leggings down== and held him at arm’s length as I ==peed== .

By the end of that ==ordeal== , I felt accomplished and capable. I didn’t feel like sobbing; ==I felt like high-fiving myself== . I’ve let go in other ways, too. I show up at important meetings without makeup on. I say weird stu­ff to strangers and don’t analyze it obsessively later. Evan has forced me to step outside myself, to break from the relentless self-focus that has contributed to both my success and my unhappiness.

My remaining neuroses are ==laser-directed== on his well-being. I had initially planned not to breastfeed, but once I started, I got so into it that when a doctor suggested that Evan would spit up less if I cut food ==allergens== from my diet, I stopped eating virtually anything but oats and ==spinach for months== . When I was pregnant, we’d ==signed the unborn Evan up for day care== , but as the end of my ==maternity== ==leave loomed== , I embarked on a frantic search for a ==nanny== so he could stay close to me while I worked from home. I had always mentally mocked parents who checked to be sure their babies were still breathing at night, then found myself standing in front of his crib at 3 a.m., feeling for ==puffs of air from two tiny nostrils== .

I yell at Rich less than I used to, because not only is he employee No. 1 of Baby Inc., but he’s the only employee, and frankly there are no other applicants for the job. In fact, the whole experience has made me kinder and more tender, like the Grinch, post–heart enlargement. I’m less worried about wasting time, because all time with a baby is essentially wasted—the most important nothing you’ll ever do in your life. I even love Evan’s wet, violent “kisses,” which leave his baby-teeth imprints on our jaws. When my friend Anton visited recently, he watched me make ==horsey== noises for Evan for what probably felt like hours. “I can’t believe you love an infant!” he said.

During my interview with Ratli­ , I told her that Evan had lately been losing interest in breastfeeding. I had awaited this day through months of ==bleeding nipples and frustration== , but now that it was here, it was making me a bit sad. “Your baby’s moving to the next stage,” she alarmed, “and this one is not going to come back again.” I started ==tearing up== —both at the memory of those bleary, milk-soaked months together and at the realization that he wouldn’t even be a baby for much longer.

During my personality-change experiment, my meditation teacher had tried to hammer home the idea that “ ==this too shall pass== ” is both ==uplifting== and sad: Nothing bad lasts forever, but neither does anything good. Before I had Evan, I was focused on ==impermanence== ’s upsides: This uncomfortable improv show will end; this awful pregnancy will too. But now I’m more keenly aware of its downsides. The sleepless nights will end, but so too will the times Evan squeals at a game of peekaboo, or spends an entire swim class gazing up at me in awe. Every day brings a sigh of relief and a pang of nostalgia. Having someone who loves you, I’ve decided, is a good reason to have kids.

Olga Khazan is a staff writer at The Atlantic. The is essay was adapted from her forthcoming book, Me, but Better: The Science and Promise of Personality Change.

Vocabulary, Phrases and Sentences

Word Chinese Definition Phonetic Symbol
figure out 弄清楚,想出 /ˈfɪɡjə aʊt/
a fertility test 生育能力测试 /ə fəˈtɪləti test/
effortlessly 毫不费力地 /ˈefətlsli/
dribble 使滴下;滴流 /ˈdrɪbl/
gingerly 小心翼翼地 /ˈdʒɪndʒəli/
meridian 子午线;经络 /məˈrɪdiən/
procreate 生育;繁殖 /ˈprəʊkreɪt/
shudder 颤抖;战栗 /ˈʃʌdə(r)/
admittedly 诚然;公认地 /ədˈmɪtɪdli/
neuroticism 神经质;神经过敏 /ˌnjʊəˈrɒtɪsɪzəm/
agreeable 令人愉快的 /əˈɡriːəbl/
extroversion 外向性;外向性格 /ˌekstrəˈvɜːʃn/
clench 紧握;咬紧 /ˈklentʃ/
knit 编织;针织;使紧密结合 /ˈnɪt/
geriatric 老年的;老年医学的 /ˌdʒeriˈætrɪk/
serviceable 有用的;耐用的 /ˈsɜːvəbl/
glossy 光滑的;有光泽的 /ˈɡlɒsi/
lancet 柳叶刀;刺血针 /ˈlɑːnsɪt/
stab 刺;戳;刺痛 /ˈstæb/
graveyard 墓地;坟场 /ˈɡreɪvjɑːd/
gauze 纱布;薄纱 /ˈɡɔːz/
droplet 小滴 /ˈdrɒplət/
dark day 黑暗的日子 /ˈdɑːk deɪ/
cooing 轻声咕咕叫;温柔低语 /ˈkuːɪŋ/
rife 流行的;普遍的;充斥着 /ˈraɪf/
deprivation 剥夺;匮乏 /ˌdeprɪˈveɪʃn/
torn 撕裂的;破损的 /ˈtɔːn/
miscarriage 流产;小产 /ˈmɪskærɪdʒ/
horrific 可怕的;恐怖的 /ˈhɒrɪfɪk/
anecdote 轶事;奇闻 /ˈænɪkdəʊ/
dementia 痴呆 /ˈdemənʃə/
Her face lit up at the sight of him 她一见到他,脸上就露出了喜色。 /hɜː feɪs lɪt ʌp æt ðə saɪt ɒv hɪm/
a wake-up call 警钟;叫醒电话 /ə ˈweɪk ʌp kɔːl/
the existence of and use case for NoseFrida NoseFrida(一种吸鼻器)的存在和使用案例 /ðə ɪɡˈzɪstəns ɒv ænd juːs keɪs fɔː(r) ˈnəʊz friːdə/
sourdough 酸面团;全麦面包 /ˈsaʊədəʊ/
perinatal 围产期的 /ˌperiˈneɪtl/
cohort 一群人;一组;队列 /ˈkəʊhɔːt/
amp up 提高;放大;增强 /ˈæmp ʌp/
agreeableness 宜人;和蔼可亲 /əˈɡriːəblnəs/
iteration 迭代;重复 /ˌɪtəˈreɪʃn/
mindfulness 正念;专注 /ˈmaɪndflnəs/
alleviate 减轻;缓解 /əˈliːvieɪt/
improv 即兴表演 /ˈɪmprɒv/
parenthood 父母身份;亲子关系 /ˈpeərənhʊd/
transform me further 进一步改变我 /ˈtrænsfɔːm miː ˈfɜːðə(r)/
neurotic 神经质的;神经过敏的 /ˈnɜːrɒtɪk/
surrendering 投降;屈服;交出 /ˈsʌrəndərɪŋ/
mold 模具;霉菌;塑造 /ˈməʊld/
embark 上船;着手;开始 /ˈembɑːk/
arduous 艰巨的;费力的 /ˈɑːdjuəs/
choppy 波涛汹涌的;不连贯的 /ˈtʃɒpi/
lean over 俯身;倾斜 /ˈliːn ˈəʊvə(r)/
catamaran 双体船 /ˌkætəməˈræn/
hurl 猛投;猛掷;大声说出 /ˈhɜːl/
as the boat crew force-fed me pita bread 当船员强迫我吃皮塔饼时 /æz ðə bəʊt kruː ˈfɔːs fed miː ˈpiːtə bred/
insane 疯狂的;精神错乱的 /ˈɪnˈseɪn/
glowy 发光的;红润的 /ˈɡləʊi/
goddessy 如女神般的 /ˈɡɔdəsi/
tattoo 纹身;刺青 /ˈtætuː/
supposedly 据说;据推测 /ˈsəʊpəʊzɪdli/
vomit 呕吐;吐出 /ˈvɒmɪt/
swaddles 襁褓;包裹 /ˈswɒdlz/
a kind tide of hormones 一股温和的荷尔蒙潮 /ə kaɪnd taɪd ɒv ˈhɔːməʊnz/
irritability 易怒;过敏 /ˌɪrɪtəˈbɪləti/
spike 尖状物;穗;激增 /ˈspaɪk/
trimester 三个月;孕期的三个月 /ˈtraɪmestə(r)/
womb 子宫 /ˈwuːm/
set me off 使我开始;使我发作 /ˈset miː ˈɔːf/
overhear 无意中听到;偷听 /ˈəʊvəˈhɪə(r)/
contempt 轻视;蔑视 /ˈkəntempt/
divvy 分配;分摊 /ˈdɪvi/
engulf 吞没;吞噬 /ˈɪnˈɡʌlf/
stroller 婴儿车;散步者 /ˈstrəʊlə(r)/
that’s not really something you can take back 那可不是你能收回的事情 /ˈðæts nɒt ˈriːəli ˈsʌmθɪŋ juː kæn ˈteɪk bæk/
spheroid 球体;类球体 /ˈsfɪərɔɪd/
dissident 持不同政见者;异议者 /ˈdɪsɪdənt/
imprisonment 监禁;关押 /ˈɪmˈprɪznmənt/
tastiest 最美味的 /ˈteɪstɪɪst/
plop down on top of a closed trash 扑通一声坐在一个关闭的垃圾桶上 /ˈplɒp daʊn ˈɒn tɒp ɒv ə ˈkləʊzd træʃ/
placenta 胎盘 /ˈplæsntə/
walk over to the delivery wing of the hospital 走到医院的产房区 /ˈwɔːk ˈəʊvə(r) tuː ðə dɪˈlɪvəri wɪŋ ɒv ðə ˈhɒspɪtl/
In the antechamber of the operating room 在手术室的前厅 /ˈɪn ðə ˈæntiˌtʃeɪmbə(r) ɒv ðə ˈɒpəreɪtɪŋ ruːm/
hyperventilate 换气过度;呼吸急促 /ˈhaɪpəˈventɪleɪt/
the medical resident 住院医生 /ˈðə ˈmedɪkl ˈrezɪdənt/
innard 内脏;内部 /ˈɪnəd/
grumpy 脾气暴躁的;易怒的 /ˈɡrʌmpi/
whisk 拂;挥动;迅速带走 /ˈwɪsk/
NICU 新生儿重症监护室 /ˈnɪkjuː/
discharge paperwork 出院文件 /ˈdɪstʃɑːdʒ ˈpeɪpəweɪk/
breastfed 母乳喂养的 /ˈbrestfed/
sleep deprivation 睡眠剥夺 /ˈsliːp ˌdeprɪˈveɪʃn/
addle 使混乱;使糊涂;使变质 /ˈædl/
pediatrician 儿科医生 /ˌpiːdiəˈtrɪʃn/
bit into a piece of chicken 咬了一口鸡肉 /ˈbɪt ˈɪntuː ə ˈpiːs ɒv ˈtʃɪkɪn/
bloody 血腥的;流血的;该死的 /ˈblʌdi/
loosen a crown 松开牙冠 /ˈluːsn ə ˈkraʊn/
agonize 感到极度痛苦;苦苦思索 /ˈæɡənaɪz/
gyration 旋转;回转 /ˌdʒaɪˈreɪʃn/
ointment 药膏;油膏 /ˈɔɪntmənt/
ounce 盎司;少量 /ˈaʊns/
boob 乳房;蠢材 /ˈbuːb/
serenade 小夜曲;唱小夜曲 /ˈserəneɪd/
tear rolling down my cheeks 泪水顺着我的脸颊滚落 /ˈteə(r) ˈrəʊlɪŋ daʊn maɪ ˈtʃiːks/
motherhood 母亲身份;母性 /ˈmʌðəhʊd/
babyhood 婴儿期;幼儿期 /ˈbeɪbihʊd/
feral 野生的;未驯化的 /ˈferəl/
toddler 学步的儿童;蹒跚学步者 /ˈtɒdlə(r)/
precocious 早熟的 /ˈpriːkəʊʃəs/
Signing up to be a parent is signing up to have a lifetime of some degree of depression and anxiety 报名成为父母意味着报名要经历某种程度的一生的抑郁和焦虑。 /ˈsaɪnɪŋ ˈʌp tuː biː ə ˈpeərənt ɪz ˈsaɪnɪŋ ˈʌp tuː hæv ə ˈlaɪftaɪm ɒv səm dɪˈɡriː ɒv dɪˈpreʃn ænd æŋˈzaɪəti/
guilt is another universal 内疚是另一个普遍存在的 /ˈɡɪlt ɪz əˈnʌðə(r) ˈjuːnɪvɜːsl/
masterscence 这个词可能有误,你想问的可能是“mastery”,意为“精通;掌握” /ˈmɑːstəri/
the creeping sense 那种逐渐蔓延的感觉 /ˈðə ˈkriːpɪŋ sens/
attune 使协调;使适应 /ˈəˈtjuːn/
prosocial 亲社会的 /ˈprəʊˈsəʊʃl/
gory 血腥的;暴力的;令人毛骨悚然的 /ˈɡɔːri/
colic 绞痛;疝气 /ˈkɒlɪk/
jiggly confines of his SNOO 他那摇晃的SNOO婴儿床 /ˈdʒɪɡli ˈkɒnfaɪnz ɒv hɪz ˈsnuː/
doula 助产士;导乐 /ˈduːlə/
sarcastically 讽刺地;挖苦地 /ˈsɑːˈkæstɪkli/
stimuli 刺激物;刺激因素(复数形式) /ˈstɪmjəlaɪ/
wailed 哀号;痛哭 /ˈweɪld/
comedown 衰落;落魄;药效消退 /ˈkʌmdəʊn/
sterilize 消毒;使绝育;使贫瘠 /ˈsterəlaɪz/
entrail 内脏;肠 /ˈentreɪl/
spill out 溢出;涌出 /ˈspɪl aʊt/
with his arm blown off 他的手臂被炸掉了 /ˈwɪð hɪz ˈɑːm ˈbləʊn ˈɔːf/
conscientious 认真的;尽责的 /ˈkɒnʃiˈenʃəs/
the big takeaway 最重要的收获 /ˈðə ˈbɪɡ ˈteɪkəweɪ/
extroverted 外向的 /ˈekstrəvɜːtɪd/
the delivery room 产房 /ˈðə ˈdɪlɪvəri ruːm/
soothing boo-boos 抚慰伤痛 /ˈsuːðɪŋ ˈbuːbuːz/
make life unfold perfectly 让生活完美展开 /ˈmeɪk ˈlaɪf ˈʌnfəʊld ˈpɜːfɪktli/
I had a meltdown 我情绪崩溃了 /ˈaɪ hæd ə ˈmeltdaʊn/
chug half a bottle of wine 大口喝了半瓶酒 /ˈtʃʌɡ hɑːf ə ˈbɒtl ɒv ˈwaɪn/
get stuck in traffic 被困在交通堵塞中 /ˈɡet ˈstʌk ɪn ˈtræfɪk/
haule 这个词可能有误,你想问的可能是“haul”,意为“拖;拉;运送” /ˈhɔːl/
trendy 时髦的;流行的 /ˈtrendi/
he was now snaked with pee 他现在被尿弄得到处都是 /ˈhiː wəz naʊ ˈsneɪkt wɪð ˈpiː/
armpit 腋窝 /ˈɑːmpɪt/
scoot 迅速移动;溜走 /ˈskuːt/
postage-stamp-size-bathroom 邮票大小的浴室 /ˈpəʊstɪdʒ stæmp saɪz ˈbɑːθruːm/
changing table 换尿布台 /ˈtʃeɪndʒɪŋ teɪbl/
misaligned 未对齐的;错位的 /ˈmɪsəˈlaɪnd/
yank my leggings down 猛地拉下我的紧身裤 /ˈjæŋk maɪ ˈleɡɪŋz daʊn/
peed 撒尿(过去式和过去分词) /ˈpiːd/
ordeal 折磨;严峻考验 /ˈɔːdiːl/
I felt like high-fiving myself 我想给自己击掌 /ˈaɪ felt laɪk ˈhaɪ faɪvɪŋ maɪˈself/
laser-directed 激光制导的 /ˈleɪzə daɪˈrektɪd/
allergent 这个词可能有误,你想问的可能是“allergen”,意为“过敏原” /ˈælədʒən/
spinach for months 几个月的菠菜 /ˈspɪnɪdʒ fɔː(r) ˈmʌnθs/
signed the unborn Evan up for day care 为未出生的埃文报名参加日托 /ˈsaɪnd ði ˈʌnˈbɔːn ˈevən ˈʌp fɔː(r) ˈdeɪ keə(r)/
maternity 产妇的;孕妇的;产科的 /məˈtɜːnəti/
leave loom 产假临近 (loom有“逼近”的意思,这里推测是leave is looming,表示产假即将来临,你这里原词可能有误,如果不是这个意思,请你纠正) /ˈliːv luːm/
nanny 保姆;奶妈 /ˈnæni/
puff 吸;抽(香烟、烟斗等);吹气;喘息 /ˈpʌf/
air from two tiny nostrils 来自两个小鼻孔的空气 /ˈeə(r) frəm tuː ˈtaɪni ˈnɔstrɪlz/
horsey 马的;像马的;爱马的(常用于儿语) /ˈhɔːsi/
bleeding nipples and frustration 乳头流血和挫折感 /ˈbliːdɪŋ ˈnɪplz ænd frʌˈstreɪʃn/
tear up 撕碎;流泪 /ˈteə(r) ˈʌp/
this too shall pass 这一切也会过去的 /ˈðɪs tuː ˈʃæl pɑːs/
uplift 振奋;提高;举起 /ˈʌplɪft/
impermanence 无常;暂时性;不 permanence /ɪmˈpɜːmənəns/ (这个词本身是名词,没有动词形式,你这里原词permanence是名词“永久,持久”,前面加im - 构成反义词“无常”)

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在hexo博客中启用图片支持

hexo对图片的引用格式比较反人类,笔者习惯使用typora写文章,因此有了这篇博客,图片将会保存在.md同级目录下的同名文件夹内

参考中文互联网上众多方法后,笔者在此直接给出有效的解决方案

  • typora的图片设置为复制到指定路径${filename}
  • 编辑_config.yml修改并添加以下内容
1
2
3
4
post_asset_folder: true
marked:
prependRoot: true
postAsset: true
  • 需要安装的插件是hexo-render-marked
1
npm install hexo-renderer-marked --save
  • typora中格式-图像-设置图片根目录-选择与.md同名的文件夹

  • 保存推出然后重新进入,typora中能正常显示

  • hexo clean && hexo deploy
  • hexo博客上也能正常显示图片

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Why don’t Companies Want you to Repair your Stuff?

