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Li1.5Al0.5Ge1.5(PO4)3
JOURNAL OF MEMBRANE SCIENCE · 2023 · IF 9.5

Li1.5Al0.5Ge1.5(PO4)3 membrane electrodialysis for lithium enrichment

Zhouyang Jiang,Wenhan Kong,Fenglin Zhao,Qingyue Han,Yangxi Liu,Suqing Wang,Haihui Wang

Highly purified LiOH is a common raw material of cathode active materials of lithium-ion batteries. Its demand is rapidly increasing with the fast development of the electric vehicles. The traditional enrichment process of LiOH relying on water evaporation requires a lot of energy. Here, we demonstrate the ability of NASICON-type Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 membrane electrodialysis to enrich the LiOH aqueous solution with a low concentration. This Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 membrane electrodialysis could extract 99.7% and 96.5% of Li + in 0.1, and 0.01 M LiOH feed solution, respectively, into 1 M LiOH receiving solution. And the transmembrane resistance between feed solution and receiving solution increased by 37.4, 389.5, and 964.6 Ω cm 2 , compared to the value for 1 M of LiOH feed solution as the feed solution concentration decreased to 0.1, 0.01 and 0.001 M, respectively. This quantitative assessment method for the resistance variation is crucial to the potential separation application of Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 membrane electrodialysis in salt-lake brine.

✓ 已验证 DOI 高影响因子
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JOURNAL OF SOLID STATE ELECTROCHEMISTRY · 2020 ·Vol. 25 ·期 2 ·527-534 · IF 2.646

Boron group element doping of Li1.5Al0.5Ge1.5(PO4)3 based on microwave sintering

Yan Binggong,Kang Lei,Kotobuki Masashi,He Linchun,Liu Bin,Jiang Kaiyong

We report effectiveness of dopants selected from group 13, such as B, Ga, and In, on the conductivity of Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) that is recognized as one of the promising solid electrolytes for next-generation solid-state lithium batteries. To minimize loss of versatile element, crystallization of LAGP using a microwave irradiation is introduced. Experimental results demonstrate that B enhances grain boundary conductivity, while Ga improves the bulk ionic conductivity. Co-doping of B and Ga leads to enhanced total ionic conductivity and remarkably reduced activation energy.

✓ 已验证 产品关联 DOI 高影响因子
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MATERIALS CHEMISTRY AND PHYSICS · 2024 · IF 4.3

Composite batteries consisted of three dimensional structured Li1.5Al0.5Ge1.5(PO4)3 and ionic liquid

Yang Qu,Hongrui Jin,Li Lu,Yumei Wang,Kotobuki Mashashi,Binggong Yan

In all-solid-state batteries , the rigid point contact between the solid electrolyte and electrode results in poor cell interface wettability and generates large interfacial impedance, which hinders the application of solid-state batteries. To enhance ionic conductivity and interfacial wettability of NASICON-structured solid-state electrolyte Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP), microporous LAGP with a hexagonal surface pattern is prepared using femtosecond laser followed by filling an ionic liquid electrolyte to form a solid-liquid composite electrolyte (HPL&IL). The effect of surface textures on the electrolyte-electrode interface is investigated. Experimental results demonstrate that cycling stability for Li|HPL&IL|Li cells can reach up to 350 h at a constant current density of 0.05 mA cm −2 at room temperature, and hexagonal surface textures promote uniform interfacial film formation while increasing contact area between electrode and electrolyte, providing more space for charge transfer at the interface.

✓ 已验证 产品关联 DOI 高影响因子
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CHEMICAL ENGINEERING JOURNAL · 2021 · IF 13.273

A Janus Li1.5Al0.5Ge1.5(PO4)3 with high critical current density for high-voltage lithium batteries

