Pub Date : 2024-10-16DOI: 10.1016/j.ssi.2024.116717
K. Mitsuishi , T. Ohnishi , K. Niitsu , T. Masuda , S. Miyoshi , K. Takada
For realizing oxide-based all-solid-state lithium-ion batteries, lowering sintering temperature of LiCoO2 cathode during battery fabrication is important subject to prevent undesired chemical reaction with other constituent substances. Here we report that the addition of LiOH aqueous solution to the LiCoO2 powder upon sintering improves the battery performance. Comparative study for the samples with and without LiOH solution, and with pure water by in situ transmission electron microscopy reveals that the liquid phase appears at much lower temperatures for the sample with the LiOH addition that improves the connectivity of LiCoO2 particles.
{"title":"Lowering the sintering temperature of LiCoO2 using LiOH aqueous solution","authors":"K. Mitsuishi , T. Ohnishi , K. Niitsu , T. Masuda , S. Miyoshi , K. Takada","doi":"10.1016/j.ssi.2024.116717","DOIUrl":"10.1016/j.ssi.2024.116717","url":null,"abstract":"<div><div>For realizing oxide-based all-solid-state lithium-ion batteries, lowering sintering temperature of LiCoO<sub>2</sub> cathode during battery fabrication is important subject to prevent undesired chemical reaction with other constituent substances. Here we report that the addition of LiOH aqueous solution to the LiCoO<sub>2</sub> powder upon sintering improves the battery performance. Comparative study for the samples with and without LiOH solution, and with pure water by <em>in situ</em> transmission electron microscopy reveals that the liquid phase appears at much lower temperatures for the sample with the LiOH addition that improves the connectivity of LiCoO<sub>2</sub> particles.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116717"},"PeriodicalIF":3.0,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142441522","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-15DOI: 10.1016/j.ssi.2024.116712
Fei Ruan, Chonggui Lei, Xi Wu, Jinxiao Bao, Fen Zhou, Jianquan Gao, Guoqi Liu
Zr-site doped CaZrO3 is a promising high temperature proton conductor solid electrolyte material used for metal melt hydrogen sensor. To understand the electrochemical properties of ytterbium doped calcium zirconate electrolyte in more detail, the CaZr1−xYbxO3−α (x = 0, 0.025, 0.05, 0.075 and 0.1, hereafter named CZY) solid electrolyte specimens were prepared by use of high temperature solid state reaction process. The structure of the electrolyte samples was characterized by Raman spectrum, XRD and SEM. The densities of the specimens were measured based on Archimedes method. The electrical conductivities of the CZY specimens were measured at the temperature of 573–1373 K in hydrogen-rich or oxygen-rich atmosphere by the two-terminal AC impedance spectroscopy method. The H/D isotope effect of the CZY electrolyte at 973–1373 K was tested to clarify the dominant conducting carrier in predetermined temperature and atmosphere. It is demonstrated that proton is the predominant charge carrier both in oxygen-rich and hydrogen-rich atmosphere at the lower temperature below 1073 K. However, at higher temperature above 1073 K, the dominant charge carrier seems to be to be electron hole in oxygen-rich atmosphere, whereas, oxygen ion vacancy in hydrogen-rich based on the analysis of the atmospheric dependence of the electrical conductivity and the H/D isotope effect. Besides, partial conductivities of conducting species(such as interstitial proton, electron hole and oxygen ion vacancy), the active doping amount of ytterbium and the standard Gibbs free energy changes for interstitial proton production by dissolution of water and hydrogen in the CZY electrolyte were estimated based on crystal defect chemistry theory.