For centuries, to build any device, ==artisans== had to ==painstakingly== cut every ==screw== , ==bolt== , or ==nut== by hand.

But all this changed in the 1790s, when British ==metalworker== Henry Maudslay developed this highly precise ==lathe== .

Suddenly, ==these previously handmade components could be reproduced mechanically and at scale== .

This may seem like a simple innovation, but it had a profound effect on the world.

The standardization of these parts helped ==usher== in the Industrial Revolution.

From cars to home appliances, the 20th century was ==defined== by mass production and readily available ==interchangeable== parts.

This made repairing items relatively easy.

If your shower head ==gasket== failed or the hose for your washing machine ==sprang a leak== , a hardware store likely carried replacements.

Today, interchangeable parts are as important as ever for mass production.

However, some companies are working hard to prevent consumers from ==swapping out== components on their own.

In many cases, repair can only be done by the original manufacturer, ==if at all== .

With limited repair options available, we end up buying new and throwing more items out.

This is especially true for electronics.

In 2022, we discarded about 62 million tons of e-waste, along with billions of dollars’ worth of precious metals inside them.

So how exactly do companies prevent repair?

Some make it physically more difficult to fix items.

They can glue parts in place rather than using screws.

Others limit the information they share with consumers, like blocking public access to product information and ==schematics== .

During the pandemic, for instance, when hospitals struggled to maintain breaking medical equipment, the repair company iFixit compiled a comprehensive database of repair manuals for hospitals to use.

==Yet manufacturers like Steris fought for them to be taken down== .

Yet perhaps the most important, yet least obvious, way companies limit repair is by preventing the interchangeability of parts.

In a process known as parts pairing, companies assign individual parts like screens, batteries, or sensors a unique serial number.

The device’s internal software can then detect if those components are replaced and limit their functionality as a result.

If you swap the screen on two ==brand== new iPhones, for example, the automatic ==brightness== adjustment will no longer work.

In other cases, unauthorized replacements can cause the device to stop functioning altogether.

If a farmer uses an independent shop to repair certain parts in a John Deere tractor, it won’t operate until a company technician ==authenticates== the new part using authorized software.

With only a limited number of company technicians available, this can easily create a ==bottleneck== , costing farmers precious time and money, and even jeopardizing crops.

Manufacturers can also use software to give devices ==predetermined== ==end-of-life dates== , after which they no longer receive important updates and slowly become unusable.

All this gives manufacturers unprecedented control over the products we buy and limits the way we repair them.

Critics ==liken== these tactics to a form of planned ==obsolescence== , a manufacturing strategy where a product is deliberately designed to fail to keep both demand and profits high.

But companies pose two main arguments in defense of these practices.

First, they claim that giving consumers and third-party repair shops access to their software could create ==cybersecurity== risks.

They also argue that they could be ==liable== if a product malfunctions after a third party or consumer repair.

A ==shoddy== repair to a medical device, for instance, could have deadly consequences, and the manufacturer could be blamed.

However, major reports, like those from the U.S. Federal Trade Commission and the Food and Drug Administration, find little support for these company claims.

==Parts pairing and repair-limiting practices== are now being closely ==scrutinized== in courts all over the world, as consumers fight for the right to repair.

States, including Colorado and Oregon, have passed laws banning parts pairing.

Community-led movements have also taken root.

Over 2,500 cities across the globe, from Amsterdam to Boise to Bangalore, have established repair ==cafes== .

Here, people trade and share their knowledge, ==reinvigorating== a culture of repair at a time when it often feels easier to ==toss== our things than fix them.

Vocabulary, Phrases and Sentences

Word Chinese Definition Phonetic Symbol
artisan 工匠,技工 [ˈɑːtɪzn]
painstakingly 煞费苦心地,费力地 [ˈpeɪnzteɪkɪŋli]
screw 螺丝;拧,旋 [skruː]
bolt 螺栓;门闩;突然说出;逃跑 [bəʊlt]
nut 螺母,螺帽;坚果 [nʌt]
metalworker 金属加工工人 [ˈmetlwɜːkə(r)]
lathe 车床 [leɪð]
These previously handmade components could be reproduced mechanically and at scale 这些以前手工制作的部件可以大规模地机械复制
usher 引座员;招待员;引领,带领 [ˈʌʃə(r)]
interchangeable 可互换的,通用的 [ˌɪntəˈtʃeɪndʒəbl]
gasket 垫圈,密封垫 [ˈɡæskɪt]
spring a leak 出现裂缝
swap out 替换,更换
if at all 如果真的能(做某事)的话,表示一种很不确定的语气
schematics 原理图,示意图 [skiːˈmætɪks]
Yet manufacturers like Steris fought for them to be taken down 然而像斯特里思这样的制造商努力争取让它们被下架
brand new 全新 [brænd]
brightness 亮度;明亮;聪明 [ˈbraɪtnəs]
authenticate 鉴定,认证;证明……是真实的 [ɔːˈθentɪkeɪt]
bottleneck 瓶颈;阻碍 [ˈbɒtlnek]
predetermine 预先确定,预先决定 [ˌpriːdɪˈtɜːmɪn]
end-of-life date 使用寿命结束日期
liken 把……比作 [ˈlaɪkən]
obsolescence 过时,淘汰 [ˌɒbsəˈlesns]
cybersecurity 网络安全 [ˈsaɪbəkɪərɪti]
liable 有责任的,可能的 [ˈlaɪəbl]
shoddy 劣质的,粗制滥造的 [ˈʃɒdi]
parts pairing and repair-limiting practices 零件配对和限制维修的做法
scrutinize 仔细检查,审查 [ˈskruːtənaɪz]
cafe 便利商店 [ˈkæfeɪ]
reinvigorate 使恢复活力,使重新振作 [ˌriːɪnˈvɪɡəreɪt]
toss 扔,抛;猛抬(头);摇匀;辗转反侧 [tɒs]

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Table Manners in Anglo-America

“Oh, no! Here I am at an American family’s home at the dinner table. There are all kinds of plates, saucers, cups, and silverware at my place. Which should I use for which food? Should I sit down first or wait for the host to invite me? Should I have brought a gift? Someone please tell me what to do!”

Have you ever been in or had a nightmare about this situation? Don’t worry! This article will help ==steer== you through ==the rocks and reefs== of Anglo-American table manners so that if you are ever abroad in Canada or the United States, or at someone’s home from one of those countries, you will feel right at home.

It is important to distinguish what kind of occasion you will be attending before you plan for a pleasant evening. Most Anglo-Americans enjoy entertaining at home, but they don’t enjoy ==stuffy== , formal dinners. They invite their friends over for a fun evening, not as a test of one’s knowledge of cultural traditions. If, however, you are invited to a formal affair, such as a so-called “sit-down” dinner, you may want to know in advance some basic rules of “black tie” ==etiquette== .

The first thing to remember when attending a dinner at a Western home is that you are the guest and that you are a foreigner. No one will invite you if he does not really want you to enter his “castle;’ so you can be sure that you are wanted. Additionally, as you do not come from the same country or culture as your host, he or she or they will surely be aware of this, and will be very ==forgiving== if you ==unintentionally== do or say something which would otherwise offend them .Keeping these two simple tips in mind should greatly ease your concern about being present at a dinner in someone else’s home.

Before arriving at your host’s home, you may want to make sure of three things. First, be a few minutes late, say, about five to ten minutes if possible. Never be early, as the host may not have everything prepared yet. Nor should you be more than 20 minutes late. Your host may begin to worry about whether you are able to attend the dinner or not. Next, as to whether to bring a gift, in most informal gatherings, it is not necessary. If you like, you can bring some fruit or sweets, or, especially if there is a hostess, some flowers. These are ==thoughtful== cheerful gifts sure to please. Do not bring alcoholic beverages unless you are sure of your host’s or hostess’s preferences in drinks. Above all, do not spend a lot of money, and never give money. As we say in English, ” ==it’s the thought that counts== !’ finally, wear comfortable clothing. One can overdress as well as appear ==sloppy== . For a special occasion or religious holiday, such as a retirement party or Christmas, a tie and jacket would be suitable for the gentlemen and a dress or sweater and skirt for the ladies.

For more formal affairs, you will probably be told what to wear, such as “formal dress requested,” etc. A tie and jacket or ==tuxedo== for the gents and an evening gown for the ladies would be in order here. If you are unsure what to wear, you can always ask the host. Gifts are seldom appropriate for these affairs, unless for a wedding reception, at which gifts are more ==customary== than cash.

Your host in his home will usually ==motion== you where to sit. At formal gatherings, name cards are sometimes provided, or you will be told where to sit. Do not be alarmed by a great deal of ==cutlery== : simply start from the outside and work your way in. Formal affairs often have several courses of food with the appropriate cutlery for each dish. There is no harm in checking with your neighbor to see what ==implement== he is using. After all, ” ==When in Rome, do as the Romans do== :’ It is customary to ask others to pass dishes to you for self-serving; at a formal dinner party, there is usually catering (service). Again, do not hesitate to ask others for information or advice. They are usually pleased to help you.

The most important piece of advice is this: enjoy yourself. No host enjoys seeing nervous or fearful guests who are struggling to “do the right thing” at his home or expensive formal dinner party. Watch others or ask for their advice, and join in the conversation and good times as best you can .If you do, after the first such evening out, you will certainly look forward to the next!

“哦,不!我现在身处一个美国家庭的餐桌旁。我面前摆放着各种各样的盘子、茶碟、杯子和银餐具。吃不同的食物该用哪件餐具呢?我应该先坐下还是等主人邀请呢?我该带个礼物来吗?谁能告诉我该怎么做啊!”

你是否曾经历过这种情况或者做过关于它的噩梦呢?别担心!本文将帮助你避开英美餐桌礼仪的暗礁险滩,这样一来,如果你身处加拿大或美国,或者在来自这两个国家之一的某个人家里,你会感觉宾至如归。

在你为一个愉快的夜晚做准备之前,区分你要参加的是哪种场合很重要。大多数英美人士喜欢在家招待客人,但他们不喜欢古板、正式的晚宴。他们邀请朋友来共度欢乐时光,而不是来考验某人对文化传统的了解。然而,如果你被邀请参加一个正式活动,比如所谓的“坐下来吃”的晚宴,你可能想提前了解一些“黑领结”礼仪的基本规则。

当你在西方人家中参加晚宴时,首先要记住的是你是客人,而且你是个外国人。如果主人不是真心想邀请你进入他的“城堡”,就不会邀请你,所以你可以确定你是受欢迎的。此外,由于你和主人来自不同的国家或文化,他或她或他们肯定会意识到这一点,如果你无意中做了或说了某些否则会冒犯他们的事情,他们会非常宽容。记住这两个简单的要点应该会大大减轻你对在别人家参加晚宴的担忧。

在到达主人家之前,你可能想确认三件事。首先,稍微迟到几分钟,比如说,如果可能的话,大约迟到五到十分钟。绝不要早到,因为主人可能还没有把一切都准备好。你也不应该迟到超过二十分钟。你的主人可能会开始担心你是否能来参加晚宴。其次,关于是否带礼物,在大多数非正式聚会上,这不是必需的。如果你愿意,你可以带些水果或糖果,或者,特别是如果有女主人的话,带些花。这些都是贴心又讨喜的礼物。除非你确定主人或女主人对饮品的喜好,否则不要带酒精饮料。最重要的是,不要花很多钱,而且绝对不要给钱。就像我们在英语里说的,“心意最重要!”最后,穿舒适的衣服。一个人既可能穿得过于讲究,也可能显得邋遢。对于特殊场合或宗教节日,比如退休派对或圣诞节,男士穿领带和夹克会很合适,女士穿连衣裙或毛衣加裙子。

对于更正式的活动,你可能会被告知该穿什么,比如“要求着正装”等等。这里男士穿领带和夹克或无尾礼服,女士穿晚礼服。如果你不确定穿什么,你总是可以问主人。在这些活动中,礼物很少合适,除非是婚礼招待会,在婚礼上送礼物比送现金更常见。

在他家,主人通常会示意你坐在哪里。在正式聚会上,有时会提供名片,或者会告诉你坐在哪里。不要被大量的餐具吓到:只需从外面开始,按顺序往里用。正式活动通常有好几道菜,每道菜都配有合适的餐具。向你的邻座询问他正在使用什么餐具并无坏处。毕竟,“入乡随俗”。按习俗,人们会请别人把菜递给自己以便自取食物;在正式晚宴聚会上,通常会有餐饮服务(侍者服务)。同样,不要犹豫向别人寻求信息或建议。他们通常很乐意帮助你。

最重要的一条建议是:尽情享受。没有哪个主人喜欢看到紧张或害怕的客人在他家里或昂贵的正式晚宴聚会上努力“做对事情”。观察别人或者向他们请教,尽你所能加入谈话并享受美好时光。如果你这样做了,在第一次这样的外出晚宴之后,你肯定会期待下一次!

Vocabulary & Idioms

  • suacer——小茶碟
  • steer——引导
  • the rocks and reefs——重重障碍
    • rock——岩石
    • reef——暗礁
  • distinguish——辨别
  • stuffy——沉闷的
  • in advance——提前
  • etiquette——礼仪
  • some basic rules of “black tie” etiquette——黑领带礼仪的一些基本规则
  • be aware of——意识到
  • thoughtful——体贴的,周到的
  • It’s the thought that counts——心意最重要
  • overdress——过度打扮
  • appropriate——合适的
  • customary——惯例的
  • motion——以姿态或手势示意
  • cultery——刀叉类餐具
  • There is no harm in + V-ing——做……无妨
  • implement——器具
  • hesitate——犹豫
  • look forward to——盼望

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本文排版非常混乱,笔者无心整理,请见谅,不要看大纲

无机固态电解质基础性质

多尺度离子传输

原子尺度

  • 离子扩散路径与环境:

阳离子沿着有利的路径扩散,这些路径由阴离子构成的框架所决定。==阳离子扩散可看作是在基态稳定位点与中间亚稳位点之间的离子跳跃==,能量主要由其局部离子配位环境决定(晶体中通常为四配位和六配位),==体心立方阴离子框架==就是一种常见的优秀离子导体框架,因为这种框架能让离子在相邻四面体位点间直接跳跃,且活化能Ea较低,无需经过高 Ea 的四面体 - 八面体跳跃过程(fcc, hcp)

Nature Mater 14, 1026–1031 (2015)
  • 阳离子迁移机制

    • 空位扩散
    • 直接间隙
    • 协同扩散
    三种扩散方式
    b:空位扩散或直接间隙,c:协同扩散
  • 离子电导率相关因素

$$ \sigma=qnu=\sigma_0T^me^{-\frac{E_a}{k_BT}} $$

  • 缺陷与离子传导的关系

在本征状态下,移动带电物种的浓度 n3 与温度有关,并且和空位及间隙的缺陷形成能 Ef 相关。离子掺杂可以创造出电荷补偿空位或者间隙,从而改变缺陷的浓度,但也可能影响离子传导机制(如锂超离子导体(LISICON)型的大量离子掺杂可能使传导机制变为“超离子”机制)。

  • 其他影响离子迁移的因素
    • 机械性能较软的阴离子框架
      • 传到活化能更低,有助于离子扩散
      • 较低的晶格振动频率会导致较低的跳跃尝试频率νo和迁移熵ΔSm减小,从而降低阿氏方程的指前因子
    • 多阴离子基团($\rm{SO_4^{2-}, \rm{PO_4^{3-}}}$)的旋转有助于离子传导(桨轮效应)
  • 非晶态材料中的离子传导

无长程有序的结构,尚未建立统一的非晶态传导理论,跳跃理论的部分内容仍可应用,但需要进行统计处理,似乎和理论计算相关……

微观和介观尺度

  • 晶界的影响

多数情况下,晶界会增加离子迁移电阻,不利于宏观离子传导,在某些材料中,晶界也可能通过形成低配位位点的路径,促进平行于晶界表面的离子传导。总体而言,控制晶界的浓度和原子特性,有助于调节离子电导率