Wenping Zha,Yadong Ruan,Zhaoyin Wen

The application of Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) is hindered by chemical instability with lithium (Li) metal and poor interfacial compatibility with high-voltage cathodes. Herein, an in-situ Janus LAGP is fabricated to solve the above two issues simultaneously. On the cathodic side, a succinonitrile-based interlayer with good oxidation stability is applied to facilitate ion transport at the interface and inside the cathode. On the anodic side, Fluoroethylene carbonate (FEC)-based polymer interlayer is chosen to ameliorate side reactions on LAGP/Li interface and inhibit the dendrite growth. Consequently, the Li symmetric cell with the Janus LAGP possesses a high critical current density of 5.4 mA cm −2 and operates stably for over 500 h at a high current density of 1.0 mA cm −2 . Moreover, the Janus LAGP exhibits excellent ionic conductivity (4.76 × 10 −4  S cm −1 ), wide electrochemical window (0–5.2 V vs. Li + /Li) and stable interfacial compatibility with high-voltage cathodes. The solid-state lithium battery (LiNi 0.8 Co 0.1 Mn 0.1 O 2 /Li) delivers a maximum discharge capacity of 178 mAh g −1 with a retention of 85.7% after 100 cycles at 0.5C. Notably, when the mass loading is increased to 10.0 mg cm −2 , the battery delivers a maximum discharge capacity of 134.1 mAh g −1 (1.52 mAh) at 0.5C, and the capacity remains 76.1% after 100 cycles.

✓ 已验证 DOI 高影响因子
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JOURNAL OF THE EUROPEAN CERAMIC SOCIETY · 2018 · IF 3.794

Preparation and ionic conduction of Li1.5Al0.5Ge1.5(PO4)3 solid electrolyte using inorganic germanium as precursor

Zhijian Sun,Lei Liu,Yuxiao Lu,Guangyue Shi,Jiajun Li,Lei Ma,Jie Zhao,Hongli An

NASION-type Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) is prepared by a novel sol-gel method using low cost inorganic germanium (GeO 2 ) as the precursor. The composition and phase transformation during the heating of the LAGP precursors are analyzed using thermogravimetric-differential scanning calorimetry (TG-DSC) and X-ray diffraction (XRD). The structures and morphologies of the LAGP are characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results show that the LAGP annealed at 900 ℃ is partially crystallized and consists of a large number of nanoscale grains surrounded by amorphous regions. The LAGP particles present an irregular morphology with a large size distribution over a range of 0.2–1 μm. In addition, ionic conductivities of the prepared LAGP first increase and then decrease with an increase in the sintering temperature and time. A high ionic conductivity (4.18 × 10 −4 Scm -1 ) with an activation energy of 0.30 eV are obtained for the LAGP sample sintered at 900 °C for 8 h.

CAS / MDL: 1310-53-8
✓ 已验证 产品关联 DOI 高影响因子
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International Journal of Applied Ceramic Technology · 2023 ·Vol. 20 ·期 4 ·2125-2130 · IF 2.1

Rapid crystallization of Li1.5Al0.5Ge1.5(PO4)3 glass ceramics via ultra-fast high-temperature sintering (UHS)

Jinghua Wu,Milad Kermani,Lei Cao,Bohan Wang,Zhiquan Dai,Le Fu,Chunfeng Hu,Salvatore Grasso

Lithium aluminum germanium phosphate solid electrolyte is a promising candidate for all-solid-state batteries. The currently available processing techniques based on melting-quenching require a rather lengthy crystallization step lasting up to 8 hours. In this work, the newly emerged ultra-fast high-temperature sintering (UHS) was proposed to achieve in a single step reactive consolidation of powder mixture (GeO 2 , Al(PO 3 ) 3 , LiPO 3 ) and crystallization of the electrolyte within 16 minutes. Samples produced using UHS had a better phase purity, reduced Li loss, and improved ionic conductivity when compared to the counterparts prepared using conventional crystallization at 850°C for 6 h. In fact, specimens prepared by UHS achieved a crystallinity of 90% and ionic conductivity as high as 1.31 × 10 −4 S cm −1 .

✓ 已验证 DOI 高影响因子
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International Journal of Electrochemical Science · 2023 · IF 1.5

Interface Modification of NASICON-structured Li1.5Al0.5Ge1.5(PO4)3 (LAGP) by Femtosecond Laser Structuring and Ionic Liquid

Binggong Yan,Yongchao Wang,Hongliang Ren,Xizhao Lu,Masashi Kotobuki,Bin Liu,Kaiyong Jiang

NASICON-structured solid-state electrolyte, namely Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) possesses high ionic conductivity and good compatibility with lithium metal that make it an ideal electrolyte for next-generation lithium battery. However, high interfacial impedance and possible dendrite limit its practical applications. To reduce interfacial impedance, herein, surface texturing on the LAGP is conducted using a femtosecond laser, and further wetted by ionic liquids. The femtosecond laser-modified surface can effectively increase wettability and improve the interfacial contacts. Low area specific impedance of 81.4Ω cm -2 is obtained and the full battery demonstrates good electrochemical performances.