掺杂锆酸钙的 CaZrO3 是一种很有前途的高温质子导体固体电解质材料，可用于金属熔体氢传感器。为了更详细地了解掺杂镱的锆酸钙电解质的电化学特性，研究人员采用高温固态反应工艺制备了 CaZr1-xYbxO3-α （x = 0、0.025、0.05、0.075 和 0.1，以下简称 CZY）固体电解质试样。拉曼光谱、XRD 和 SEM 对电解质样品的结构进行了表征。根据阿基米德法测量了试样的密度。采用两端交流阻抗光谱法测量了 CZY 试样在富氢或富氧气氛中于 573-1373 K 温度下的电导率。测试了 973-1373 K 温度下 CZY 电解质的氢/氧同位素效应，以明确在预定温度和气氛下的主要导电载体。但在 1073 K 以上的高温条件下，根据电导率的大气依赖性和 H/D 同位素效应分析，在富氧大气中，主导电荷载流子似乎是电子空穴，而在富氢大气中，主导电荷载流子则是氧离子空穴。此外，还根据晶体缺陷化学理论估算了导电物种（如间隙质子、电子空穴和氧离子空位）的部分电导率、镱的活性掺杂量以及水和氢在 CZY 电解质中溶解产生间隙质子的标准吉布斯自由能变化。
{"title":"The electrical conductive properties analysis of ytterbium doped calcium zirconate proton conductor solid electrolyte based on crystal defect chemistry","authors":"Fei Ruan, Chonggui Lei, Xi Wu, Jinxiao Bao, Fen Zhou, Jianquan Gao, Guoqi Liu","doi":"10.1016/j.ssi.2024.116712","DOIUrl":"10.1016/j.ssi.2024.116712","url":null,"abstract":"<div><div>Zr-site doped CaZrO<sub>3</sub> is a promising high temperature proton conductor solid electrolyte material used for metal melt hydrogen sensor. To understand the electrochemical properties of ytterbium doped calcium zirconate electrolyte in more detail, the CaZr<sub>1<em>−x</em></sub>Yb<sub><em>x</em></sub>O<sub>3<em>−α</em></sub> (<em>x</em> = 0, 0.025, 0.05, 0.075 and 0.1, hereafter named CZY) solid electrolyte specimens were prepared by use of high temperature solid state reaction process. The structure of the electrolyte samples was characterized by Raman spectrum, XRD and SEM. The densities of the specimens were measured based on Archimedes method. The electrical conductivities of the CZY specimens were measured at the temperature of 573–1373 K in hydrogen-rich or oxygen-rich atmosphere by the two-terminal AC impedance spectroscopy method. The H/D isotope effect of the CZY electrolyte at 973–1373 K was tested to clarify the dominant conducting carrier in predetermined temperature and atmosphere. It is demonstrated that proton is the predominant charge carrier both in oxygen-rich and hydrogen-rich atmosphere at the lower temperature below 1073 K. However, at higher temperature above 1073 K, the dominant charge carrier seems to be to be electron hole in oxygen-rich atmosphere, whereas, oxygen ion vacancy in hydrogen-rich based on the analysis of the atmospheric dependence of the electrical conductivity and the H/D isotope effect. Besides, partial conductivities of conducting species(such as interstitial proton, electron hole and oxygen ion vacancy), the active doping amount of ytterbium and the standard Gibbs free energy changes for interstitial proton production by dissolution of water and hydrogen in the CZY electrolyte were estimated based on crystal defect chemistry theory.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116712"},"PeriodicalIF":3.0,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142434261","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tracer diffusion coefficients of lithium-ions in the sintered samples of Li1.5Al0.5Ge1.5(PO4)3 (LAGP) have been measured through the neutron radiography (NR) technique in the wide temperature range from 25 °C to 500 °C. The diffusion data above and below 300 °C were collected using pulsed and reactor-generated neutrons, respectively, which coincide with each other at 300 °C exhibiting a single curve in the Arrhenius plot. The room-temperature diffusion coefficient and the activation energy below 300 °C are obtained as 1.47 × 10−9 cm2 s−1 and 0.37 eV, respectively. The activation energy of the conductivity diffusion coefficient almost agrees with the tracer one, and the deduced Haven ratio of 0.40 is consistent with the concerted migration model of the lithium-ions.
