基于LLZTO@Ag復合層負極改性的硫化物全固態鋰電池及其性能

李凡群; 孫振; 訚碩; 劉絲靚; 張宗良; 劉芳洋

doi:10.13374/j.issn2095-9389.2022.09.26.003

基于LLZTO@Ag復合層負極改性的硫化物全固態鋰電池及其性能

doi: 10.13374/j.issn2095-9389.2022.09.26.003

李凡群^{1, 2},
孫振^{1, 3, 4},
訚碩⁵,
劉絲靚^{1, 3, 4},
張宗良^{1, 3, 4, ,},
劉芳洋^{1, 3, 4}

1.
中南大學冶金與環境學院，長沙 410083
2.
萬向一二三股份公司，杭州 311215
3.
有色金屬增值冶金湖南省重點實驗室，長沙 410083
4.
先進電池材料教育部工程研究中心，長沙 410083
5.
中偉新材料股份有限公司，銅仁 554001

基金項目: 國家重點研發計劃資助項目（2018YFE0203400）；國家自然科學基金資助項目（51720105014）

詳細信息

通訊作者:
E-mail: zongliang.zhang@csu.edu.cn

中圖分類號: TM912
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- 被引次數: 0
出版歷程
- 收稿日期: 2022-09-26
- 網絡出版日期: 2023-03-14

Novel LLZTO@Ag composite layer for the stable anode of sulfide all-solid-state lithium battery

LI Fanqun^{1, 2},
SUN Zhen^{1, 3, 4},
YIN Shuo⁵,
LIU Siliang^{1, 3, 4},
ZHANG Zongliang^{1, 3, 4
, ,},
LIU Fangyang^{1, 3, 4}

1.
School of Metallurgy and Environment, Central South University, Changsha 410083, China
2.
Wanxiang A123 Systems Corp., Hangzhou 311215, China
3.
Hunan Key Laboratory of Nonferrous Metals Value-Added Metallurgy, Changsha 410083, China
4.
Engineering Research Center for Advanced Battery Materials, Ministry of Education, Changsha 410083, China
5.
CNGR Advanced Material Co., Ltd., Tongren 554001, China