✓ 已验证 DOI 高影响因子
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JOURNAL OF POWER SOURCES · 2021 · IF 9.127

Gravity-driven Poly(ethylene glycol)@Li1.5Al0.5Ge1.5(PO4)3 asymmetric solid polymer electrolytes for all-solid-state lithium batteries

Shujiao Yang,Zhihua Zhang,Lin Shen,Peng Chen,Zhi Gu,Mingyuan Chang,Yue zhao,Hao He,Xiayin Yao

An asymmetric solid polymer electrolyte (ASPE) is designed as two-in-one layered structure driven by gravity and in-situ polymerization. The rigid layer composed of polymer embedded three-dimensional continuous Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) framework improves the Li + transference number and critical current densities. The soft poly(ethylene glycol) (PEG) layer prepared via thermal polymerization by poly(ethylene glycol) methyl ether methacrylate (PEGMEM) makes good interfacial contact with cathodes. Driven by gravity, the two layers are automatically stratified during the polymerization. By virtue of this structural merit, the Li + transference number of PEG@LAGP ASPE extends to 0.144 (vs. 0.083 of PEG SPE), and symmetric Li/PEG@LAGP ASPE/Li cells can stably cycle over 400 h at current density of 0.5 mA cm −2 under 60 °C. LiFePO 4 /PEG@LAGP ASPE/Li cell exhibits excellent electrochemical performance at 2.5 C (0.5 mA cm −2 ) under 60 °C, reaching to a maximum specific capacity of 130.8 mA h g −1 and a capacity retention of 87.2% after 1000 cycles. Furthermore, the cells operating at high rates or high temperatures also have been demonstrated. This work provides a promising electrolyte design strategy for all-solid-state batteries with superior interface compatibility and long cycle life.

研究领域: 材料科学 · 电化学 · 储能技术 · 高分子科学 · 电池技术
✓ 已验证 DOI 高影响因子
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Energy & Environmental Materials · 2020 ·Vol. 4 ·期 2 ·208-212 · IF 0

Effects of Heat Treatment and Additive LiF on the Properties of Solid-State Electrolyte of Li1.5Al0.5Ge1.5(PO4)3

Jinhang Lv,Ruilin Zheng,Peng Lv,Wei Wei

A solid electrolyte of LAGP [Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 ] contained 0.5 wt% LiF was prepared by using low-volatile raw materials. The effects of different heat treatment conditions (750–900 °C, 4–10 h) and additive (LiF) on the ionic conductivity, structural morphology, and crystal transformation process were investigated in detail. EIS (electrochemical impedance spectroscopies) showed that the ionic conductivity of LAGP contained 0.5 wt% LiF had a highest value of 3.17 × 10 −4 S cm −1 with low activation energy (0.31 eV) after treating 825 °C for 6 h, more than LAGP of 2.45 × 10 −4 S cm −1 . DSC analysis and SEM images indicated that adding a small amount of LiF to LAGP not only can lower the glass transition temperature (from 513 °C to 507 °C) and crystallization temperature (from 622 °C to 605 °C), but also can modify the grain boundary and increase the relative density of LAGP (from 95.8% to 97.7%).

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ELECTROCHIMICA ACTA · 2018 · IF 5.116

Stable cycling of all-solid-state lithium battery with surface amorphized Li1.5Al0.5Ge1.5(PO4)3 electrolyte and lithium anode

Zhihua Zhang,Shaojie Chen,Jing Yang,Gaozhan Liu,Xiayin Yao,Ping Cui,Xiaoxiong Xu

The severe instability with lithium (Li) anode of NASICON-structure Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) solid-state electrolyte (SSE) greatly hinders its practical applications in the all-solid-state lithium batteries (ASSLBs) with high energy density and safety. In order to alleviate this issue, here we employed an artificial protective layer of LAGP glass on the surface of ceramic LAGP sheet to construct a surface amorphized electrolyte via a spin-coating co-sintering method. AC impedance test and galvanostatic charge-discharge cycling of Li/electrolytes/Li symmetrical cell suggest that enabled by this glass layer, the surface amorphized LAGP can exhibit better compatibility with Li anode. In addition, with a poly(ethylene oxide) polymer electrolyte in the cathode side , at 0.1 C under 60 °C, the LiFePO 4 /Li ASSLB using surface amorphized LAGP can keep stable for 120 cycles with a retention of 93.6%, which is more than 13 times of the cell using ceramic LAGP (6.9%). The formation mechanisms of unstable interphases in LAGP/Li interface were briefly summarized, and probable reasons behind the good compatibility between and LAGP glass and Li were discussed.