  • 玻璃陶瓷离子导体的特性

玻璃陶瓷离子导体是由非晶相受控结晶形成的材料,在一些材料中,玻璃陶瓷微观结构能稳定亚稳晶体结构,大幅提高离子电导率

  • 物理接触与孔隙对离子传导的影响

固态电解质和固态电池中,固体颗粒间的物理接触不足会增加离子传输阻力。相反,孔隙的存在会导致离子传导路径曲折,电流密度不均匀,增加宏观离子传输的可观测电阻。因此,有效致密化多晶固态电解质和复合电极对增强离子传输至关重要。

宏观尺度

  • 离子电导率的测量
    • 方法:阻抗谱
    • 影响因素:点接触、晶界、非晶相、杂质等,需要通过拟合抽象模型来分解,这些模型通常基于观察到的电容等经验假设
  • 宏观上离子电导率的优化
    • 减少孔隙率
    • 控制晶界
    • 玻璃陶瓷离子导体
  • 未来研究方向
    • 高通量计算
    • 新型电极材料
    • 界面工程

电化学稳定性

界面反应

  • 氧化还原分解:固态电解质与电极接触时,通过得失电子和 / 或移动阳离子发生的可逆或不可逆反应(半反应)

$$ \rm{2Li_3PS_4+2e^−+2Li^+\longrightarrow Li_4P_2S_6+2Li_2S} $$

应产物可能形成离子电阻层或电子导电相,导致界面阻抗增加

  • 化学反应:电解质与电极材料在成分空间中混合形成新相的反应

稳定窗口的热力学与动力学

  • 热力学稳定性窗口窗口:电解质在不发生分解的电压范围内的热力学极限,由分解反应的自由能(ΔG)决定
    • 影响因素
      • 阳离子的还原稳定性
      • 阴离子的氧化稳定性
  • 动力学稳定性:即使热力学不稳定,反应可能因动力学障碍(如高活化能)而被抑制
    • 关键参数
      • 过电位
      • 离子迁移率
    • 界面工程策略
      • 界面工程分类
        • 本征稳定
        • 动力学稳定
        • 人工保护
      • 典型保护策略
        • 涂层
        • 双电极设计
        • 界面结构优化
    • 界面表征技术
      • 原位XPS
      • 高分辨TEM
      • 阻抗谱
      • 分子动力学模拟

力学性能

  • 界面粘附:电解质与电极间的粘附力决定接触面积和离子传输效率。

  • 应力响应:电极材料在充放电过程中的体积变化会引发应力,导致裂纹或界面分层。

  • 抗断裂能力:电解质的断裂韧性决定其抵抗裂纹扩展的能力

关键力学参数

  • 界面粘附

    • 影响因素

      • 化学界面能

      • 机械应变

      • 电荷重组

    • 表征

      • 接触角测量
      • 界面电阻与粘附力相关性
  • 电化学应变:电极材料在离子嵌入 / 脱嵌时的体积变化

    • 影响
      • 局部应力集中
      • 宏观压力变化
    • 解决方案
      • 零应变电极
      • 优化电极/电解质界面结构
  • 弹性模量:杨氏模量(抗拉伸/压缩形变的能力)和剪切模量

    • 低模量材料(如硫化物)理论上可更好地适应应力,但实验发现其仍表现脆性(如 $\rm{Li_2S-P_2S_5}$玻璃的 E≈20 GPa,G≈7 GPa)。

    • 高模量材料(如氧化物)刚性强,但易因应力集中导致断裂

  • 断裂韧性:料抵抗裂纹扩展的能力

    • 影响因素
      • 微观结构
      • 化学组成
    • 实验方法
      • 压痕法
      • 裂纹扩展测试

力学失效机制

  • 裂纹形成与扩展
    • 电极体积变化引起的机械应力
    • 锂枝晶生长
  • 界面分层
    • 机制
      • 循环应力下界面粘附力不足以抵抗应变。
      • 界面反应产物(如电子导电层)削弱结合力
  • 锂枝晶生长
    • 提高电解质的断裂韧性(如通过纳米晶结构)
    • 降低电解质的电子电导率以减少枝晶成核点

合成

  • 合成方法
    • 机械化学法:球磨可细化晶粒,提高断裂韧性(如 Li₆PS₅Cl 的 K₁c 从 0.5→1.2 MPa・m¹/²)。
    • 火花等离子烧结(SPS):通过控制冷却速率优化微观结构,减少孔隙率。
  • 致密化工艺
    • 高致密度(>95%)可降低裂纹扩展风险,但需平衡加工压力与材料软化(如硫化物在高温下易变形)。
  • 涂层技术
    • 界面涂层(如 Al₂O₃)可抑制应力集中,提高界面粘附力
材料类型 杨氏模量(GPa) 剪切模量(GPa) 断裂韧性(MPa・m¹/²) 应用挑战
硫化物(Li₆PS₅Cl) 20–30 7–10 0.5–1.0 低韧性导致循环裂纹
氧化物(LLZO) 150–200 60–80 1.0–2.0 高模量引发应力集中
硼氢化物(LiBH₄) 4–6 1–2 0.3–0.5 化学稳定性差

固态电解质的合成与处理方法

合成

固态合成法 软化学法 机械化学法
工艺 将原料粉末混合后高温烧结(通常 > 600°C) 在液态溶剂(如乙腈、水)中溶解原料,通过沉淀、溶胶 - 凝胶等反应生成前驱体,再经干燥和退火 通过球磨(高能碰撞)引发固态反应
优点 简单易行,可淬火保留高温相 低温合成(<300°C),精确控制纳米结构 低温合成(室温至 400°C),晶粒细化至纳米级
缺点 高温导致易挥发成分,可能引入杂质 溶剂回收成本高,前驱体纯度依赖溶剂纯度 工艺参数(球磨时间、转速)对产物影响大,重复性差,可能引入杂质
案例 石榴石型 LLZO($\rm{Li_7La_3Zr_2O_{12}}$)的合成 水热法合成$\rm{Na_3SbS_4}$ 球磨法制备$\rm{Li_{11}Si_2PS_{12}}$

致密化技术:将合成后的粉末加工成高密度膜或片,以降低电阻并提高机械强度

烧结 火花等离子烧结 冷压
工艺 常压或加压下(如热压)将粉末在高温(通常 > 500°C)下烧结 脉冲电流加热粉末至目标温度(如 LLZO 在 1000°C),同时施加压力(50–100 MPa) 室温下对粉末施加高压(如 500 MPa)形成素坯,再烧结
缺点 高温可能导致晶界析出杂质或者不稳定 设备成本高,规模化生产受限

集成工艺

薄膜法 冷压集成 湿法纸浆 熔体铸造
工艺 溅射、蒸镀或脉冲激光沉积(PLD)制备纳米级电解质膜 将电解质粉末与电极材料(如 LiCoO₂)混合后冷压(1–5 GPa)成多层结构 将电解质粉末分散在溶剂(如 NMP)中,与电极材料、粘结剂混合成浆料,涂覆后干燥 将低熔点电解质(如 Li₂OHCl,熔点≈400°C)加热至液态后倒入模具,冷却固化
优点 厚度可控,适合微型电池,高致密性,介面接触良好 适合规模化生产,溶剂辅助形成均匀界面,提高离子接触面积 一步成型,适合复杂形状
缺点 设备昂贵,难以规模化生产 界面接触面积不足,导致高阻抗 硫化物对水敏感,需严格控制环境湿度 仅适用于低熔点材料,应用范围有限

工艺对材料性能的影响

工艺 对离子电导率的影响 对机械性能的影响 对界面的影响
固态合成 高温可能促进结晶,提高电导率(如 LLZO) 晶粒粗大,断裂韧性较低(如 LLZO 的 K₁c=1.2 MPa・m¹/²) 晶界杂质导致高电阻(如 LLZO 的晶界电阻占比 > 50%)
机械化学法 纳米晶粒增加晶界传导(如 Li₃PS₄的 σ=2 mS/cm) 晶粒细化提高断裂韧性(如 Li₆PS₅Cl 的 K₁c=0.8→1.5 MPa・m¹/²) 界面接触面积大,但晶界缺陷可能增加阻抗
SPS 致密化 高致密度减少孔隙,提高 σ(如 LLZO 的 σ=0.8 mS/cm) 高致密度降低裂纹扩展风险(如 LLZO 的孔隙率 < 1%) 界面结合紧密,但可能因快速冷却引入应力
湿法制浆 溶剂辅助形成均匀接触,降低界面电阻(如 Li₆PS₅Cl/NCM 的界面电阻 < 50 Ω・cm²) 粘结剂(如 PVDF)增加柔性,但降低机械强度 溶剂残留可能导致界面副反应(如硫化物水解)

关键挑战与解决方案

挑战 解决方案
锂枝晶穿透电解质 提高电解质断裂韧性(如纳米晶 LLZO 的 K₁c=2.5 MPa・m¹/²),降低电子电导率(<10⁻⁹ S/cm)
界面阻抗增长 设计自钝化界面(如 LiPON/Li₂O 双层涂层),优化接触面积(如纳米颗粒复合电极)
高能量密度与高功率权衡 开发双离子传导路径(如 Li⁺/ 空位协同迁移),采用超薄电解质(<10 μm)
硫化物电解质的环境敏感性 表面包覆 $\rm{Al_2O_3}$$\rm{Li_3BO_3}$,开发水稳定电解质(如 $\rm{Li_3OCl}$

潜在突破点

  1. 室温全固态钠电池
    • 采用 $\rm{Na_3PS_4}$基电解质与 $\rm{Na_3V_2(PO_4)_3}$阴极,实现能量密度 > 200 Wh/kg。
  2. 固态锂硫电池
    • 利用 $\rm{Li_{10}GeP_2S_{12}}$电解质抑制多硫化物穿梭,循环寿命超 500 次。
  3. 固态电解质燃料电池
    • 开发质子传导电解质(如 $\rm{BaZr_{0.8}Y_{0.2}O_3}$),实现氢氧燃料电池的小型化。

关于Li-Argyrodite

对于$\rm{Li_7PS_6}$,由于缺乏卤素离子,导致没有阴离子无序,电解质仅表现出笼内跳跃(蓝色)和双重跳跃(绿色),且笼间跳跃(红色)最少,导致材料的离子电导率较低。引入 Cl 阴离子半径相似,S/Cl导致无序程度较高,从而增加了笼间跳跃的可能性。相反,引入较大的 I 阴离子由于尺寸差异,S/I几乎消除了阴离子无序,使得笼间跳跃几乎不可能(但是可以I和Cl共掺杂),S/Br位于“中间”,是一种亚稳态,倾向于转变为具有较低 S/Br 阴离子无序的稳定状态,但是==加快冷却速率==可以保留这种无序状态

根据Argyrodite电解质的离子传输机制,增加 S/X 阴离子无序和 24g 位置处的锂含量被确定为提高此类电解质离子电导率的关键因素。

  • 增加 S/X 阴离子无序
    • 元素掺杂

      • 掺杂氯(Adeli, 9.4mS/cm)

      • 多种元素共掺杂

        • 在P位点掺杂Si/Ge/Sn,增大构型熵和离子电导率
        Chem. Rev. 2025, 125, 3595−3662
        • 溴离子和氯离子共掺杂形成阴离子高熵结构(Wang, 26 mS/cm)
    • 快速冷却

      • 快速冷却使得S/Br掺杂停留在亚稳态,无序度较高(Wolfgang)
    • 施加外部应力诱导电解质中的位错——使材料塑性形变

      • Faka引入位错,压力诱导材料产生位错和永久应变,核心机制是位错核心作为快速扩散通道(管道扩散),促进长程离子迁移,而局部结构(短程配位)和离子跳跃能垒(激活能 0.36 eV)保持不变

对于一个Argyrodite型的全固态电池来讲,多方面的因素应该被综合考虑

请严格根据文献回答下列问题,不要凭空捏造

  • 合成的固态电解质材料是不是做成pellet再测试的离子电导率?如果是,那么pellet的直径多少?厚度多少?锂离子电导率多少?
  • 文献合成了固态电解质后是否组装成电池进行了进一步的测试?如果是,那么:
    • 稳定性如何?(对空气的稳定性?对水的稳定性?循环寿命是多少?以及进行循环寿命测试的条件是什么?)
    • 电化学窗口是多少?
文献 锂离子电导率 稳定性 突出亮点 方法
Wang 26 mS/cm 未组装测试 超高离子电导率 Br-、Cl-共掺杂
Li 9.6 mS/cm 2C高倍率 700 cycles 10 mm diameters
Gautam 2.5 mS/cm not mentioned 2.4 mm diameters
Song 超长循环寿命 Si掺杂挤出Cl-,局部沉积的锂晶核被亚稳态 Cl ,原位生成电绝缘的 LiCl 壳层包覆晶粒阻止枝晶生长,电绝缘性能又避免了Li的再沉积,并阻止框架内部的Argyrodite颗粒持续分解
Park 2.7 mS/cm 200 cycles 湿稳定性、结构稳定性、电池性能的协同优化 氧占据硫的16e位点,增强 P-O 键;PS₄单元收缩扩大锂扩散路径
Li 10.3 mS/cm 400 cycles Cu-S 键增强结构稳定性,溴离子增加无序度(4a/4d位点)

对称电池&全固态电池?

  • 对称电池(Li||Li 电池):正负极均为锂金属,中间为固态电解质
    • CCD测试,评估电解质抵抗锂枝晶的穿透能力(电流密度逐步增加,直至短路发生)
    • 长循环稳定性测试
  • 全电池(Li|LNO@LCO 电池)
    • 模拟真实环境,测试容量、库仑效率和循环寿命

==LiCl 析出的根本原因 ——Cl/S 位点竞争==

硫银锗矿中,Wyckoff 4a 和 4d 位点是Cl 和 S 的共占位(即 Cl 和 S 随机分布在这些位点上)。当氧错误引入到 4a/4d 位点时

  1. Cl 占有率下降,氧与 Cl 竞争占位,迫使 Cl 从晶格中析出,形成 LiCl 杂质(反应式:Li₆PS₅Cl + O²⁻ → LiCl↓ + Li₅PS₄O + S²⁻)
  2. 化学平衡破坏,Cl 是维持高离子电导率的关键(Cl 的无序分布可形成 Li⁺迁移通道),Cl 流失会导致通道堵塞,同时降低 SE 的化学稳定性(Cl 不足时,S 更易与水反应生成 H₂S)

LiCl 析出会破坏硫银锗矿的立方 F43m 结构,LiCl 析出导致 HR-LiPSCl 的界面电阻(R_SE,CAM)在 100 次循环后达 62 Ω,比 HR-LiPSOCl3(39 Ω)高 60%,直接导致容量衰减加快。

Li₆PS₅Cl的降解问题

阶段 暴露条件 主要变化 关键产物 / 数据
1 原始态(手套箱) 多晶结构,P/S/Cl 均匀分布,氧极少 无 secondary phase,O/S 比接近 0
2 干燥室短期(1 周) 晶界氧含量增加,反应启动 氧沿晶界分布,硫损失可忽略
3a 干燥室 1-4 周 相分离为 LPSO(富 S/P)和 LiCl(晶界) 硫损失 20%(S/P 比从 5→4),O/S 比显著上升
3b 干燥室 3a 后 LiCl 从晶界扩散至表面形成厚壳 LiCl 壳层厚度~微米级,颗粒保持部分原始形貌
4 环境空气 10 秒 剧烈多孔化、晶粒拆解,LiCl 团聚 氧富集相(Li₂O/LiOH)分离,气泡状形貌
5 干燥室长期(>1 月) 致密化,氧 / 碳富集,原始形貌消失 Li₂CO₃形成(EDX 检测 C/O 共分布),O/S 比达阶段 1 的~5 倍
image-20250507102203925

文献通过实验(同步辐射 X 射线衍射、电化学阻抗、固态 NMR)+ 计算(机器学习分子动力学模拟),研究了一种含氰化物的固态电解质 Li₆PS₅CN 的结构与动力学行为,核心目标是回答两个问题:

  1. 阴离子位点无序(氰离子 CN⁻和硫离子 S²⁻如何混合分布)如何影响锂离子的 “搬家速度”(扩散)?
  2. 位点无序是否会改变氰离子自身的 “旋转运动”,进而间接影响锂离子传输?