{"title":"Tracer diffusion coefficient measurements on NASICON-type Lithium-ion conductor LAGP using neutron radiography between 25 °C and 500 °C","authors":"Honoka Takagi , Takeshi Yabutsuka , Hirotoshi Hayashida , Fangzhou Song , Tetsuya Kai , Takenao Shinohara , Keisuke Kurita , Hiroshi Iikura , Norio Yamamoto , Minoru Nakajima , Shigeomi Takai","doi":"10.1016/j.ssi.2024.116716","DOIUrl":"10.1016/j.ssi.2024.116716","url":null,"abstract":"<div><div>Tracer diffusion coefficients of lithium-ions in the sintered samples of Li<sub>1.5</sub>Al<sub>0.5</sub>Ge<sub>1.5</sub>(PO<sub>4</sub>)<sub>3</sub> (LAGP) have been measured through the neutron radiography (NR) technique in the wide temperature range from 25 °C to 500 °C. The diffusion data above and below 300 °C were collected using pulsed and reactor-generated neutrons, respectively, which coincide with each other at 300 °C exhibiting a single curve in the Arrhenius plot. The room-temperature diffusion coefficient and the activation energy below 300 °C are obtained as 1.47 × 10<sup>−9</sup> cm<sup>2</sup> s<sup>−1</sup> and 0.37 eV, respectively. The activation energy of the conductivity diffusion coefficient almost agrees with the tracer one, and the deduced Haven ratio of 0.40 is consistent with the concerted migration model of the lithium-ions.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116716"},"PeriodicalIF":3.0,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142434262","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-11DOI: 10.1016/j.ssi.2024.116715
Pengsen Wu , Longfei Zhao , Yang Wang , Jiajia Ge , Zijin Li , Zhenzhen Li , Guanzhou Qiu
In this paper, FePO4∙2H2O and FePO4 have been successfully accomplished by utilizing titanium white by-product ferrous sulfate via two-step synthesis method, which is further employed to react with Li2CO3 via carbothermal reduction to prepare LiFePO4 cathode materials. The composition and structure characteristics of obtained samples are studied in detail by TG-DSC, XRD, XPS, FESEM and TEM, and the electrochemical performances of prepared LiFePO4 are also carefully investigated. The results indicate that the discharge specific capacity of LiFePO4 synthesized from FePO4 achieves 162.4 and 153.7 mAh∙g−1 at 0.1C and 1C, which is 2.2 and 2.9 mAh∙g−1 higher than that from FePO4∙2H2O, and the capacity retention rate reaches as high as 97.5 % after 450 cycles at 1C, correspondingly 94.8 % for LiFePO4 from FePO4∙2H2O. It is mainly ascribed to the smaller particle size of LiFePO4 synthesized from FePO4, and the intimately ordered interface structure between the carbon layer and LiFePO4, which greatly promotes the migration of lithium ions in the lithiation and delithiation process.
{"title":"Preparation of lithium iron phosphate with superior electrochemical performances from titanium white by-product ferrous sulfate","authors":"Pengsen Wu , Longfei Zhao , Yang Wang , Jiajia Ge , Zijin Li , Zhenzhen Li , Guanzhou Qiu","doi":"10.1016/j.ssi.2024.116715","DOIUrl":"10.1016/j.ssi.2024.116715","url":null,"abstract":"<div><div>In this paper, FePO<sub>4</sub>∙2H<sub>2</sub>O and FePO<sub>4</sub> have been successfully accomplished by utilizing titanium white by-product ferrous sulfate via two-step synthesis method, which is further employed to react with Li<sub>2</sub>CO<sub>3</sub> via carbothermal reduction to prepare LiFePO<sub>4</sub> cathode materials. The composition and structure characteristics of obtained samples are studied in detail by TG-DSC, XRD, XPS, FESEM and TEM, and the electrochemical performances of prepared LiFePO<sub>4</sub> are also carefully investigated. The results indicate that the discharge specific capacity of LiFePO<sub>4</sub> synthesized from FePO<sub>4</sub> achieves 162.4 and 153.7 mAh∙g<sup>−1</sup> at 0.1C and 1C, which is 2.2 and 2.9 mAh∙g<sup>−1</sup> higher than that from FePO<sub>4</sub>∙2H<sub>2</sub>O, and the capacity retention rate reaches as high as 97.5 % after 450 cycles at 1C, correspondingly 94.8 % for LiFePO<sub>4</sub> from FePO<sub>4</sub>∙2H<sub>2</sub>O. It is mainly ascribed to the smaller particle size of LiFePO<sub>4</sub> synthesized from FePO<sub>4</sub>, and the intimately ordered interface structure between the carbon layer and LiFePO<sub>4</sub>, which greatly promotes the migration of lithium ions in the lithiation and delithiation process.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116715"},"PeriodicalIF":3.0,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142423114","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The demand for advanced energy storage drives an urgency to accelerate material discovery in solid-state electrolytes. In pursuit of this aim, this study presents an innovative methodology that integrates materials science insights with machine learning techniques to improve the ionic conductivity prediction in garnet-based solid electrolytes. Utilizing an expanded dataset comprising 362 data points, and exploiting easily obtainable pre-synthesis inputs, our approach incorporates rigorous data preprocessing inspired by materials science and machine learning methodologies. Through systematic feature selection and hyperparameter tuning, the model achieved an improved R-squared value of 0.85. This study highlights the efficacy of the proposed approach and underscores the potential of machine learning in streamlining materials discovery and design for next-generation solid-state batteries.