More Information

Corresponding author: E-mail: zongliang.zhang@csu.edu.cn

摘要

摘要: 硫化物全固態鋰金屬電池以其高比能和高安全性得到了越來越多的關注，但是電解質與正負極極材料之間嚴重的界面問題仍然限制其進一步發展. 為解決Li₆PS₅Cl固態電解質對金屬鋰不穩定的難點，許多工作提出引入合金負極、引入中間界面層以及電解質直接改性等策略，但是都和實際應用存在一定的差距. 考慮到石榴石氧化物固態電解質Li_6.4La₃Zr_1.4Ta_0.6O₁₂（LLZTO）具有較高的鋰離子電導率和極好的材料穩定性，而Ag金屬具有良好的導鋰性，因此創新性地提出采用LLZTO與Ag的復合界面層來解決Li₆PS₅Cl全固態電池的金屬負極界面問題，提高全電池的循環穩定性. 研究了LLZTO和Ag簡單分散復合、均勻分散包覆復合、以及納米球磨復合等不同組成的LLZTO–Ag復合界面層方式對Li₆PS₅Cl全固態鋰金屬電池負極界面的改善作用. 并探究了優化后的全固態電池的電化學性能. 結果表明，納米球磨復合得到的LLZTO@Ag復合界面層能有效阻止鋰枝晶生長和電池短路. 在最佳工藝下，全固態鋰金屬電池的0.1C首圈效率為77.5%，放電比容量為187.3 mA·h·g^?1，經0.3C循環100圈后容量保持率為81.7%.
- 固態電解質 /
- 鋰負極 /
- 復合界面層 /
- Li₆PS₅Cl /
- 性能提升
Abstract: Sulfide all-solid-state lithium batteries have received increasing attention owing to their high specific energy density and remarkable safety. However, serious interfacial problems still limit their further development. To solve the problem of instability of the interface between the solid-state electrolyte argyrodite (Li₆PS₅Cl) and lithium anode, strategies such as introducing an alloy cathode, introducing an intermediate interface layer, and directly modifying the electrolyte have been proposed; however, these methods are not suitable for practical applications. Notably, lithium lanthanum zirconium oxide (LLZTO) exhibits high lithium-ion conductivity and remarkable material stability, and silver (Ag) metal shows satisfactory lithium conductivity. Accordingly, a composite interface layer made of LLZTO and Ag was innovatively proposed to solve the lithium metal anode/Li₆PS₅Cl interface problem and increase the cycle stability of all-solid-state lithium batteries. We studied the effects of LLZTO–Ag composite interface layers with different combination manners, such as simply dispersed LLZTO–Ag composite, evenly dispersed and coated composite, and ball-milled composite, on the anode interface of Li₆PS₅Cl all-solid-state lithium metal batteries. The electrochemical performance of an optimized all-solid-state battery was also investigated. The results show that the surface of the LLZTO@Ag composite layer obtained by ball milling is relatively smoother and denser, which can effectively prevent lithium dendrite growth and battery short circuit. Compared with the simply dispersed LLZTO–Ag composite method and the evenly dispersed and coated composite method, the ball-milled composite layer anode method can be used to effectively reduce local lithium deposition current density and successfully solve the short circuit problem of the sulfide solid electrolyte. The first cycle efficiency of the LLZTO_pw@Ag_pw–Li_pl all-solid-state battery is 77.5%, and the discharge specific capacity is 187.3 mA·h·g^?1. After 100 cycles at 0.3C, the discharge specific capacity is still 125.5 mA·h·g^?1, and the capacity retention rate is 81.7%. Additionally, we investigated the electrochemical behavior of all-solid-state lithium metal batteries upon the introduction of the LLZTO–Ag composite interfacial layer by using the AC impedance (EIS) and constant-current intermittent titration technique. The LLZTO_pw@Ag_pw anode shows satisfactory cycle stability for lithium batteries. The impedance of the LLZTO_pw@Ag_pw–Li_pl all-solid-state battery exhibits periodic oscillations, indicating that lithium vacancies will be generated in the NCM811 crystal upon extraction of lithium ions, thereby increasing the conductivity of the lithium ions and reducing their migration resistance as well. The effect is most prominent when half of the lithium ions are extracted, but further extraction of lithium ions will lead to too many vacancies in the material, following which extraction of lithium ions will be impeded, thereby increasing the migration resistance of the lithium ions. The interfacial impedance on the cathode side considerably increased during long cycling, thus affecting the subsequent cycling performance, while the interface on the anode side remained essentially stable, highlighting the stabilizing effect of the LLZTO–Ag composite interfacial layer.
- solid state electrolyte /
- lithium anode /
- composite interface layer /
- Li₆PS₅Cl /
- performance improvement

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圖 1 NCM811/LPSC/LLZTO/Ag電池的（a）充放電曲線和（b）循環性能圖；NCM811/LPSC/LLZTO/Ag/Li電池的（c）充放電曲線和（d）循環性能圖

Figure 1. (a) Charge–discharge curve and (b) cycle performance diagram of the NCM811/LPSC/LLZTO/Ag battery; (c) charge–discharge curve and (d) cycle performance diagram of the NCM811/LPSC/LLZTO/Ag/Li battery

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圖 2 （a, b）LLZTO_pw–Ag_pl–Li_pl全固態電池循環后在不同放大倍數下的截面圖；（c）15 kV下的SEM圖；（d）圖(c)對應的EDS面掃圖

Figure 2. (a, b) Cross-sectional views at different magnifications of the LLZTO_pw–Ag_pl–Li_pl all-solid-state battery after cycling; (c) SEM image at 15 kV; (d) EDS mapping patterns of the image in (c)

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圖 3 （a）Ag箔表面的SEM圖；（b, c）不同放大倍數下LLZTO沉積在Ag箔表面的SEM圖；（d）圖c對應的EDS面掃圖