什么是 “有序结构” 和 “无序结构”?(用通俗语言解释)

  1. 结构背景:Li₆PS₅CN 的 “原子棋盘”
  • 该材料的晶体结构中,阴离子(CN⁻和 S²⁻)占据两种 “格子”:4a 位点(立方体顶点)和4d 位点(立方体体对角线中点),形成类似 “钻石晶格” 的排列(图 1)。
  • 锂离子(Li⁺)住在这些阴离子格子的 “间隙” 里,需要在间隙中跳跃移动。
  1. 有序结构:阴离子 “分区而治”
  • 定义

    :CN⁻和 S²⁻各自 “乖乖” 待在自己的格子里,比如:

    • 4a 位点全是 S²⁻,4d 位点全是 CN⁻(或反过来),两种离子 “互不串门”(图 8 中的 Configuration 1/6)。
  • 特点:阴离子分布整齐,结构对称性高,但锂离子的间隙环境较单一。

  1. 无序结构:阴离子 “混合混居”
  • 定义

    :CN⁻和 S²⁻在 4a/4d 位点上 “随机混搭”,比如:

    • 4a 位点 67% 是 S²⁻、33% 是 CN⁻,4d 位点 33% 是 S²⁻、67% 是 CN⁻(实验测得的实际结构,图 2 / 表 1),或 50%/50% 混合(模拟中的 Configuration 3/4)。
  • 特点:阴离子分布混乱,结构对称性降低,但锂离子的间隙环境更 “多样化”。

哪种结构促进锂离子传输?无序结构是 “加速器”

  1. 无序结构如何让锂离子 “跑更快”?
  • 实验证据
    • 电化学阻抗谱(EIS)显示,无序结构的 Li₆PS₅CN 在 30°C 时的体电导率为 6.8×10⁻⁵ S/cm,比完全有序的类似材料(如 Li₆PS₅I,碘离子太大无法混合)高几个数量级。
    • 固态 NMR(⁷Li)显示,无序结构中锂离子在 194 K 开始 “运动窄化”,即从 “原地振动” 变为 “短程跳跃”,高温下(500 K)扩散系数达 10⁻⁶ cm²/s(有序结构仅 10⁻⁷~10⁻⁸ cm²/s)。
  • 模拟机制
    • 有序结构中,锂离子被局限在固定的 “锂笼” 里,只能在小范围内跳跃(MSD 曲线快速平台化,图 9a)。
    • 无序结构中,阴离子混合打破了 “锂笼” 的规则性,创造了更多低能量的 “跨笼跳跃路径”,锂离子能更频繁地进行长程扩散(MSD 曲线线性增长,图 9b)。
  1. 关键结论只要阴离子能混合(如 CN⁻/S²⁻、Cl⁻/S²⁻),就能促进锂离子长程传输
  • 这是整个 argyrodite 家族(Li₆PS₅X,X=Cl/Br/CN)的共性:位点无序是高电导率的关键(碘离子因太大无法混合,导致电导率暴跌)

“阴离子像跳广场舞一样混合分布(无序)时,锂离子的‘跑道’更畅通,跑得更快;而氰离子自己是否旋转(有序时快、无序时慢)对锂离子的影响不大,关键是阴离子别‘排排站’(别有序)。”

Br、BH4掺杂 14.4 mS cm

银矿型电解质(如 Li₆PS₅X,X=Cl、Br、I)因高电导率和 Li 金属兼容性受关注,此前报道的 BH₄⁻取代银矿电解质(如 Li₅.₃PS₄(BH₄)₂.₃)电导率 > 10 mS cm⁻¹。本文研究目的:通过 Br⁻部分取代 BH₄⁻位点,进一步提升银矿型电解质的离子电导率

文献中采用的是两步球磨法,无需加热

x 组成 室温离子电导率(mS cm⁻¹)
0 Li₃PS₄·2.5LiBH₄ 10.6
0.5 Li₃PS₄·2LiBH₄·0.5LiBr 13.6
0.7 Li₃PS₄·1.8LiBH₄·0.7LiBr 14.4(最高)
1.0 Li₃PS₄·1.5LiBH₄·1LiBr 8.4
2.5 Li₃PS₄·2.5LiBr 0.49

关键问题

  1. 为什么 Br⁻和 BH₄⁻共取代能提升离子电导率?
    • 答案:Br⁻取代 BH₄⁻位点后,银矿相(argyrodite相)的结晶度提高,且两种阴离子共存增加了晶格无序度,降低 Li⁺迁移的活化能。³¹P NMR 显示,含两种阴离子的银矿相中 PS₄³⁻单元总比例显著增加(如 x=0.5 时达 95.7%),而银矿相比例与离子电导率正相关,从而提升整体电导率。
  2. 两步球磨法相比传统方法有何优势?
    • 答案:传统方法可能需热处理以促进相形成,但本研究通过两步球磨法(先制备 β-Li₃PS₄,再与 LiBH₄/LiBr 混合研磨),无需热处理即可生成高结晶度的银矿相,简化工艺并降低能耗。同时,球磨过程中添加甲苯作为工艺控制剂,避免粉末黏附,确保均匀混合。
  3. 含 Br⁻和 BH₄⁻电解质的全固态电池性能提升的关键因素是什么?
    • 答案:关键因素包括两方面: ① 高离子电导率:室温下 14.4 mS cm⁻¹ 的电导率加速 Li⁺传输,提升电池速率性能(如 2 C 时仍保持有效容量)。 ② 界面稳定性:Br⁻可能促进 Li 金属负极表面形成稳定的固态电解质界面(SEI),减少副反应,使电池在 300 次循环后容量保持率达 92%

文献通过 Sn/Sb/I 三元掺杂,在磷基 SSE 中实现电导率、界面稳定性、耐湿性的协同提升,突破传统单一元素掺杂的局限性

1. 锑基硫银锗矿掺杂如何提升磷基电解质的离子电导率?

答案

  • 晶格膨胀:Sn⁴⁺(离子半径 0.069 nm)和 Sb⁵⁺(0.062 nm)替代 P⁵⁺(0.038 nm),I⁻(0.206 nm)替代 Cl⁻(0.181 nm),增大晶格参数(LPSC-0.05 晶格常数 9.967 Å vs LPSC-0 的 9.851 Å),拓宽 Li⁺迁移通道。
  • 载流子增加:Sn⁴⁺的异价掺杂引入额外 Li⁺补偿电荷,提升载流子浓度。
  • 能垒降低:DFT 计算显示,Sn/Sb 与 S 的强键合削弱 S 对 Li⁺的吸引力,使笼内 / 笼间迁移能垒分别降至 0.496 eV 和 0.592 eV(LPSC-0 为 0.873 eV 和 0.976 eV)

2. 掺杂电解质如何实现优异的锂金属界面稳定性?

答案

  • 原位形成稳定界面相
    • LiI 保护层:I⁻与 Li 反应生成离子导电但电子绝缘的 LiI,抑制界面副反应。
    • Li-Sn/Sb 合金:Sn/Sb 与 Li 形成低电阻合金(如 Li₁₇Sn₄、Li₃Sb),促进 Li⁺均匀传输,减少枝晶生长。
  • 抑制分解产物:LPSC-0.05 界面的 Li₂S/Li₃P 等绝缘产物显著减少,界面电阻增长缓慢(300 小时仅从 81.8 增至 160.3 Ω cm²),而 LPSC-0 界面电阻激增 3 倍。

3. 耐湿性提升的化学机制是什么?

答案

  • 软硬酸碱理论(HSAB):P⁵⁺(硬酸)易与 H₂O 中的 O²⁻(硬碱)反应,而 Sn⁴⁺/Sb⁵⁺(软酸)倾向与 S²⁻(软碱)结合,形成稳定的 (Sn,Sb)-S 键(键能高于 P-S 键),抑制水解反应。
  • 结构保护:(P, Sn, Sb) S₄单元的形成增强了晶格稳定性,空气暴露后仅少量生成 Li₃PO₄等氧化物,而 LPSC-0 的 PS₄³⁻单元大量分解为 Li₄P₄O₇・5H₂O 等水合物,导致结构崩塌
  • H₂S 释放抑制:LPSC-0.05 在28%RH 下 30 分钟释放 H₂S 量为 0.46 cm³ g⁻¹,仅为 LPSC-0(1.38 cm³ g⁻¹)的 1/3,证明水解程度显著降低

文献探究了球磨处理对电解质的影响

处理方法 频率 / 转速 时间 研磨介质尺寸 目标应用
频率球磨 40 Hz 10 min 5 mm 常规正极复合材料制备
行星球磨 500 rpm 10 min 5 mm 快速混合(如 Li-S 电池)
行星球磨(长期) 500 rpm 240 min 5 mm 极端条件下的结构变化

结论

  • 双重效应:球磨通过减小颗粒尺寸(有利)和降低结晶度(不利)共同影响性能,短期处理因颗粒效应占优而提升电池性能;
  • 优化方向:控制球磨能量输入(如转速、时间),平衡结构退化与颗粒尺寸,是提升固态电池性能的关键。

关键问题与答案

问题 1:球磨处理如何影响 Li₅.₅PS₄.₅Cl₁.₅的晶体结构?

答案:球磨导致结晶度下降相干长度减小(如行星球磨 240 分钟后相干长度从≈30 nm 降至≈15 nm),同时增加局部结构无序度(PS₄³⁻聚阴离子和 Li⁺配位环境更无序)。XRD 峰宽化、NPDF 高 r 区域强度衰减及 NMR 谱宽化均证实了这一点。颗粒尺寸从 pristine 的 > 100 μm 降至行星球磨 10 分钟后的≈5 μm,分布更均匀。

问题 2:为什么球磨会降低固态电解质的离子电导率?

答案:球磨引起的结晶度下降和相干长度减小导致长程离子传输路径受阻。尽管活化能(≈0.38 eV)未变,但晶界或无序区域增加了离子迁移阻力。例如,行星球磨 240 分钟后,室温离子电导率从 6.8 mS/cm 降至 2.8 mS/cm,退火后部分恢复(5.3 mS/cm),表明结构退化是主要原因。

问题 3:颗粒尺寸减小对正极复合材料性能有何积极影响?

答案:较小的电解质颗粒(如行星球磨 10 分钟后的≈5 μm)可降低复合材料的曲折度,改善离子传输路径。有效离子电导率随颗粒减小而增加(行星球磨 10 分钟样品最高),进而提升电池倍率性能。例如,在 0.05 C 下,该样品放电容量比 pristine 高约 30 mAh/g,证明颗粒尺寸效应能补偿 bulk 电导率的轻微下降。

掺杂In2O3

  1. 成分与结构
    • 目标电解质:Li₅.₅₊₂ₓInₓP₁₋ₓS₄.₅₋₁.₅ₓO₁.₅ₓCl₁.₅(x=0.02 时最优,记为 LPSC-In₀.₀₂)
    • 结构特征:In³⁺取代 P⁵⁺,O²⁻取代 S²⁻,形成稳定晶格(晶格参数减小至 9.8073 Å)。
  2. 性能提升
    • 离子电导率:室温下达7.5 mS cm⁻¹(纯 Li₅.₅PS₄.₅Cl₁.₅为 9.0 mS cm⁻¹,掺杂后略降但界面相容性显著提升)。
    • 空气 / 水分稳定性
      • 暴露于 30% 湿度空气 20 min 后,H₂S 生成量减少,电导率保留率56%(纯电解质仅 10%)。
      • 在−60 °C 低露点干燥室暴露 12 h 后,电导率保留率高达92%(纯电解质 78.9%)。
    • 锂金属相容性:临界电流密度(CCD)从纯电解质的0.1 mA cm⁻²提升至1.8 mA cm⁻²,抑制锂枝晶初始生长。
  3. 机理分析
    • 硬 - 软酸碱理论(HSAB):In(软酸)与 S(软碱)结合力强于 P,减少 S²⁻与水反应;O(硬碱)提高 P-O 键稳定性,降低水解风险。
    • DFT 计算:P-O 键能(5.12 eV)高于 P-S 键(3.46 eV),水吸附能(ΔE_ad)从−0.35 eV(纯电解质)提升至−0.12 eV(改性后),抑制水解反应

LSPC在 Cl 离子占据 4c 位点 25% 时达到峰值,而不是在无序度最大时

  • 锂离子电导率受笼间和笼内跳跃相互作用影响。在 25% Cl@4c 时,笼内快速旋转运动,特别是围绕 4c 位点的双峰路径,使更多 Li 原子能够参与长程扩散;同时,S→S 笼间跳跃路径在 25% Cl@4c 时比 50% 和 75% Cl@4c 时更有利,这两个因素综合作用,使得锂离子电导率在 25% Cl@4c 时达到峰值 。而在 50% Cl@4c 时,虽然无序度最大,有利于扩散路径的渗透,但笼内旋转运动相对较弱,综合效果不如 25% Cl@4c 时。
  • 明确了锂离子扩散呈现非阿累尼乌斯行为,在高温((>400K))时具有不同的活化能。这种行为是由于温度升高时,锂离子围绕 4a 位点的旋转频率增加,促进了长程扩散,原本在低温下限制笼间跳跃的因素不再关键,更多有效的锂离子跳跃路径得以开启,进而降低了活化能

(Li5.4Al0.1P1 − xSbxS4.7 − 2.5xO2.5xCl1.3)

合成了x = 0、0.02、0.04、0.06、0.08的电解质

离子电导率:Li6PS5Cl室温离子电导率为1.56x10−2S cm−1,Li5.4Al0.1PS4.7Cl1.3(x = 0)提升至2.79 x 10−3 S cm−1

1.1 结构改变增加离子传输通道

  • 在合成Li5.4Al0.1PS4.7Cl1.3电解质时引入ClAl3+
    • Al3+半径(53 pm) < Li+半径(68 pm)
    • Al3+占据Li+的24g和48h位点 → Li位点空位浓度增加
    • 新增空位为Li+扩散提供更多通道

1.2 优化晶体结构促进离子迁移

  • XRD Rietveld精修显示Li5.4Al0.1P0.94Sb0.06S4.55O0.15Cl1.3结构优化:
    • Sb3+位于P5+的4b位点 → 形成SbS43−四面体
    • O2−位于S2−的16e位点 → 形成PS3O4−四面体
  • 性能对比: | 电解质组成 | 离子电导率 (S/cm) | | —————- | —————– | | Li6PS5Cl | 1.56 × 10−3 | | 优化后电解质 | 2.22 × 10−3 |
  1. 空气稳定性提升的原因

2.1 化学键增强抑制水解反应

  • 硬软酸碱理论应用
    • Sb5+(软酸)与S2−(软碱)形成强Sb − S
    • 相比P − S键更稳定,减少与H2O反应
  • 实验数据:
    • H2S排放量降低78%

2.2 结构稳定减少与水分反应

  • O2−掺杂效应:
    • 部分取代S2− → 形成稳定P − O
  • 结构稳定性对比(60%RH暴露20min后): | 电解质类型 | XRD衍射峰变化 | | ———————————————————– | ————- | | Li6PS5Cl | 几乎完全消失 | | Li5.4Al0.1P0.94Sb0.06S4.55O0.15Cl1.3 | 保持稳定结构 |

Li6 + xMxSb1 − xS5I——阳离子无序

Nb,O共掺杂

研究通过在 Li₆PS₅Cl 电解质中进行 Nb 和 O 共掺杂,制备了系列 Li₆P₁₋ₓNbₓS₅₋₂.₅ₓO₂.₅ₓCl 电解质,显著提升了全固态锂电池的性能。其中,当 x=0.05 时,电解质室温离子电导率达4.19 mS cm⁻¹,较原始电解质提高约 35%;在 30% 相对湿度下,释放的 H₂S 气体量仅为原始电解质的一半,湿度稳定性显著增强。得益于界面处形成的离子导体 Li₃OCl,电解质与锂金属的临界电流密度(CCD)提升至1.55 mA cm⁻²,且在 0.2 mA cm⁻² 电流密度下循环稳定性达3600 h。组装的 LiCoO₂/ 电解质 / Li 电池在 1C 下循环 1000 次后容量保持率为83.5%,展现出优异的综合性能。

双掺杂——Li₆.₂Ge₀.₁P₀.₉S₄.₈O₀.₂Cl

研究针对锂硫固态电解质(LPSC)空气稳定性差和锂金属兼容性不足的问题,通过 Ge-O 双掺杂策略合成了 Li₆.₂Ge₀.₁P₀.₉S₄.₈O₀.₂Cl 电解质,其室温离子电导率达 2.47 mS cm⁻¹,较原始 LPSC 提升 1.6 倍,且活化能低至 0.24 eV。该电解质显著抑制 H₂S 气体释放,空气暴露后离子电导率保留率达 37%,同时临界电流密度(CCD)提升至 1.4 mA cm⁻²,有效抑制锂枝晶生长。基于此电解质的 NCM811/Li 全电池在 0.1 C 下比容量 164.2 mA h g⁻¹,0.5 C 循环 300 次容量保持 86%,库仑效率近 99.7%,为固态电池实用化提供了新路径

Mg、Zn、Si和Ge被确定为调节Li离子浓度及其离子电导率的最有希望的掺杂剂

  1. 卤素掺杂优势:除了碘外,卤素掺杂剂(如Cl、Br、I)在八面体和四面体位点上的替代是可行的,与实验结果一致。
  2. 最有希望的掺杂剂:Mg、Zn、Si和Ge被确定为调节Li离子浓度及其离子电导率的最有希望的掺杂剂,而三价掺杂剂在热力学上是不利的。
  3. 共掺杂的影响:阳离子共掺杂剂对阴离子掺杂剂浓度的影响通常不大,但Si共掺杂可以显著增加阴离子浓度,为F掺杂argyrodite的合成提供了可能;而阴离子共掺杂(特别是在卤素家族内)会显著改变其他阴离子在Li7PS6 argyrodites中的浓度。