研究领域: 材料科学 · 电化学 · 储能技术 · 固态电池 · 陶瓷材料
✓ 已验证 DOI 高影响因子
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JOURNAL OF POWER SOURCES · 2017 · IF 6.395

An ion-conductive Li1.5Al0.5Ge1.5(PO4)3-based composite protective layer for lithium metal anode in lithium-sulfur batteries

Changzhi Sun,Xiao Huang,Jun Jin,Yang Lu,Qing Wang,Jianhua Yang,Zhaoyin Wen

Lithium (Li) metal plays an indispensable role in Li-S batteries , but its fast degradation seriously impedes the practical application of Li-S batteries. Here, an ion-conductive LAGP-based composite protective layer (CPL) consisting of lithium aluminum germanium phosphate (Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 ) and polyvinylidene fluoride (PVDF) is prepared on Li metal anode via a facile casting method. In the presence of LAGP, the negative effect of CPL on the diffusion of Li + is minimized. Hence, it can not only effectively resist corrosive action of lithium polysulfides (LiPSs) on Li metal anode, but also reduce interfacial polarization and restrain dendritic Li growth. The protected Li anode exhibits exceptional cycling stability and low voltage polarization (∼30 mV at 0.5 mA cm −2 ) for 300 h. The electrochemical performance of Li-S batteries with protected Li anode is also greatly enhanced. The discharge specific capacity of 832.1 mAh g −1 and an average coulombic efficiency of 92% are obtained for up to 100 cycles at 0.5 C in LiNO 3 -free electrolyte. Additionally, the rate capability of Li-S batteries is significantly improved, delivering a reversible capacity of 565 mAh g −1  at 4 C. Our results also indicate this protection strategy can be extended to the Li-S pouch cells.

✓ 已验证 DOI 高影响因子
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ACS Applied Energy Materials · 2019 · IF 0

Titanium Dioxide Doping toward High-Lithium-Ion-Conducting Li1.5Al0.5Ge1.5(PO4)3 Glass-Ceramics for All-Solid-State Lithium Batteries

Jing Yang,Zhen Huang,Peng Zhang,Gaozhan Liu,Xiaoxiong Xu,Xiayin Yao

Developing solid electrolytes with high lithium-ion conductivity is crucial to realize high-performance all-solid-state lithium batteries. The substitution of ions with larger ionic radius can enlarge the Li+ migration tunnels and therefore enhance the lithium-ion conductivity. In this work, Ti4+ is employed to partially replace Ge4+ in Li2O–Al2O3–GeO2–P2O5 glass-ceramics electrolyte in order to improve its conductivity. The highest total lithium-ion conductivity of 1.07 × 10–3 S cm–1 at room temperature is obtained from Li1.5Al0.5Ge1.5(PO4)3-7.5 wt % TiO2 sample sintered at 900 °C for 6 h. The bulk and grain boundary conductivities are 1.67 × 10–3 S cm–1 and 2.99 × 10–3 S cm–1, respectively, which are superior than that of the pristine Li1.5Al0.5Ge1.5(PO4)3 counterpart. Both bulk and grain boundary conductivities of the sample have been significantly improved, which could be attributed to the increase of bottleneck sizes of the Li+ migration tunnels and the decrease of grain boundary area. All-solid-state lithium batteries employing LiFePO4 as cathode and solid electrolyte as separator and ionic conductor are assembled. A reversible capacity of 132.3 mAh g–1 is delivered after 200 cycles under a current density of 0.1C with a capacity retention ratio of 91.1%, showing the solid electrolyte is ideal for all-solid-state lithium-battery applications.

研究领域: 材料科学 · 固体离子学 · 储能技术 · 电化学 · 陶瓷与玻璃
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