对先进储能技术的需求推动了加快固态电解质材料发现的紧迫性。为了实现这一目标，本研究提出了一种创新方法，将材料科学见解与机器学习技术相结合，以改进石榴石基固体电解质的离子电导率预测。利用由 362 个数据点组成的扩展数据集，并利用容易获得的合成前输入，我们的方法结合了受材料科学和机器学习方法启发的严格数据预处理。通过系统的特征选择和超参数调整，模型的 R 方值提高到了 0.85。这项研究凸显了所提方法的功效，并强调了机器学习在简化下一代固态电池的材料发现和设计方面的潜力。
{"title":"Data refinement for enhanced ionic conductivity prediction in garnet-type solid-state electrolytes","authors":"Zakaria Kharbouch , Mustapha Bouchaara , Fadila Elkouihen , Abderrahmane Habbal , Ahmed Ratnani , Abdessamad Faik","doi":"10.1016/j.ssi.2024.116713","DOIUrl":"10.1016/j.ssi.2024.116713","url":null,"abstract":"<div><div>The demand for advanced energy storage drives an urgency to accelerate material discovery in solid-state electrolytes. In pursuit of this aim, this study presents an innovative methodology that integrates materials science insights with machine learning techniques to improve the ionic conductivity prediction in garnet-based solid electrolytes. Utilizing an expanded dataset comprising 362 data points, and exploiting easily obtainable pre-synthesis inputs, our approach incorporates rigorous data preprocessing inspired by materials science and machine learning methodologies. Through systematic feature selection and hyperparameter tuning, the model achieved an improved R-squared value of 0.85. This study highlights the efficacy of the proposed approach and underscores the potential of machine learning in streamlining materials discovery and design for next-generation solid-state batteries.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116713"},"PeriodicalIF":3.0,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142423113","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-10DOI: 10.1016/j.ssi.2024.116714
Asma Hajji, Ahmed Souemti, Adel Megriche
This study aimed to provide insight into how ultrasonic treatment affects microstructure, electrical properties, and physicochemical characteristics. Sonochemical ultrasound synthesis offers a distinct advantage over traditional methods by creating precise reaction conditions through acoustic cavitation. This process induces high temperatures and pressures in a liquid environment, facilitating the synthesis of materials with specific structures, sizes, and properties. In response to this capability, we developed low-cost M2P2O7 (M = Co, Mn) phosphate materials known as CoP and MnP. The samples were analysed for their crystalline structure, surface morphology, and elemental composition via X-ray diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM).
The electrochemical performance of the samples was assessed via complex impedance spectroscopy methods. The results demonstrate that the samples exhibit excellent semiconductor behavior, indicating their potential for use in energy and catalytic applications.