Li₅.₄P₀.₉₅Sb₀.₀₅S₄.₃₂₅Se₀.₀₇₅Cl₁.₆

研究通过锑(Sb)和硒(Se)双掺杂策略,优化了银矿型硫化物电解质 Li₅.₄P₀.₉₅Sb₀.₀₅S₄.₃₂₅Se₀.₀₇₅Cl₁.₆的化学稳定性和离子导电性,其室温离子电导率达 11.34 mS cm⁻¹,暴露于干燥室 12 小时和潮湿空气 30 分钟后,电导率分别保持 9.42 和 1.73 mS cm⁻¹,显著优于未掺杂电解质。通过乙基乙酸酯和聚偏二氟乙烯的湿涂覆工艺,制备了厚度仅 14 μm、电导率 2.19 mS cm⁻¹ 的超薄电解质膜。该电解质与锂金属界面兼容性优异,对称电池在 0.1 mA cm⁻²/5 mAh cm⁻² 下稳定循环 6000 小时,全固态电池在 1 C 下 500 次循环后容量保持率 81.9%,软包电池在 0.1 C 下循环 500 次容量保持率 82.6%,为高能量密度全固态锂电池提供了有效策略。

性能 结构 - 机理关联 文献直接依据
界面相容性 1. Sb-S 键强于 P-S 键,抑制 Li 还原电解质生成 Li₂S 等副产物 2. 电子电导率降低,抑制锂枝晶 3. 极化电压稳定,界面阻抗低 原位 XPS(图 3e-f)、临界电流密度(图 3a-b)、对称电池循环(图 3c)、电子电导率数据(Figure S4)
空气稳定性 1. Sb 软酸替代 P 硬酸,减少与 H₂O/O²⁻的硬 - 硬酸碱反应 2. SbS₄³⁻单元稳定,抑制PS₄³⁻水解和结构降解 3. H₂S 释放量减半,晶体结构保持完整 硬软酸碱理论分析、Raman 光谱(图 2b、2f、2h)、XRD(图 2e)、H₂S 释放测试(图 2c)

Li₆₊ₓP₁₋ₓSiₓS₅Br(x=0~0.4)中阴离子位点无序动力学

淬火温度 /°C 主要现象 无序度变化(x=0.4) 晶格参数趋势
350 无序度低,Si 影响小 约 20% 随 Si↑线性增大
450 无序度中等,Si 效应显现 约 30% 增大趋势变缓
550 无序度最高,Si 显著促进无序 约 35% 增大趋势最弱(因无序度↑)

npj计算

  • 区分孤立硫阴离子(Siso)与键合硫阴离子(Sbond)

关键意义:确认材料中是否存在孤立 Siso,是形成 “笼状传输通道” 的前提(文献中 Li₆PS₅Cl 的高电导率归因于 Siso 诱导的 frustration 现象)

  • 高温退火或压力调控合成不同空间群的硫基 argyrodite(如文献中 Li₈SiSe₆的 F43m、Pna2₁等相),目标是提高孤立阴离子的局部点群对称性(如 Td、Oh)

Li₆₊₂ₓP₁₋ₓYₓS₅₋₁.₅ₓO₁.₅ₓCl(x=0~0.1)

研究针对硫化物电解质 Li₆PS₅Cl(LPSC)与锂负极界面反应和枝晶生长问题,提出通过钇(Y)和氧(O)共掺杂调节 PS₄四面体的 d-p 轨道杂化,实现硫原子的电子局域化。 该策略增强了 Y 与 S 的 Madelung 能,抑制 Li 与 S 的相互作用,同时原位形成 Li₂O 界面保护层,提升空气稳定性。改性后的 LPSC-YO 电解质使 Li 对称电池稳定循环超 4800 小时(0.1 mA cm⁻²),LiCoO₂/Li-In 全电池在 0.5 C 下循环 1300 次容量保持率 100%。研究通过轨道杂化驱动的电子局域化策略,为硫化物基全固态锂电池的界面稳定提供了新路径

x=0.05时最优,Li6.1P0.95Y0.05S4.925O0.075Cl

核心目标

  • 调节 PS₄四面体的d-p 轨道杂化(Y 的 d 轨道与 S 的 p 轨道),增强 S 原子电子局域化,抑制 Li 与 S 的相互作用;同时原位形成Li₂O 界面保护层,提升界面稳定性和空气稳定性

Y 和 O 共掺杂如何提升 LPSC 电解质的界面稳定性?

  • 答案:Y 替代P形成Y-S键,通过d-p轨道杂化增强S原子的电子局域化,提升Y-S键的Madelung能(库仑相互作用),抑制 Li 与 S 的还原反应;O 掺杂部分替代 S,通过硬软酸碱理论减少水解反应,同时原位生成 Li₂O 界面层,作为物理屏障阻止 Li 与电解质直接接触,协同抑制枝晶生长和副产物生成。

Li₇₋ₓ(GeSi)₍₁₋ₓ₎/₂SbₓS₅I(LGSSSI)

研究开发了一种新型超离子导体硫化物固态电解质 Li₇₋ₓ(GeSi)₍₁₋ₓ₎/₂SbₓS₅I(LGSSSI),通过 Ge、Si、Sb 对 Li₆PS₅I 中 P 的多阳离子取代,增加了结构熵和阴离子位点无序度,使 Li⁺迁移活化能降至0.17 eV,实现了12.7 mS cm⁻¹ 的冷压室温离子电导率(热压后达32.2 mS cm⁻¹)。将 LGSSSI 与 Li₃InCl₆(LIC)复合构建全固态电池(ASSBs),电池在 0.1 C 下容量达219 mAh g⁻¹,1 C 下 550 次循环后容量保持率84.4%,并能在 -20 至 60 °C宽温范围及100 mg cm⁻² 超高阴极负载 下稳定运行,为高性能宽温固态电池提供了新策略。

(Li5.33PS4.27O0.12Cl1.58)(HR − LiPSOCl)

16e位置上引入氧,显著提升了材料的耐湿性、结构稳定性及电池性能

(Li6 − xAsS5 − xBr1 + x)(0.0 < x < 0.6)

基于硬软酸碱理论(HSAB),通过中子衍射、NMR 光谱和电化学阻抗谱分析发现,(Br 部分取代 (S2−) 削弱了锂离子 “笼” 内相互作用,增加了额外的 T4 锂离子位点,降低了跨笼迁移能垒。其中 (Li5.5AsS4.5Br1.5) 表现出卓越的室温离子电导率(15.4 mS cm−1)和空气稳定性,其 (H2S) 释放量仅为硫代磷酸盐电解质的四分之一,为开发高导电、稳定的硫化物固体电解质提供了新思路。

问题 1:为什么 Br 取代 S 能提高离子电导率?

  • 答案:Br⁻取代 S²⁻降低了 4d 位点的平均阴离子电荷密度,减弱 Li⁺与笼中心阴离子的相互作用,使锂离子笼体积扩大Rmean 增大),同时缩短跨笼迁移距离(如 T5-T4-T5 从 3.80 Å 降至 3.70 Å),降低迁移能垒。此外,Br 引入 Li⁺空位,增加离子传输路径的连通性,协同提升电导率至 15.4 mS cm−1

问题 2:As 取代 P 对材料性能的核心作用是什么?

  • 答案:As⁵⁺作为软酸中心(相较 P⁵⁺),根据 HSAB 理论,与软碱(S²⁻、Br⁻)结合更稳定,减少材料在潮湿环境中的分解,降低 (H_2S) 释放量。同时,As 的较大离子半径使 (AsS4)3− 四面体体积扩大(从 4.41 ų 到 5.2 ų),为 Li⁺提供更宽敞的扩散路径,辅助提升电导率和空气稳定性。

问题 3:如何通过实验验证锂离子的跨笼迁移路径?

  • 答案:通过中子衍射精修确定锂离子位点(T4、T2、T5 等),发现 Br 含量增加时 T4 位点占据率上升,结合 NMR 自旋 - 晶格弛豫(7Li T1)分析,观察到跨笼迁移相关的不对称弛豫曲线(β 值降低),表明长程迁移比例增加。电化学阻抗谱和 PFG NMR 测得的扩散系数与电导率正相关,进一步证实 Br 诱导的结构变化促进了跨笼迁移,降低了离子传输阻力。

研究聚焦大气气体(CO₂和 O₂)对银矿型硫化物固体电解质 Li₆PS₅Cl 在水分暴露下的影响

研究聚焦大气气体(CO₂和 O₂)对银矿型硫化物固体电解质 Li₆PS₅Cl 在水分暴露下的影响,通过电化学阻抗谱、X 射线衍射、X 射线吸收光谱和光电子能谱分析发现:H₂S 生成量与大气气体无关,但 CO₂促进碳酸盐形成,O₂促进磷酸盐和磺酸盐形成,导致电解质表面降解,进而显著降低锂离子电导率。研究结果表明,除水分外,大气气体成分是影响硫化物固体电解质性能的关键因素,为全固态电池的制造环境控制提供了新视角。

一篇综述

策略 典型组成 离子电导率(RT) 活化能(eV) 优势 / 应用场景
卤素掺杂 (Li_6PS_5Cl_{0.5}Br_{0.5}) 3.63 mS/cm⁻¹ 0.31 通用型电解质,界面兼容性好
锂位空位 + 卤化 (Li_{5.5}PS_{4.5}Cl_{1.5}) 14.5 mS/cm⁻¹ 0.23 高能量密度电池,快充需求
磷位取代(Si/Ge) (Li_{6.5}[P/Si/Ge/Sb]S_5I) 13.2 mS/cm⁻¹ 0.20 高压电池(耐 7 V 正极)
全卤化结构 (Li_{5.2}Si_{0.2}Sb_{0.8}S_4Br_{0.25}I_{1.75}) 13.23 mS/cm⁻¹ 0.17 柔性电池,机械稳定性优先

反着来的,反面教材?

1. Zn²⁺取代如何影响锂银锗矿的晶体结构和离子传输?

答案:Zn²⁺仅占据 Li⁺的 T5 位点,导致 Li⁺笼内传输路径阻塞。晶格参数因 Zn²⁺的高库仑吸引力和离子半径差异线性减小,形成固溶体。离子电导率随取代度增加而下降(如 Cl 基从 7.4 mS・cm⁻¹ 降至 6.0 mS・cm⁻¹),活化能升高(从 406 meV 升至 415 meV),主要由于 T5 位点阻塞减少 Li⁺迁移路径,同时载流子密度降低和晶格收缩进一步限制传输。

2. Zn²⁺取代对固态电池界面(CEI)的形成有何影响?

答案:取代加速 CEI 形成并改变其组成。阻抗谱显示,取代材料的界面电阻(R₂+R₃)在初始循环中增长更快,尤其在高截止电位(≥3.8 V)下差异显著。XPS 分析表明,取代样品生成更多含氧降解产物(如亚硫酸盐、硫酸盐),而未取代样品以多硫化物为主。这表明 Zn²⁺可能促进氧化分解反应,形成更电阻性的 CEI 层,导致容量衰减加快。

3. 为什么选择 Zn²⁺作为取代离子?其取代策略的潜在优势与局限性是什么?

答案

  • 优势:Zn²⁺离子半径与 Li⁺接近(0.60 Å vs 0.59 Å),且在 NCM 工作电位范围内无氧化还原活性,理论上可稳定存在于电解质结构中;Zn 的化合物(如 ZnS)可能吸收分解产物(如 SO₂),改善界面稳定性。
  • 局限性:Zn²⁺占据 Li⁺位点阻塞传输路径,导致电导率下降和活化能升高,抵消了界面调控的潜在优势;实验表明,取代反而加速 CEI 形成,可能因 Zn²⁺促进界面反应动力学或生成高电阻产物。 结论:Zn²⁺取代策略在界面调控中具有挑战性,需平衡离子导电性与界面相容性,为后续过渡金属取代研究提供参考。

又一篇综述?

3. 掺杂策略及性能提升

3.1 离子电导率优化
  • 阴离子掺杂
    • 卤素掺杂:Cl/Br/I 无序化增加 Li⁺迁移路径,如 Li₅.₅PS₄.₅Cl₁.₅电导率达 9.4 mS cm⁻¹(烧结后 12.0 mS cm⁻¹)。
    • 非化学计量掺杂:Li 过剩(如 Li₆.₂₅PS₅.₂₅Cl₀.₇₅)增加间隙 Li⁺,电导率 14 mS cm⁻¹,活化能 211 meV。
    • BH₄⁻/Se²⁻掺杂:Li₅.₃₅PS₄.₃₅(BH₄)₁.₁₅Cl₀.₇₅电导率达 26.1 mS cm⁻¹,通过团簇动态效应降低迁移能垒。
  • 阳离子掺杂
    • Ge/Si/Sb 取代 P:扩大 Li⁺笼间距,如 Li₆.₇₅Sb₀.₂₅Si₀.₇₅S₅I 活化能低至 0.17 eV,电导率 13.1 mS cm⁻¹。
    • 高熵电解质:多阳离子掺杂(如 Li₆.₅P₀.₂₅Si₀.₂₅Ge₀.₂₅Sb₀.₂₅S₅I)提升结构无序性,促进长程迁移。
  • 共掺杂策略
    • Bi-O/In-O 掺杂:协同增强结构稳定性,如 Li₆.₁₆P₀.₉₂In₀.₀₈S₄.₈₈O₀.₁₂Cl 电导率 2.67 mS cm⁻¹,临界电流密度 1.4 mA cm⁻²。

表 1:不同掺杂策略下的离子电导率与活化能

掺杂类型 典型组成 室温电导率 (mS cm⁻¹) 活化能 (eV)
阴离子掺杂 Li₅.₃₅PS₄.₃₅(BH₄)₁.₁₅Cl₀.₅ 26.1 -
阳离子掺杂 Li₆.₇₅Sb₀.₂₅Si₀.₇₅S₅I 13.1 0.17
共掺杂 Li₆.₀₄P₀.₉₈Bi₀.₀₂S₄.₉₇O₀.₀₃Cl 3.4 0.261
3.2 空气稳定性增强
  • 理论基础:HSAB 理论,硬碱 O²⁻增强 Li⁺键合,抑制 P⁵⁺与 H₂O 反应。DFT 计算显示,O 掺杂使分解能从负值升至正值(如 x>0.5 时 Li₆POₓS₅₋ₓBr₀.₅Cl₀.₅分解能 > 0)。

  • 实验验证

    • Sb/Zn 掺杂:Sb-PS₅电解质 H₂S 生成量从 0.57 cm³ g⁻¹(纯 Li₆PS₅Cl)降至 0.09 cm³ g⁻¹,电导率下降幅度 < 10%。
    • 氧化物掺杂:Li₂O/P₂O₅掺杂使 Li₆.₂₅PS₄O₁.₂₅Cl₀.₇₅在 53% 湿度下 30 min 内 H₂S 生成量显著降低。
3.3 热稳定性与界面调控
  • 热稳定性:BH₄⁻掺杂电解质在 160°C 以下稳定,高温退火(550°C)导致 BH₄⁻分解,结构破坏。
  • 界面稳定性
    • 阴极界面:LiNbO₃掺杂抑制 S²⁻/O²⁻交换,界面层厚度从 80 nm 减至 50 nm,如 LiCoO₂电池循环 100 次容量保持 92.2%。
    • 阳极界面
      • 卤素掺杂形成 LiF/LiCl 界面层,如 Li₆PS₅Cl₀.₃F₀.₇临界电流密度 1.45 mA cm⁻¹(纯 Li₆PS₅Cl 为 0.55 mA cm⁻¹)。
      • 氧化物掺杂生成 Li-In/Li-Sb 合金,降低 Li⁺迁移能垒,如 Li₆.₁₆P₀.₉₂In₀.₀₈S₄.₈₈O₀.₁₂Cl 界面电阻降低 3.5 倍。

关键问题及答案

问题 1:掺杂如何提升锂 - 银辉石电解质的离子电导率?

答案:掺杂通过三种主要机制提升电导率:

  1. 增加 Li⁺迁移路径:阴离子掺杂(如 Cl/Br)引入无序化,扩大 Li⁺笼间距(如 Ge 掺杂使晶格膨胀),降低迁移能垒(活化能从 0.41 eV 降至 0.17 eV);
  2. 提升 Li⁺浓度:非化学计量 Li 过剩(如 Li₆.₂₅PS₅.₂₅Cl₀.₇₅)增加间隙 Li⁺位点,促进长程扩散;
  3. 动态结构调节:BH₄⁻等团簇掺杂通过旋转 / 平移调整 Li⁺迁移通道,如 Li₆POS₄(SH) 中 SH⁻阴离子动态降低能垒。

问题 2:为什么掺杂能改善电解质的空气稳定性?其理论依据是什么?