Figure 3. (a) SEM image of Ag foil surface; (b, c) SEM images of LLZTO deposited on Ag foil surface under different magnifications; (d) EDS mapping patterns of the image in (c)

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圖 4 NCM811/LPSC_/LLZTO_pl/Ag電池的（a）充放電曲線和（b）循環性能圖；NCM811/LPSC_/LLZTO_pl/Ag/Li電池的（c）充放電曲線和（d）循環性能圖

Figure 4. (a) Charge–discharge curve and (b) cycle performance diagram of the NCM811/LPSC/LLZTO_pl/Ag battery; (c) charge–discharge curve and (d) cycle performance diagram of the NCM811/LPSC/LLZTO_pl/Ag/Li battery

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圖 5 （a～c）體積比1∶1時LLZTO_pw@Ag_pw顆粒在不同放大倍數下的SEM圖；(d～e)質量比1∶1時LLZTO_pw@Ag_pw片表面在不同放大倍數下的SEM圖和（f）對應的EDS面掃圖；（g～h）體積比1∶1時LLZTO_pw@Ag_pw片表面在不同放大倍數下的SEM圖和（i）對應的EDS面掃圖

Figure 5. (a–c) SEM images of LLZTO_pw@Ag_pw particles at different magnifications with a volume ratio of 1∶1; (d–e) SEM images of the surface of LLZTO_pw@Ag_pw sheets with a mass ratio of 1∶1 under different magnifications and (f) the corresponding EDS mapping patterns; (g–h) SEM images of the surface of LLZTO_pw@Ag_pw sheets under different magnifications at a volume ratio of 1∶1 and (i) the corresponding EDS mapping patterns

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圖 6 NCM811/LPSC/LLZTO_pw@Ag_pw電池的（a）充放電曲線和（b）循環性能圖；NCM811/LPSC_/LLZTO_pl/LLZTO_pw@Ag_pw/Li電池的（c）充放電曲線和（d）循環性能圖

Figure 6. (a) Charge–discharge curve and (b) cycle performance of the NCM811/LPSC/LLZTO_pw@Ag_pw battery; (c) charge–discharge curve and (d) cycle performance of the NCM811/LPSC/LLZTO_pl/LLZTO_pw@Ag_pw/Li battery

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圖 7 NCM811/LPSC_/LLZTO_pw@Ag_pw/Li全固態電池的Nyquist圖.（a）充電前;（b）第一圈充滿電;（c）第一圈放完電時

Figure 7. Nyquist plots of the NCM811/LPSC_/LLZTO_pw@Ag_pw/Li all-solid-state battery∶ (a) before charging; (b) fully charged in the first cycle; (c) fully discharged in the first cycle

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圖 8 GITT_{NCM811/LPSC/LLZTOpw@Agpw/Li}全固態電池的（a）GITT圖和（b）對應的細節圖；（c）第一圈充電時、（d）第一圈放電時、（e）第二圈充電時的瞬時壓降變化圖和（f）對應的歐姆阻抗結果

Figure 8. (a) GITT diagram and (b) the corresponding detailed diagram of the GITT_{NCM811/LPSC/LLZTOpw@Agpw/Li} all-solid-state battery; (c) during the first cycle of charging, (d) during the first cycle of discharge, (e) graph of the instantaneous voltage drop during the second cycle of charging, and (f) the corresponding ohmic impedance results

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圖 9 （a）LLZTO@Ag/LPSC/Li電池的CV循環曲線圖和（b）對應的局部放大圖

Figure 9. (a) CV cycling curve of the LLZTO@Ag/LPSC/Li battery and (b) the corresponding local magnified view

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表 1 不同比例的LLZTO@Ag復合層表面的面掃原子比結果表

Table 1. Surface scan atomic ratio results of LLZTO@Ag composite layers with different ratios

Sample（LLZTO@Ag） O Ta Zr La Ag

Mass ratio of 1∶1 55.97 1.35 4.94 7.66 30.05
Volume ratio of 1∶1 43.15 0.85 4.08 6.58 45.24

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