{"title":"Ultrasound-assisted sonochemical synthesis of M2P2O7 (M = Co, Mn) nanomaterials: Enhanced structural morphology and ionic conduction mechanism","authors":"Asma Hajji, Ahmed Souemti, Adel Megriche","doi":"10.1016/j.ssi.2024.116714","DOIUrl":"10.1016/j.ssi.2024.116714","url":null,"abstract":"<div><div>This study aimed to provide insight into how ultrasonic treatment affects microstructure, electrical properties, and physicochemical characteristics. Sonochemical ultrasound synthesis offers a distinct advantage over traditional methods by creating precise reaction conditions through acoustic cavitation. This process induces high temperatures and pressures in a liquid environment, facilitating the synthesis of materials with specific structures, sizes, and properties. In response to this capability, we developed low-cost M<sub>2</sub>P<sub>2</sub>O<sub>7</sub> (M = Co, Mn) phosphate materials known as CoP and MnP. The samples were analysed for their crystalline structure, surface morphology, and elemental composition via X-ray diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM).</div><div>The electrochemical performance of the samples was assessed via complex impedance spectroscopy methods. The results demonstrate that the samples exhibit excellent semiconductor behavior, indicating their potential for use in energy and catalytic applications.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116714"},"PeriodicalIF":3.0,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142423115","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-07DOI: 10.1016/j.ssi.2024.116703
Jiawang Ma, Yajie Wang, Tao Ban, Song Liu, Maolian Guo, Xinxin Wang, Zihui Wang, Xiuling Zhu
Proton exchange membrane (PEM) is an important component that affects the cost and cell performance of PEM water electrolysis (PEMWE). In this study, a series of ether-free poly(p-terphenyl-isatin- dimethylfluorene) (PID-x) polymers were synthesized by superacid-catalyzed Friedel-Crafts alkylation. The transparent PEMs of sulfonated poly(p-terphenyl-isatin- dimethylfluorene) (SPID-x) were prepared by the solution casting method. Introduction of dimethylfluorene groups enhances proton conductivity of PEMs while also preserving their high dimensional stability. The results indicate that the synthesized PID-x has excellent solubility in non-protic polar solvents. SPID-5, prepared with 5 % dimethylfluorene in the backbone structure exhibits a high conductivity of 0.176 S·cm−1 at 80 °C (compared to 0.155 S·cm−1 at 80 °C for Nafion115) and excellent dimensional stability, with a swelling ratio of only 10 % at 80 °C (compared to 20 % at 80 °C for Nafion115). In the water electrolysis cell performance test, SPID-25 achieved a current density of 167 mA·cm−2 at 2.5 V, outperforming the commercial Nafion 211 (151 mA·cm−2) at a similar membrane thickness.
{"title":"Efficient ether-free poly(p-terphenyl-isatin-dimethylfluorene) for proton exchange membrane water electrolysis","authors":"Jiawang Ma, Yajie Wang, Tao Ban, Song Liu, Maolian Guo, Xinxin Wang, Zihui Wang, Xiuling Zhu","doi":"10.1016/j.ssi.2024.116703","DOIUrl":"10.1016/j.ssi.2024.116703","url":null,"abstract":"<div><div>Proton exchange membrane (PEM) is an important component that affects the cost and cell performance of PEM water electrolysis (PEMWE). In this study, a series of ether-free poly(<em>p</em>-terphenyl-isatin- dimethylfluorene) (PID-x) polymers were synthesized by superacid-catalyzed Friedel-Crafts alkylation. The transparent PEMs of sulfonated poly(<em>p</em>-terphenyl-isatin- dimethylfluorene) (SPID-x) were prepared by the solution casting method. Introduction of dimethylfluorene groups enhances proton conductivity of PEMs while also preserving their high dimensional stability. The results indicate that the synthesized PID-x has excellent solubility in non-protic polar solvents. SPID-5, prepared with 5 % dimethylfluorene in the backbone structure exhibits a high conductivity of 0.176 S·cm<sup>−1</sup> at 80 °C (compared to 0.155 S·cm<sup>−1</sup> at 80 °C for Nafion115) and excellent dimensional stability, with a swelling ratio of only 10 % at 80 °C (compared to 20 % at 80 °C for Nafion115). In the water electrolysis cell performance test, SPID-25 achieved a current density of 167 mA·cm<sup>−2</sup> at 2.5 V, outperforming the commercial Nafion 211 (151 mA·cm<sup>−2</sup>) at a similar membrane thickness.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116703"},"PeriodicalIF":3.0,"publicationDate":"2024-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142423116","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-28DOI: 10.1016/j.ssi.2024.116708
Heng Pan, Lingcong Fan, Yongxi Zhang, Lei Zhang, Ying Shi, Jianjun Xie, Fang Lei
Garnet-type electrolytes are regarded as one of the most promising solid-state electrolytes (SSEs) for lithium-ion batteries due to their potential advantages in terms of energy density, electrochemical stability and safety. To achieve the maximum energy density, it is necessary to ensure that the electrolyte layer is as thin as possible. Nevertheless, thin sheet SSE is more challenging to sinter than pellet due to the greater lithium volatilization from the high surface/volume ratio. Garnet-type SSE (Li6.5La3Zr1.5Ta0.5O12, LLZTO) green tape was prepared by the tape-casting technique. The effects of supporter, sintering temperature and dwell time on the relative density, microstructure and ionic conductivity of thin sheet were investigated. A ceramic SSE sheet with a thickness of 173 μm, a relative density of 97.2 %, an ionic conductivity of 2.02 × 10−4 S/cm at 25 °C and an activation energy of 0.25 eV, was achieved using a rapid pressureless sintering at 1250 °C for 25 min with a MgO supporter. This work offers insights into the practical production of LLZTO sheets.