答案:掺杂改善空气稳定性的核心是抑制水解反应,理论依据为HSAB 理论

  • 未掺杂电解质中,软碱 S²⁻与硬酸 P⁵⁺结合,易与空气中 H₂O(硬碱)反应生成 H₂S;
  • 掺杂 O²⁻(硬碱)后,形成更强的 Li⁺-O 键,提升分解能(如 O 掺杂使 Li₆POₓS₅₋ₓBr₀.₅Cl₀.₅分解能从 - 0.03 eV 升至 + 0.04 eV),抑制 P⁵⁺与 H₂O 反应;
  • 阳离子掺杂(如 Sb/Zn)通过形成稳定的 SbS₄/ZnS 单元,减少水吸附(如 Sb-PS₅电解质水吸附能降低 50%)。

问题 3:界面稳定性对全固态电池的影响及掺杂如何解决?

答案:界面稳定性直接影响电池阻抗和循环寿命,掺杂通过形成稳定界面层解决:

  • 阴极界面:Nb/O 掺杂抑制 S²⁻向阴极迁移(如 LiNbO₃掺杂使 Ni 离子扩散深度从 80 nm 减至 50 nm),降低副反应;

  • 阳极界面

    1. 卤素掺杂生成 LiF/LiCl 层(高界面能),阻碍 Li 枝晶生长(如 Li₆PS₅Cl₀.₃F₀.₇临界电流密度提升 2.6 倍);
    2. 氧化物掺杂形成 Li-In/Li-Sb 合金(低迁移能垒),促进 Li⁺均匀沉积(如 In-O 掺杂使界面电阻降低 3.5 倍);
  • 共掺杂协同增强界面机械强度与离子导通性,如 Bi-O 掺杂形成 Li-Bi 合金与 Li₂O 保护层,兼顾绝缘性与 Li⁺传输。

Li-Sb合金

研究通过在锂银辉石固态电解质 Li₆PS₅Cl 中掺杂锑(Sb)形成 Li–Sb 合金,显著提升全固态锂电池的界面稳定性。Sb 掺杂使电解质获得9.206 mS cm⁻¹ 的室温离子电导率,并在锂金属界面形成 Li–Sb 合金,促进均匀锂沉积,实现14.5 mA cm⁻² 的超高临界电流密度(CCD,硫化物电解质中最高),以及1900 小时(0.1 mA cm⁻²)和 900 小时(1.0 mA cm⁻²)的长循环稳定性,无锂枝晶穿透。此外,Sb 与硫的强键合增强了电解质的抗水解能力,空气暴露 30 分钟仅产生 0.7 cm³ g⁻¹ 的 H₂S 气体,验证了合金形成策略在提升界面稳定性和空气稳定性中的关键作用。

  1. 材料设计
    • 合成系列 Sb 掺杂电解质Li₆P₁₋ₓSbₓS₅Cl(x=0~0.08),其中 LPSC-0.04(x=0.04) 表现最佳。
    • Sb 取代 P 位点,形成 (P/Sb) S₄³⁻单元,导致晶格膨胀(a=11.047 Å vs 纯样 10.354 Å),利于 Li⁺迁移。

1. Li–Sb 合金如何提升界面稳定性?

答案: Li–Sb 合金在锂金属与电解质界面形成后,通过以下机制提升稳定性:

  • 均匀锂沉积:合金作为锂沉积的核位点,促进锂均匀成核,避免局部电流集中导致的枝晶生长;
  • 降低界面电阻:合金层保持良好的界面接触,减少循环中因体积变化产生的孔洞和裂纹,抑制钝化层形成;
  • 抑制副反应:Sb 的引入减少电解质中 P 与 Li 的直接反应,降低 Li₂S 等绝缘产物的生成,维持界面离子导通性。

2. 为何 Sb 掺杂能改善电解质的空气稳定性?

答案: 根据硬 - 软酸碱理论(HSAB),Sb⁵⁺(软酸)与 S²⁻(软碱)的键合强度高于 P⁵⁺与 S²⁻,具体表现为:

  • 抗水解能力增强:Sb-S 键能更高,抑制 H₂O 中 O²⁻(硬碱)取代 S²⁻,减少 H₂S 生成(暴露 30 分钟 H₂S 产量从 2.0 cm³ g⁻¹ 降至 0.7 cm³ g⁻¹);
  • 结构稳定性提升:DFT 计算显示,Sb 掺杂后 S 被 O 取代的反应能(ΔE)从 - 963 J mol⁻¹ 升至 - 698 J mol⁻¹,表明水解反应更难发生,晶体结构不易分解。

3. LPSC-0.04 的临界电流密度(CCD)为何显著高于纯样?

答案

  • 枝晶抑制机制

    :高 CCD(14.5 mA cm⁻² vs 纯样 0.75 mA cm⁻²)源于 Li–Sb 合金的形成:

    • 合金层作为物理屏障,阻碍锂枝晶穿透电解质;
    • 均匀的锂沉积减少局部应力集中,避免电解质裂纹形成,维持界面完整性;
    • 低电子电导率(Sb 掺杂降低电子传导)抑制枝晶的电子诱导生长,进一步提升 CCD。

调节硫的p带中心

研究通过 Sb/O 共掺杂调节 Li₆PS₅Cl 电解质中硫的 p 带中心,形成 SbS₄四面体,使 S-p 带中心下移,促进 Li/LPSC-SbO 界面原位生成稳定的 LiₓSbᵧS_z 界面相,抑制锂枝晶生长(Li 对称电池稳定循环超 4000 h),同时增强 SbS₄四面体与 Li 原子的相互作用,减少向 S₈的电荷转移,提升硫正极界面稳定性。O 掺杂提高了电解质的空气稳定性。基于 LPSC-SbO 的全固态锂硫电池在 0.1 C 下比容量达 932.6 mAh g⁻¹,150 次循环后容量保持率 83.7%,且 pouch 电池展现出良好的实际应用安全性。

二、研究策略:Sb/O 共掺杂调控 p 带中心

  1. 掺杂设计
    • Sb 替代 P:形成 SbS₄四面体,利用 Sb 与 P 的电负性和离子半径差异,降低 S-p 带中心(更远离费米能级)。
    • O 替代 S:提高电解质空气稳定性(HSAB 理论:硬碱 O²⁻替代软碱 S²⁻,抑制水解产生 H₂S)。

1. Sb/O 共掺杂如何同时改善锂负极和硫正极界面稳定性?

答案

  • 锂负极:Sb 掺杂形成 SbS₄四面体,S-p 带中心下移使导带靠近费米能级,促进 Li 向 S 提供电子,原位生成离子导电的 LiₓSbᵧS_z 界面相(如 Li₃Sb、LiSbS₂),均匀 Li 沉积并抑制枝晶。
  • 硫正极:S-p 带中心远离费米能级,增强 SbS₄四面体与 Li 原子的相互作用,减少 Li 向 S₈的电荷转移,抑制电解质分解,保持导电网络稳定。

2. LPSC-SbO 电解质的空气稳定性为何显著提升?

答案: O 掺杂通过硬碱替代软碱(O²⁻替代 S²⁻),依据 HSAB 理论,减少硫化物与水的反应活性。实验显示,LPSC-SbO 暴露 60 min 后 H₂S 释放量比 LPSC 减少 270%,X 射线衍射(XRD)和拉曼光谱(Raman)表明其结构无明显分解,离子电导率仅下降 22%(LPSC 下降 67.3%)。

3. LPSC-SbO 在全固态电池中的实际性能优势有哪些关键数据支撑?

答案

  • 循环稳定性:0.1 C 下 150 次循环容量保持 83.7%(LPSC 仅 50 次循环保持 53.9%)。
  • 高倍率性能:1 C 下比容量 396.3 mAh g⁻¹(LPSC 仅 179.4 mAh g⁻¹)。
  • 安全性: pouch 电池经弯曲、刺穿后仍稳定放电,初始容量 773.4 mAh g⁻¹,20 次循环后无明显衰减。

掺三价离子和氟离子

本文提出通过In³⁺取代 P⁵⁺、F⁻取代 Cl⁻的共掺杂策略,在锂银锗矿型硫化物电解质(Li5.7PS4.7Cl1.3)中引入InF3,制备了高性能硫化物电解质Li5.82P0.94In0.06S4.7Cl1.12F0.18(LPSC-InF)。该电解质在 25℃下具有2.5 mA/cm² 的临界电流密度,锂对称电池在 1 mA/cm² 下循环寿命超1000 小时,且对空气和有机溶剂表现出优异稳定性。通过浆料浇铸和热压工艺制备了35 μm 超薄电解质薄膜,离子电导率达 1.4 mS/cm,组装的全固态电池(如 LiCoO₂和 FeS₂正极)展现出长循环寿命和高能量密度(FeS₂体系达 410 Wh/kg),为超薄硫化物电解质薄膜的规模化生产提供了设计策略。

  • 掺杂策略
    • In³⁺取代 P⁵⁺:降低晶格能,增加 Li⁺空位,提升离子电导率;形成 Li-In 合金界面,抑制 Li 枝晶。
    • F⁻取代 Cl⁻:减小阴离子半径,调节晶格参数,增强化学稳定性(HSAB 原理:软酸 In³⁺与软碱 S²⁻结合更稳定)。
  • 最优组成Li5.82P0.94In0.06S4.7Cl1.12F0.18(x=0.06,LPSCInF),通过固相烧结法合成。
性能指标 原始 LPSC LPSCInF(x=0.06) 优势分析
离子电导率 4.8 mS/cm 5.6 mS/cm(块体) 1.4 mS/cm(35 μm 薄膜) In³⁺增加 Li⁺空位,降低扩散能垒(0.236 eV vs 原始 0.662 eV)
临界电流密度 1.0 mA/cm² 2.5 mA/cm² 抑制 Li 枝晶,提升电池功率密度
循环稳定性 75 小时短路 1 mA/cm² 下 > 1000 小时 0.5 mA/cm² 下 > 2000 小时 界面形成 LiF(电子绝缘)和 Li-In 合金(高 Li⁺扩散),均匀 Li 沉积
电子电导率 - (2.94×10^{-9} S/cm)(低电子导电抑制枝晶) -

4. 稳定性提升机制

  • 空气稳定性
    • H₂S 释放量降低:LPSCInF 在 60 分钟内释放 1.16 cm³/g,原始 LPSC 为 3.82 cm³/g。
    • 机制:F⁻增强 Li-F 键,减少 Li-O 键形成;In³⁺与 S²⁻结合稳定,抑制水解。
  • 溶剂稳定性
    • 离子电导率下降幅度小:甲苯中下降 8.75%(原始 37.5%),二氯甲烷 17.5%(原始 56.3%)。
    • 机制:In³⁺作为软酸减少与极性溶剂(硬碱)的反应,DFT 计算显示溶剂吸附能降低。

问题 1:In 和 F 共掺杂如何提升硫化物电解质的 Li 金属相容性?

答案

  • In³⁺取代 P⁵⁺形成 Li-In 合金界面,其 Li⁺扩散系数(10⁻⁸~10⁻⁶ cm²/s)远高于纯 Li 金属(5.69×10⁻¹¹ cm²/s),促进 Li⁺均匀沉积,降低成核过电位。
  • F⁻掺杂生成 LiF 界面层(带隙 7.4 eV),作为电子绝缘体阻断 SE 与 Li 的副反应,抑制枝晶生长。
  • 二者协同作用使临界电流密度提升至 2.5 mA/cm²,循环寿命超过 1000 小时(1 mA/cm²)。

问题 2:溶剂稳定性对硫化物电解质薄膜制备的意义是什么?如何通过掺杂实现?

答案

  • 意义:传统硫化物 SEs 与极性溶剂反应导致结构降解,限制浆料浇铸等溶液加工工艺。稳定的 SEs 可实现超薄薄膜(如 35 μm)的连续制备,降低电解质层厚度和重量,提升电池能量密度。

  • 掺杂机制

    • In³⁺(软酸)替代 P⁵⁺(硬酸),减少与极性溶剂(硬碱)的 HSAB 反应,DFT 计算显示溶剂吸附能从 - 0.41 eV(原始)降至 - 0.12 eV(LPSCInF)。
  • F⁻增强晶格稳定性,抑制 S²⁻与溶剂中亲电 C 原子的反应,Raman 和 XRD 证明掺杂后 SEs 在溶剂中无明显分解产物。

问题 3:超薄电解质薄膜(35 μm)相比传统厚膜(>500 μm)的核心优势是什么?如何平衡薄膜厚度与离子电导率?

答案

  • 核心优势

    • 厚度减少 90% 以上,降低非活性材料占比,提升电池能量密度(FeS₂体系达 410 Wh/kg)。
    • 缩短 Li⁺扩散路径,结合高电导率(1.4 mS/cm),实现高倍率性能(1 C 时容量保持率 80%)。
  • 平衡策略

    • 通过 PIB binder 增强薄膜机械强度,填充颗粒间隙,保持离子导电通路连续性。
    • 优化掺杂浓度(x=0.06),在晶格膨胀(In³⁺)和阴离子半径减小(F⁻)间取得平衡,确保薄膜态电导率损失可控(块体 5.6 mS/cm → 薄膜 1.4 mS/cm),同时满足机械柔韧性。

阴离子对锂离子扩散的影响

研究通过基于神经网络势(NNP)的机器学习模拟,探究了锂银矿固体电解质(Li₆PS₅X, X=Cl/Br)中阴离子对锂离子扩散的影响。将锂框架分为八面体笼(Oₕ笼)和走廊笼,发现笼中心的硫离子通过更强的库仑相互作用束缚锂离子,导致其局部化。通过分子动力学模拟揭示离子扩散系数(D)与笼中心卤素离子比例的乘积成正比(D ∝ Rₓ,ₒₕ × Rₓ,ₙₒᵣᵣᵢ𝒹ₒᵣ),提出通过减少笼中心硫离子占据、优化卤素掺杂比例来提升锂离子电导率,为固态电解质的离子传输机制和性能优化提供了理论基准。

详细总结

1. 研究背景与目标

  • 固态电解质(SSEs)重要性:锂银矿(Li₆PS₅X, X=Cl/Br)因高离子电导率、加工性和稳定性,成为下一代电池的核心材料,但阴离子对锂离子扩散的影响机制尚不明确。
  • 传统方法局限:密度泛函理论(DFT)计算成本高,难以模拟大尺度结构和长时间过程,需借助 ** 神经网络势(NNP)** 结合分子动力学(MD)扩展研究能力。

2. 晶体结构与笼分类

  • 结构特征

    :Li₆PS₅Cl 为 F43m 空间群,包含 4a 位 Cl⁻、4b 位 PS₄³⁻、4d 位 S²⁻,Li⁺位于 24g 位,形成两类笼结构:

    • Oₕ笼(八面体笼):以 4d 位阴离子(S²⁻/Cl⁻)为中心,Li⁺形成八面体框架。
    • 走廊笼(立方八面体笼):以 4a 位阴离子(Cl⁻/S²⁻)为中心,连接 Oₕ笼,促进跨笼扩散。
  • 阴离子无序:硫氯反位缺陷(Rₐₛ)导致阴离子在笼中心交换,影响 Li⁺分布(如 Rₐₛ=0 时 S²⁻占据 4d 位,Li⁺偏向 24g 位;Rₐₛ=1 时 S²⁻占据 4a 位)。

3. 分子动力学模拟与关键数据

  • 扩散系数(D)变化
    • Rₐₛ=0 时,D=9.31×10⁻¹⁰ cm²/s(300 K),因 S²⁻在 Oₕ笼中心强束缚 Li⁺。
    • Rₐₛ=0.5 时,D=1.34×10⁻⁷ cm²/s(300 K),卤素均匀分布,Li⁺局部化最弱。
    • Rₐₛ=1 时,D=8.06×10⁻⁹ cm²/s(300 K),S²⁻转移至走廊笼,重新束缚 Li⁺。
  • 激活能(Eₐ)分析
    • Oₕ笼逃逸 Eₐ:Rₐₛ=0 时最高 0.23 eV,随 Rₐₛ增加降至 0.04 eV(Rₐₛ=1)。
    • 走廊笼逃逸 Eₐ:Rₐₛ=0 时最低 0.02 eV,随 Rₐₛ增加升至 0.27 eV(Rₐₛ=1)。
    • 瓶颈 Eₐ由两类笼中较高值决定,与扩散系数趋势一致。

4. 统计分析与局部化机制

  • 自相关因子(f)

    :量化 Li⁺返回原位的倾向,f 越低表示局部化越强。

    • Rₐₛ=0/1 时,f≈0.05,Li⁺高度局部化;Rₐₛ=0.5 时,f≈0.15,局部化最弱。
  • 轨迹分析:Rₐₛ=0 时 Li⁺在 Oₕ笼形成孤立圆形轨迹;Rₐₛ=1 时在走廊笼形成菱形轨迹,均显示局部化;中间值时轨迹连通,促进跨笼扩散。

5. 卤素掺杂策略与公式推导

  • 核心公式

    :离子扩散系数与笼中心卤素比例的乘积成正比,

    D ∝ Rₓ,ₒₕ × Rₓ,ₙₒᵣᵣᵢ𝒹ₒᵣ

    (X=Cl/Br)。

    • Rₓ,ₒₕ:Oₕ笼中心卤素比例(=Rₐₛ),Rₓ,ₙₒᵣᵣᵢ𝒹ₒᵣ:走廊笼中心卤素比例(=1-Rₐₛ)。
    • 最佳条件:Rₐₛ=0.5 时,乘积最大(0.25),对应最高 D。
  • 实验验证:不同卤素掺杂浓度的电导率与公式预测一致,证实阴离子配置的关键作用。

6. 结论与意义

  • 理论突破:首次通过 NNP 模拟揭示两类笼结构中阴离子对 Li⁺局部化的影响,补充传统 DFT 的尺度限制。
  • 应用指导:提出通过调控笼中心硫 / 卤素比例(如卤素掺杂)降低 Li⁺局部化,提升电导率,为固态电解质设计提供量化基准。
  • 技术影响:推动高安全性、高能量密度固态电池的研发,助力储能技术进步。

关键问题与答案

1. 基于 NNP 的模拟方法相比传统 DFT 有何优势?

答案:NNP 模拟通过机器学习拟合 DFT 数据,可处理大尺度原子模型(如 256 个晶胞、3326 个原子)和长时间动力学过程(3 ns),显著降低计算成本,同时保持高精度(验证集均方根误差 < 10 meV/atom)。相比之下,DFT 因计算量限制,难以研究复杂缺陷和高浓度掺杂体系,而 NNP 能够捕捉 Li⁺在真实无序结构中的扩散行为,为实验提供更贴近实际的理论预测。

2. 两类笼结构(Oₕ笼与走廊笼)对锂离子扩散的影响有何差异?

答案

  • Oₕ笼:以 4d 位阴离子为中心,Li⁺形成八面体配位。硫离子占据时(Rₐₛ=0),Li⁺因强库仑作用(Li-S 键长 2.45 Å)被束缚,逃逸激活能高达 0.23 eV,导致局部化;卤素占据时束缚减弱,促进 Li⁺跨笼迁移。
  • 走廊笼:以 4a 位阴离子为中心,连接多个 Oₕ笼,结构更开放。硫离子占据时(Rₐₛ=1),Li⁺在走廊笼内局部化,逃逸激活能升至 0.27 eV;卤素占据时(Rₐₛ=0),Li⁺易逃逸(激活能 0.02 eV),成为快速扩散通道。 两者共同决定 Li⁺的整体迁移速率,需平衡双笼中心的卤素比例以最大化扩散系数。

3. 为什么卤素掺杂能提高锂离子电导率?其优化的理论依据是什么?

答案:卤素掺杂通过取代笼中心的硫离子,减少 S²⁻对 Li⁺的强束缚。理论依据为D ∝ Rₓ,ₒₕ × Rₓ,ₙₒᵣᵣᵢ𝒹ₒᵣ,即扩散系数与双笼中心卤素比例的乘积成正比:

  • 当卤素(Cl/Br)占据 Oₕ笼和走廊笼中心时,Li⁺局部化减弱,跨笼扩散路径连通(如 Rₐₛ=0.5 时,两笼卤素比例均为 50%,乘积最大)。
  • 实验中,电导率随该乘积增加呈线性上升趋势,证实通过调控卤素掺杂比例(如 Li₆PS₅Cl₀.₅Br₀.₅),可有效降低 Li⁺的激活能和局部化程度,从而提升电导率。 该策略为实验设计提供了明确的量化指标,避免过度掺杂导致副产物(如 LiCl)生成。

Brain Storm

一些疑问

  • 画出离子半径的元素周期表以方便根据HSAB来进行design

  • 如何衡量离子及离子团的空间位阻(体积)?

  • (Li5.4PS4.4Cl1.4I0.2)固态电解质膜是什么?

  • 掺入大半径的离子会导致x增加

    • Li6PS5Cl——NO
    • Li5.5PS4.5Cl1.5——9.4(sintering)
    • Li5.3PS4.3Cl0.7Br——26
      • 350°C 合成的样品结晶度低、杂质多,离子电导率仅 6.5 mS/cm
    • Li5.4PS4.4Cl1.4I0.2——11.49
  • 粉末颗粒体积与结晶度的关系?

  • 热处理(快速退火)可以促进阴离子的无序性?

  • 为什么氧掺杂可以提高稳定性?

    • 形成更强的 P-O 键
  • 要怎么降低电子电导率

  • 高熵体系

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CAN EUROPE STOP ELON MUSK ?

During an American election, a rich man can hand out $1 million checks to prospective voters. Companies and people can use secretly funded “dark money” nonprofits to donate unlimited money, anonymously, to super PACs, which can then spend it on advertising campaigns. Podcasters, partisans, or anyone, really, can tell outrageous, incendiary lies about a candidate. They can boost those ==falsehoods== through targeted online advertising. No special courts or election rules can stop the ==disinformation== from spreading before voters see it. The court of public opinion, which over the past decade has seen and heard everything, no longer cares. U.S. elections are now a political Las Vegas: Anything goes.

But that’s not the way elections are run in other countries. In Britain, political parties are, at least during the run-up to an election, limited to spending no more than £54,010 per candidate. In Germany, as in many other European countries, the state funds political parties, ==proportionate== to their number of elected ==parliamentarians== , so that politicians do not have to depend on, and become ==corrupted== by, wealthy donors. In Poland, courts ==fast-track== election-related libel cases in the weeks before a vote in order to discourage people from lying.

Nor is this unique to Europe. Many democracies have state or public media that are obligated, at least in principle, to give equal time to all sides. Many require political donations to be transparent, with the names of donors listed in an online registry. Many have limits on political advertising. Some countries also have rules about hate speech and indict people who break them.

Countries apply these laws to create conditions for fair debate, to build trust in the system, and to inspire confidence in the winning candidates. Some democracies believe that transparency matters—that voters should know who is funding their candidates, as well as who is paying for political messages on social media or anywhere else. In some places, these rules have ==a loftier goal== : to prevent the rise of anti democratic ==extremism== of the kind that has ==engulfed== democracies— and especially European democracies— in the past.

But for how much longer can democracies pursue these goals? We live in a world in which ==algorithms== controlled by American and Chinese ==oligarchs== choose the messages and images seen by millions of people; in which money can move through secret bank accounts with the help of ==crypto== schemes; and in which this dark money can then boost anonymous social-media accounts with the aim of shaping public opinion. In such a world, how can any election rules be enforced? If you are ==Albania== , or even the United Kingdom, do you still get to set the parameters of your public debate? Or are you now forced to be Las Vegas too?

ALTHOUGH IT’S EASY to get distracted by the schoolyard nicknames and ==irresponsible== ==pedophilia== accusations that Elon Musk ==flings== around, these are the real questions posed by his open, aggressive use of X to spread false information and promote extremist and anti-European politicians in the U.K., Germany, and elsewhere. The integrity of elections— and the possibility of debate ==untainted== by misinformation injected from abroad—is equally challenged by TikTok, the Chinese platform, and by Mark Zuckerberg’s Meta, whose ==subsidiaries== include Facebook, Instagram, WhatsApp, and threads. TikTok says the company does not accept any paid political advertising. Meta, which announced in January that it is abandoning ==fact-checking== on its sites in the U.S., also says it will continue to comply with European laws. But even before Zucker berg’s radical policy change, these promises were empty. Meta’s ==vaunted== content ==curation== and moderation have never been transparent. Nobody knew, and nobody knows, what exactly Facebook’s algorithm was promoting and why. Even an occasional user of these platforms encounters ==spammers== , ==scammers== , and ==opaque== accounts running foreign influence operations. No guide to the algorithm, and no real choices about it, are available on Meta products, X, or TikTok.

In truth, no one knows if any platforms really comply with political-funding rules either, because nobody outside the companies can fully monitor what happens online during an intense election campaign—and after the voting has ended, it’s too late. According to ==declassified== Romanian-intelligence documents, someone allegedly spent more than $1 million on TikTok content in the 18 months before an election in support of a Romanian presidential candidate who declared that he himself had spent nothing at all. In a belated attempt to address this and other alleged discrepancies, a Romanian court canceled the first round of that election, a decision that itself damaged Romanian democracy.

Not all of this is new. ==Surreptitious== political-party funding was a feature of the Cold War, and the Russian government has continued this practice, sometimes by offering deals to foreign businesspeople close to pro-Russian politicians. Press moguls with international political ambitions are hardly a ==novelty== . Rupert Murdoch, an Australian who has U.S. ==citizenship== , has long played an outsize role in U.K. politics through his media companies. John Major, the former British prime minister and Conservative Party leader, has said that in 1997, Murdoch threatened to pull his newspapers’ support unless the prime minister pursued a more anti-European policy. Major refused. Murdoch has said, “I have never asked a prime minister for anything,” but one of his Conservativeleaning ==tabloids== , the Sun, did endorse the Labour Party in the next election. Major lost.

That incident now seems almost ==quaint== . Even at the height of its influence, the print edition of the Sun sold 4 million copies a day. More to the point, it operated, and still does, within the ==constraints== of U.K. rules and regulations, as do all broadcast and print media. Murdoch’s newspapers take British ==libel== and ==hatespeech== laws into consideration when they run stories. His business strategy is necessarily shaped by rules limiting what a single company can own. After his journalists were accused of hacking phones and bribing police in the early 2000s, Murdoch himself had to testify before an investigative commission, and he closed down one of his tabloids for good.

Social media not only has far greater reach—Musk’s personal X account has more than 212 million followers, giving him enormous power to set the news agenda around the world— ==it also exists outside the legal system== . Under the American law known as Section 230, passed nearly three decades ago, internet platforms are not treated as publishers in the U.S. In practice, neither Facebook nor X has the same legal responsibility for what appears on their platforms as do, say, The Wall Street Journal and CNN. And this, too, has consequences: Americans have created the information climate that other countries must accept, and this allows ==deceptive== election practices to thrive. If countries don’t have their own laws, and until recently most did not, Section 230 ==effectively== requires them to treat social-media companies as if they exist outside their legal systems too.

Brazil broke with this pattern last year, when a judge demanded that Musk comply with Brazilian laws against spreading misinformation and political extremism, and forced X offline until he did. Several European countries, including the U.K., Germany, and France, have also passed laws designed to bring the platforms into compliance with their own legal systems, mandating fines for companies that violate hatespeech laws or host other illegal content. But these laws are controversial and hard to enforce. Besides, “illegal speech” is not necessarily the central problem. No laws prevented Musk from interviewing Alice Weidel, a leader of the ==far-right== Alternative for Germany (AfD) party, on X, thereby providing her with a huge platform, available to no other political candidate, in the month before a national election. the interview, which included several ==glaringly== false statements (among others, that Weidel was the “leading” candidate), was viewed 45 million times in 24 hours, a number far beyond the reach of any German public or private media.

ONLY ON INSTITUTION on the planet is large enough and powerful enough to write and enforce laws that could make the tech companies change their policies. Partly for that reason, the European Union may soon become one of the Trump administration’s most ==prominent== targets. In theory, the EU’s Digital Services Act, which ==took full effect== last year, can be used to regulate, fine, and, in extreme circumstances, ban internet companies whose practices ==clash with== European laws. Yet a primary ==intent== of the act is not ==punitive== , but rather to open up the platforms: to allow ==vetted== researchers access to platform data, and to give citizens more transparency about what they hear and see. Freedom of speech also means the right to receive information, and at the moment social-media companies operate behind a curtain. We don’t know if they are promoting or suppressing certain points of view, ==curbing== or encouraging ==orchestrated== political campaigns, discouraging or provoking violent riots. Above all, we don’t know who is paying for misinformation to be spread online.

In the past, the EU has not hesitated to try to apply European law to tech companies. Over the past decade, for example, Google has faced three fines totaling more than $8 billion for breaking antitrust law (though one of these fines was ==overturned== by the EU’s General Court in 2024).

In November, the European Commission Šned Meta more than $800 million for unfair trade practices. But for how much longer will the EU have this authority? In the fall, J. D. Vance issued an extraordinarily ==unsubtle== threat, one that is frequently repeated in Europe. “If NATO wants us to continue supporting them and NATO wants us to continue to be a good participant in this military alliance,” Vance told an interviewer, “why don’t you respect American values and respect free speech?” Mark Zuckerberg, echoing Vance’s ==misuse== of the expression free speech to mean “freedom to conceal company practices from the public,” put it even more ==crudely== . In a conversation with Joe Rogan in January, Zuckerberg said he feels “optimistic” that President Donald Trump will intervene to stop the EU from enforcing its own ==antitrust== laws: “I think he just wants America to win.”

Does America “winning” mean that European democracies, and maybe other democracies, lose? Some European politicians think it might. Robert Habeck, the German vice ==chancellor== and a leader of that country’s Green Party,

believes that Musk’s ==frenzies== of political activity on X aren’t the random ==blurts== of an ==addled== mind, but rather are “logical and systematic.” In his New Year’s address, Habeck said that Musk is deliberately “strengthening those who are weakening Europe,” including the explicitly anti-European AfD. This, he believes, is because “a weak Europe is in the interest of those for whom regulation is an inappropriate limitation of their power.”

Until recently, Russia was the most important state seeking to ==undermine== European institutions. Vladimir Putin has long disliked the EU because it restricts Russian companies’ ability to intimidate and ==bribe== European political leaders and companies, and because the EU is larger and more powerful than Russia, whereas European countries on their own are not. Now a group of American oligarchs also want to undermine European institutions, because they don’t want to be regulated—and they may have the American president on their side. Quite soon, the European Union, along with Great Britain and other democracies around the world, might find that they have to choose between their ==alliance== with the United States and their ability to run their own elections and select their own leaders without the pressure of aggressive outside manipulation. ==Ironically== , countries, such as Brazil, that don’t have the same deep military, economic, and cultural ties to the U.S. may and it easier to maintain the ==sovereignty== of their political systems and the transparency of their information ecosystems than Europeans.

A ==crunch== point is ==imminent== , when the European Commission finally concludes a year-long investigation into X. ==Tellingly== , two people who have advised the commission on this investigation would talk with me only off the record, because the potential for ==reprisals== against them and their organizations— whether it be online ==trolling== and harassment or lawsuits— is too great. Still, both advisers said that the commission has the power to protect Europe’s sovereignty, and to force the platforms to be more transparent. “¦e commission should look at the ==raft== of laws and rules it has available and see how they can be applied,” one of them told me, “always remembering that this is not about taking action against a person’s voice. ¦is is the commission saying that everyone’s voice should be equal.”

At least in theory, no country is obligated to become ==an electoral Las Vegas== , as America has. Global democracies could demand greater transparency around the use of algorithms, both on social media and in the online-advertising market more broadly. ¦ey could other consumers more control over what they see, and more information about what they don’t see. ¦ey could enforce their own campaign-funding laws. These changes could make the internet more open and fair, and therefore a better, safer place for the exercise of free speech. If the chances of success seem narrow, it’s not because of the lack of a viable legal framework— rather it’s because, at the moment, ==cowardice== is as ==viral== as one of Musk’s ==tweets== .