{"title":"A rapid pressureless sintering strategy for LLZTO ceramic solid electrolyte sheets prepared by tape casting","authors":"Heng Pan, Lingcong Fan, Yongxi Zhang, Lei Zhang, Ying Shi, Jianjun Xie, Fang Lei","doi":"10.1016/j.ssi.2024.116708","DOIUrl":"10.1016/j.ssi.2024.116708","url":null,"abstract":"<div><div>Garnet-type electrolytes are regarded as one of the most promising solid-state electrolytes (SSEs) for lithium-ion batteries due to their potential advantages in terms of energy density, electrochemical stability and safety. To achieve the maximum energy density, it is necessary to ensure that the electrolyte layer is as thin as possible. Nevertheless, thin sheet SSE is more challenging to sinter than pellet due to the greater lithium volatilization from the high surface/volume ratio. Garnet-type SSE (Li<sub>6.5</sub>La<sub>3</sub>Zr<sub>1.5</sub>Ta<sub>0.5</sub>O<sub>12</sub>, LLZTO) green tape was prepared by the tape-casting technique. The effects of supporter, sintering temperature and dwell time on the relative density, microstructure and ionic conductivity of thin sheet were investigated. A ceramic SSE sheet with a thickness of 173 μm, a relative density of 97.2 %, an ionic conductivity of 2.02 × 10<sup>−4</sup> S/cm at 25 °C and an activation energy of 0.25 eV, was achieved using a rapid pressureless sintering at 1250 °C for 25 min with a MgO supporter. This work offers insights into the practical production of LLZTO sheets.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116708"},"PeriodicalIF":3.0,"publicationDate":"2024-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142357886","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-28DOI: 10.1016/j.ssi.2024.116706
Sangtae Kim , Sergey Khodorov , Leonid Chernyak , Thomas Defferriere , Harry Tuller , Igor Lubomirsky
We propose a method for determining the density of space charge trapped at grain boundaries in polycrystalline solid state ionic conductors. The method is an extension of the earlier proposed Linear Diffusion Model (LDM) that relies on the impedance spectra-derived current-voltage characteristics of grain boundaries. The utility of the extended LDM version is demonstrated to successfully and nondestructively obtain values for the space charge density trapped at the grain boundaries in a variety of oxygen ion conductors including Sr-doped LaGaO3, Y-doped CeO2, and Gd-doped CeO2, and proton conductors including Sr-doped LaNbO3 and Y-doped BaZrO3. For all cases, the density of the space charge trapped at the grain boundaries was <0.2C/m2, corresponding to a fraction of electron charge per unit cell. The proposed technique, while it lacks the ability to determine the thickness of the grain boundary core when much smaller than the Debye length, it can be used to distinguish between space charge vs insulating layer contributions to the grain boundary resistance.
我们提出了一种确定多晶固态离子导体晶界空间电荷密度的方法。该方法是早先提出的线性扩散模型（LDM）的扩展，它依赖于从阻抗谱得到的晶界电流-电压特性。我们展示了扩展 LDM 版本的实用性，它成功地以无损方式获得了掺杂 Sr 的 LaGaO3、掺杂 Y 的 CeO2 和掺杂 Gd 的 CeO2 等多种氧离子导体以及掺杂 Sr 的 LaNbO3 和掺杂 Y 的 BaZrO3 等质子导体中晶界处捕获的空间电荷密度值。在所有情况下，晶界捕获的空间电荷密度均为 0.2C/m2，相当于每个单位晶胞的电子电荷分数。所提出的技术虽然无法确定远小于德拜长度的晶界核心厚度，但可以用来区分空间电荷和绝缘层对晶界电阻的贡献。
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