Vocabulary, Phrases and Sentences

Word Chinese Definition Phonetic Symbol
incendiary 煽动性的 /ɪnˈsendieri/
falsehood 谎言 /ˈfɔːlshʊd/
disinformation 虚假信息 /ˌdɪsɪnfəˈmeɪʃn/
run-up 前期;准备阶段 /ˈrʌn ʌp/
corrupt 腐败的 /kəˈrʌpt/
fast-track 快速推进 /ˈfæst træk/
be obligated 有义务 /ˈbiː ˈɒblɪɡeɪtɪd/
indict 指控 /ɪnˈdaɪt/
a loftier goal 更高的目标 /ə ˈlɔːftiə ˈɡəʊl/
extremism 极端主义 /ɪkˈstriːmɪzəm/
engulfed 吞没 /ɪnˈɡʌlvd/
algorithms 算法 /ˈælɡərɪðəmz/
oligarch 寡头 /ˈɒlɪɡɑːk/
crypto 加密的 /ˈkrɪptəʊ/
irresponsible 不负责任的 /ˌɪrɪˈspɒnsəbl/
fling 扔;抛 /ˈflɪŋ/
untainted 无污点的
subsidiaries 子公司 /ˈsʌbsɪdɪriːz/
It is abandoning fact-checking on its sites in the U.S. 它正在放弃对美国网站的事实核查
vaunted 吹嘘的 /ˈvɔːntɪd/
moderation 适度;节制 /ˌmɒdəˈreɪʃn/
curation 策划;挑选 /ˌkjʊəˈreɪʃn/
spammer 垃圾邮件发送者 /ˈspæmə(r)/
scammer 骗子 /ˈskæmə(r)/
opaque 不透明的 /əʊˈpeɪk/
declassified 解密的 /ˌdiːˈklæsɪfaɪd/
allegedly 据称 /əˈledʒɪdli/
belated 迟来的 /bɪˈleɪtɪd/
discrepancies 差异 /ˌdɪskrepənsiːz/
surreptitious 偷偷摸摸 /ˌsʌrəpˈtɪʃəs/
novelty 新奇 /ˈnɒvlti/
tabloid 小报 /ˈtæblɔɪd/
endorse 支持;认可 /ɪnˈdɔːs/
quaint 古雅的 /ˈkweɪnt/
constraint 限制 /kənˈstreɪnt/
libel 诽谤 /ˈlaɪbl/
hate-speech 仇恨言论 /ˈheɪt spiːtʃ/
It also exists outside the legal system
deceptive 欺骗性的 /dɪˈseptɪv/
effectively 事实上 /ɪˈfektɪvli/
far-right 极右翼 /ˈfɑː raɪt/
glaringly 明显地 /ˈɡleərɪŋli/
prominent 突出的 /ˈprɒmɪnənt/
take full effect 完全生效 /ˈteɪk fʊl ˈɪfekt/
clash with 与……冲突 /ˈklæʃ wɪð/
intent 意图 /ˈɪntent/
punitive 惩罚性的 /ˈpjuːnətɪv/
vetted 审查 /ˈvetɪd/
curbing 控制 /ˈkɜːbɪŋ/
orchestrated political campaigns 精心策划的政治运动 /ˈɔːkɪstreɪtɪd pəˈlɪtɪkl kæmˈpeɪnz/
riot 暴乱 /ˈraɪət/
overturn 推翻 /ˈəʊvətɜːn/
unsubtle 不微妙的 /ˈʌnˈsʌtl/
misuse 滥用 /ˈmɪsjuːz/
crudely 粗糙地 /ˈkruːdli/
antitrust 反垄断的 /ˈæntiˈtrʌst/
chancellor 总理;大臣 /ˈtʃɑːnsələ(r)/
frenzy 狂热 /ˈfrenzi/
blurt 脱口而出 /ˈblɜːt/
addled 糊涂的 /ˈædld/
undermine 破坏 /ˈʌndəˈmaɪn/
bribe 贿赂 /ˈbraɪb/
alliance 联盟 /ˈælaɪəns/
ironically 讽刺地 /aɪˈrɒnɪkli/
sovereignty 主权 /ˈsɒvrənti/
crunch 嘎吱作响;关键时刻 /ˈkrʌntʃ/
imminent 即将来临的 /ˈɪmɪnənt/
tellingly 有效地;显著地 /ˈtelɪŋli/
reprisals 报复 /ˈreprɪzlz/
troll 网络喷子 /ˈtrəʊl/
raft 大量 /ˈrɑːft/
an electoral Las Vegas 常被用来形容一些充满变数、热闹且带有投机性质的场景 /ˈæn ɪˈlektərəl ˈlæz ˈveɪɡəs/
cowardice 懦弱 /ˈkaʊədɪs/
viral 病毒式的 /ˈvaɪrəl/
tweet 推文 /ˈtwiːt/

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Word Chinese Definition
mute 沉默的
reckless 鲁莽的
ordeal 磨难
chronicle 编年史
warranty 担保
==eligibility== 资格
==surveillance== 监视,监控
==dissent== 异议
==conviction== 信念
turnout 投票人数,出席人数
==ammunition== 弹药
convoy 车队
sergeant 中士,警官
==verdict== 判决
==akin== 相似的,类似的
retarded 智力迟钝的
stipulate 规定
depreciate 贬值,贬低
whereabout 下落,行踪(复数形式whereabouts)
faction 派别,小集团
premium 保险费,额外费用,溢价
coup 政变,成功之举
trench 战壕,沟
motor 发动机,马达,机动车
cavity 洞,腔
consecutive 连续的,连贯的
cram 塞满,挤满,填塞,死记硬背
equitable 公平的,公正的
turnout 投票人数,出席人数
tangle 使缠结,使混乱,纠结
imminent 即将发生的,临近的
corporal 肉体的,身体的,下士
elaboration 精心制作,详尽阐述
grim 严峻的,冷酷的,糟糕的
arbitrate 仲裁,公断
venue 举办地点,会场,审判地
frantic 疯狂的,慌乱的
excerpt 摘录,节录
tropic 热带地区,回归线
anguish 痛苦,苦恼
detention 拘留,监禁,扣押
benevolence 仁慈,善举,仁爱
aspire 渴望,追求,有志于
bewilderment 困惑,迷惘
deportation 驱逐出境
beckon 招手,召唤,吸引
beetle 甲虫,甲壳虫,突出,用槌打
analogous 相似的,类似的
confide 吐露,倾诉,信赖
conceit 自负,骄傲自大,巧妙的构思
strangle 扼死,勒死,抑制,使窒息
bead 珠子,汗珠,有孔小珠
beak 鸟嘴,鹰钩鼻
bleach 漂白,使褪色,变白
deductive 演绎的,推论的
congregate 聚集,集合
bleak 荒凉的,萧瑟的,黯淡的
stagnant 停滞的,不流动的,不景气的
dub 给……起绰号,把……称为,配音,复制
uprising 起义,暴动,反抗
artifact 人工制品,手工艺品
tribe 部落,族(尤指同一语言的)
envisage 设想,想象,正视
stance 立场,态度,姿势
crunch 嘎吱嘎吱的声音, crunch 关键时刻,困境,紧缩
wholesome 有益健康的,健康的,有益的
denounce 谴责,指责,告发
constituency 选区,支持者,(一批)顾客
detain 拘留,扣押,耽搁
degeneration 退化,恶化,堕落
deterrent 威慑物,制止物
ensue 接着发生,因而产生
envoy 使者,使节,代表
alignment 队列,成直线,结盟,联合
unanimous 全体一致的,无异议的
counter 柜台,计数器,反对的,相反的,反击,反驳
assoddsrted 各种各样的,混杂的,什锦的
demographic 人口统计学的,特定人群的
clan 宗族,家族,氏族
vicious 恶毒的,恶意的,凶猛的,剧烈的
cloak 披风,斗篷,掩盖,掩饰
stun 使震惊,使昏迷,打昏
curfew 宵禁,宵禁令
disarm 解除武装,裁军,消除(敌意、疑虑等)
eloquence 口才,雄辩,说服力
ventilate 使通风,使空气流通,公开表达,发泄
stump 树桩,残肢,难住,使为难
temperament 气质,性情,性格
elapse (时间)过去,消逝
clergy 神职人员,牧师,教士
esteem 尊重,敬重, esteem 认为,把……看作
enlist 入伍,参军,征募,谋取(帮助、支持等)
discourse 演讲,论述,谈话,话语
envelop 包围,笼罩,包住
discern 看出,觉察出,识别,辨别
flutter 飘动,挥动,颤动,flutter (心脏)快速跳动,flutter 不安,紧张
superintendent 主管人,负责人,监督人,警长
syndicate 企业联合,辛迪加, syndicate (通过报业联合组织)出售(稿件)
convene 召集,召开,集合
connotation 内涵,含义,隐含意义
counterfeit 伪造的,假冒的,赝品,伪造,仿造
complement 补充,补足,补充物,补足语
hop 跳跃,单足跳, hop 快速离开, hop (飞机、直升机等)起飞
stark 光秃秃的,荒凉的, stark 严酷的,赤裸裸的, stark 完全的,十足的
shatter 粉碎,破碎,使破灭,使震惊
emancipate 解放,使摆脱束缚
preside 主持,担任主席
tread 踩,踏, tread (小心)行事, tread (在……上)行走
turmoil 混乱,骚乱,动荡
humiliation 羞辱,耻辱
stalk 茎,梗, stalk 悄悄地跟踪,追踪, stalk 昂首阔步地走
indefinite 不确定的,无限期的,模糊的
infringe 侵犯,违反, infringe on/upon 侵犯(权利等),违反(规定等)
ingenious 有独创性的,别出心裁的, ingenious 精巧的,巧妙的
badge 徽章,证章,标志,象征
redundant 多余的,过剩的,被解雇的, redundant 冗余的(计算机用语)
integral 不可或缺的,重要的, integral 完整的,整体的
intuition 直觉
intricate 错综复杂的,复杂精细的
intrinsically 本质上,内在地
sanctuary 避难所,庇护所,圣堂,神殿
infliction 痛苦,折磨,施加
leverage 影响力,杠杆作用, leverage 利用, leverage 给(某物)用杠杆力量
grill 烤架,烧烤, grill 盘问,审问
breach 违反,违背, breach 缺口,裂缝, breach of 违反,违背
plight 困境,苦境, plight 宣誓,保证
lieutenant 陆军中尉,海军上尉,副职官员
concede 承认,让步, concede to 向……让步
certify 证明,证实, certify that 证明……, certify sb/sth as 证明某人/某物为……
salvage 打捞,营救, salvage 抢救出的财物, salvage 挽回,挽救
cholesterol 胆固醇
loot 抢劫,掠夺, loot 战利品,掠夺物
rein 缰绳, rein 控制,掌管, rein in 控制,约束
interrogation 审问,审讯, interrogation 讯问,质问
ponder 仔细考虑,琢磨, ponder on/over/about 思考,考虑
besiege 围攻,包围, besiege with 用……围攻, besiege with 被……困扰
reshuffle 重新洗牌,改组, reshuffle of 对……的改组
magistrate 地方法官,治安官
inventory 存货清单,财产清单,详细目录, inventory 盘点,清查
corridor 走廊,通道
chunk 大块,厚块, chunk of 大量的,一大块……
bust 半身像,胸部,胸围, bust 打破,打碎, bust 开除,解雇
renowned 著名的,有名的
solicit 征求,请求, solicit for 为……征求, solicit 勾引,招揽(生意)
ration 定量,配给量, ration 配给,定量供应, ration out 分配,分发
entail 需要,使承担, entail on/upon 使某人承担,使某人蒙受
midwife 助产士,接生婆
trillion 万亿,兆
oar 桨,橹
amass 积累,积聚, amass wealth/power 积累财富/权力
frantically 疯狂地,拼命地
logistics 后勤,物流
militia 民兵组织,民兵
loot 抢劫,掠夺, loot 战利品,掠夺物
destiny 命运,天命, destiny 注定, destiny to 注定要……
opaque 不透明的,晦涩的,难懂的
cape 披肩,披风,海角,岬
obscurity 默默无闻,无名, obscurity 晦涩,难懂
parish 教区, parish (英国)乡村的行政区域
pact 条约,协定, pact between/with 与……之间的条约/协定
overt 公开的,明显的
foe 敌人,仇敌
cardinal 基本的,主要的, cardinal 红衣主教
delicacy 佳肴,美味, delicacy 精致,细微, delicacy of 对……的敏感
patrol 巡逻,巡查, patrol of 在……巡逻, patrol 巡逻队,巡逻车
parole 假释, parole on 在……假释期间, parole 誓言,诺言
peddle 叫卖,兜售, peddle drugs/gossip 贩卖毒品/传播流言蜚语
partition 分隔物,隔墙, partition between/of 在……之间的分隔, partition 分割,划分
implement 实施,执行, implement plan/policy 实施计划/政策, implement 工具,器具
rear 后部,后面, rear of 在……的后部, rear 饲养,养育, rear 举起,抬起
whereas 然而,但是,鉴于
poise 保持(某种姿势),使平衡, poise 沉着,镇定, poise on 在……上保持平衡
indebted 感激的, indebted to 感激……, indebted for 因……而感激
slum 贫民窟, slum 去贫民窟, slum around (在贫民窟等贫困地区)闲逛
polytechnic 理工专科学校, polytechnic education 理工教育
plaintiff 原告
refute 驳斥,反驳, refute argument/theory 驳斥论点/理论
peg 钉子, peg 用钉子钉, peg 固定, peg 限定(价格、工资等), peg at 把……限定在……
retort 反驳,回嘴, retort to 对……进行反驳, retort with 用……反驳
formulate 制定,规划, formulate policy/plan 制定政策/计划, formulate 确切表达,阐述
incur 引起,招致, incur cost/debt 引起费用/招致债务
reassure 使放心,使消除疑虑, reassure sb about/over 使某人对……放心
pending 待定的,未决的, pending on/upon 取决于……, pending 在……期间,直到……为止
excerpt 节选
whereabouts 下落
diesel 柴油机
toil 辛劳
antagonism 对抗情绪
batter 面糊
faction 派系
flank 侧翼
antonym 反义词
stoop 弯腰
premiuim 保险费
stipulate 规定
corporal 下士
forfeit 没收
formidable 强大的
wield 挥舞
trickle 涓涓细流
bout 拳击
anguish 痛苦
yacht 游艇
deplore 痛惜
secular 世俗的
deport 驱逐
astray 迷路
allude 暗指
stake 股份
brood 忧思
analogue 模拟
bloc 集团
aspire 渴望
atrocity 残忍
strangle 勒死
solidarity 团结一致
transcend 超越
detention 拘留
brigade 队列
agravate 恶化
bleak 暗淡的
stagnant 停滞不前的
tribute 贡品
doctrine 教条的
apprentice 学徒
wholesome 有益健康的
topple 颠覆
affiliation 附属
artery 动脉
slump 下跌
counter 反驳
conceive 设想
slack 懈怠的
clog 堵塞物
appraise 评估
eloquence 口才
subsidy 补贴
temperament 气质
elapse 流逝
deadlock 僵局
coalition 合作
trophy 奖杯
eccentric 古怪的
dissident 持不同意见的
divine 神圣的
vogue 时髦
elicit 引导
stipulation 契约
rigorous 严厉的
grill 烤架
grope 摸索
hitherto 目前为止
fringe 刘海
brink 边缘
advent 到来
inflict 加害于
infringe 侵害
interim 暂时的
jelly 果冻
ingenious 有独创性的
vicinity 附近
lawsuit 诉讼
majesty 帝王
indigenous 土生土长的
inmate 囚犯
lenient 宽容的
attentive 专心的
ascribe
maligant 恶性的
lyrical 感情丰富的
martyr 烈士
soothe 平静
medieval 中世纪的
reshuffle 重新洗牌
magistrate 地方执法官
menace 威胁
bust 打破
entail 继承
midwife 接生婆
frantically 疯狂的
wither 枯萎
obsess 迷恋
symposium 专题研讨会
peg 挂钩
rear 抚养
retort 反驳
nurture 培养
massacre 大屠杀
divert 转移
obstruct 妨碍
obscurity 默默无闻
delicacy 佳肴
disruptive 创新的
poultry 家禽
slum 贫民窟
plantiff 起诉
incur 引起
jack 千斤顶
quest 探索
pharmaceutical 制药的
compassionate 同情心的
premise 前提
counsel 律师
ratify 批准
endow 赋予
endorse 支持
prosecute 起诉
relentless 无情的
prone 易于
shrewd 精明的
disposition 排列
rigor 严谨
crouch
stray 迷失的
venue 发生地点
decree 法令
corporal 身体上的
corpse 尸体
wield 使用
deplore 惋惜
ascendance 优势
forfeit 丧失
appal 使震惊
solidarity 团结一致
asylum 庇护
detention 拘留
stigma 耻辱
enlist 应募
entrust 委托
discreet 谨慎的
counterfeit 仿制品
counteraction 反抗
amiable 和蔼的
discord 不和
subsistence 自给自足的,生存的
despise 轻蔑
dispatch 派送
wholesale 大规模的
stifle 憋笑
divine 神圣的
hound 猎狗
impetus 推动力
intrigue 引起兴趣
besiege 包围
frantically 疯狂的
entail 导致
poultry
trivial
sprawl
plaintiff
incur
pant
quest
ranch
verbal
reassure
whereby
wary
relish
relentless
orderly 有秩序的
magnanimous
quarry
conceive
crooked
undue
detest
bungalow
on the air
trifle 琐事
hard and fast
versed
uncalled-for
orientate oneself 确认方位
kin 亲属
get over 熬过
swarm 蜂群
ordor 气味
outweigh 比……重要
tacit 心照不宣的
latent 潜在的
delectable 美味的
set in 生效
petal 花瓣
tamper 篡改
swerve 急转弯
plantation 种植园
entangle 使缠绕
on no account 绝不
farewell 再见
semblance 相似
hatch 孵化
mesh
exasperate 激怒
bribe 贿赂
make sth. out
rip
wretched 可怜的
shanty 简陋的
take stock of 估量
elated 兴高采烈的
melancholy 犹豫
navigable 可航行的
inert 迟钝的
persevere 坚持不懈的
susceptible 易受影响的
dispense 分配
tract 一片草地
almighty 全能的
split 分配
sensational 轰动性的
concede 承认
rein 控制
speculate 推测
plantiff 原告
prosecute 控告
frugal 节俭的
crevice 裂缝
quaint 古雅的
perspire 流汗
lax 松懈的
make up with sb. 与某人和解
rise to the occasion 应付自如
imminent 迫近的
puncture 刺穿
ponderous 笨重的
bookkeeper 会计员
conjunction 连接词
toddle 蹒跚学步
junior 三年级学生
say to oneself 自言自语
come to nothing 一无所获
mackintosh 寓意
cane 手掌
tinge 染色
bet 打赌
corps 兵团
set sth. back 把钟表回拨
ridge 山脊
get somewhere 有所成就
brood 一窝
dreary 乏味的
synchronize 使同步发生
set on sb. 攻击
misdeed 罪行

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John Doe

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Changchun, China