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JOURNAL OF THE AMERICAN CERAMIC SOCIETY · 2017 ·Vol. 100 ·期 7 ·2832-2839 · IF 2.841

Reaction mechanisms of lithium garnet pellets in ambient air: The effect of humidity and CO2

Wenhao Xia,Biyi Xu,Huanan Duan,Xiaoyi Tang,Yiping Guo,Hongmei Kang,Hua Li,Hezhou Liu

Li 7 La 3 Zr 2 O 12 (LLZO) has been reported to react in humid air to form Li 2 CO 3 on the surface, which decreases ionic conductivity. To study the reaction mechanism, 0.5-mol Ta-doped LLZO (0.5Ta–LLZO) pellets are exposed in dry (humidity ~5%) and humid air (humidity ~80%) for 6 weeks, respectively. After exposure in humid air, the formation of Li 2 CO 3 on the pellet surface is confirmed experimentally and the room-temperature ionic conductivity is found to drop from 6.45×10 −4 S cm −1 to 3.61×10 −4 S cm −1 . Whereas for the 0.5Ta–LLZO samples exposed in dry air, the amount of formed Li 2 CO 3 is much less and the ionic conductivity barely decreases. To further clarify the reaction mechanism of 0.5Ta–LLZO pellets with moisture, we decouple the reactions between 0.5Ta–LLZO with water and CO 2 by immersing 0.5Ta–LLZO pellets in deionized water for 1 week and then exposing them to ambient air for another week. After immersion in deionized water, Li + /H + exchange occurs and LiOH H 2 O forms on the surface, which is a necessary intermediate step for the Li 2 CO 3 formation. Based on these observations, a reaction model is proposed and discussed.

CAS / MDL: 554-13-2
研究领域: 材料科学 · 电化学
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ANALYST · 2023 ·Vol. 148 ·期 14 ·3330-3340 · IF 4.2

Effects of olanzapine and lithium carbonate antipsychotic agents on dopamine oxidation

Kaikai Han,Jingjie Cui,Shaowei Chen,Tao Yu

Olanzapine (OLZ) and lithium carbonate (Li2CO3) are the main drugs for treating mental disorders related to dopamine (DA). A highly conductive carbon paper sensing electrode is used to investigate the effects of OLZ and Li2CO3 on DA oxidation due to its amplification of oxidation peak currents. Different chemical properties of drugs have different effects on DA oxidation. The presence of OLZ fouling on the electrode surface due to the irreversible adsorption weakens the sensing activity and thus reduces the DA oxidation peak current. However, the fixed DA oxidation peak potential at 0.22 V indicates no interaction between them. The hydrolysis effect of Li2CO3 increases the solution pH from 7.47 to 9.73, which promotes the deprotonation of DA, leading to a 156 mV negative shift of the DA oxidation peak potential. Additionally, a 94% decrease of the DA peak current may be related to the generation of polydopamine in alkaline media.

CAS / MDL: 554-13-2 132539-06-1
研究领域: 药理学 · 神经生物学 · 分析化学
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JOURNAL OF POWER SOURCES · 2014 · IF 5.211

Electrochemical performance of 5 V LiNi0.5Mn1.5O4 cathode modified with lithium carbonate addition in electrolyte

Borong Wu,Yonghuan Ren,Daobin Mu,Xiaojiang Liu,Feng Wu

LiNi 0.5 Mn 1.5 O 4 electrode modification is achieved in this work through adding inorganic lithium carbonate (Li 2 CO 3 ) into carbonate electrolyte. Superior cyclic stability of the cathode in the range of 5–2 V is attained, a capacity of 0.3698 mAh g −1 is lost per cycle, which is half of the value in the Li 2 CO 3 -free condition. The capacity loss above and below 3.5 V are both alleviated in the presence of Li 2 CO 3 . Its effect on both the electrolyte bulk and the cathode surface is analyzed with SEM , TEM and XPS measurements. The density functional theory (DFT) calculation is carried out to discuss the modification mechanism. It is speculated that Ni 4+ ⋯CO 3 2− coordination may be formed through the interaction between Ni and O, weakening the oxidizability of Ni 4+ on the electrode surface . In addition, Li 2 CO 3 can consume PF 5 in the electrolyte. The interphase film can also maintain thin and steady during the cycling within 5–2 V.

CAS / MDL: 554-13-2
研究领域: 材料科学 · 电化学
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CHEMICAL ENGINEERING JOURNAL · 2018 · IF 6.735

Preparation of lithium carbonate by thermal decomposition in a rotating packed bed reactor

Wei Liu,Guang-Wen Chu,Shao-Chen Li,Shun Bai,Yong Luo,Bao-Chang Sun,Jian-Feng Chen

With the increasing demand for lithium battery, the use amount of Li 2 CO 3 has substantially increased, especially for the well-dispersed fine particles. However, preparing and reducing the size of battery-grade Li 2 CO 3 by the thermal decomposition method is still a challenge. In this work, a rotating packed bed (RPB) reactor was applied to prepare well-dispersed fine Li 2 CO 3 particles by thermal decomposition of LiHCO 3 . Selection of dispersants in the thermal decomposition process was carried out as the first step and then ethanol was selected as the optimal dispersant, compared with polyethylene glycol (PEG) and polyvinyl alcohol (PVA). Effects of the volume fraction of dispersant, rotational speed, liquid flow rate, steam mass flow rate, and preheating temperature on the particle size were investigated. The median particle size ( d 50 ) of Li 2 CO 3 product obtained in this study can meet the requirement of Chinese National Nonferrous Metal Industry Standard of battery-grade Li 2 CO 3 (YS/T582-2013) by adjusting the operation parameters appropriately, which displays the potential and considerable application prospects.

研究领域: 化学工程 · 材料科学
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RSC Advances · 2013 ·Vol. 4 ·期 20 ·10196-10203 · IF 2.562

Effect of lithium carbonate precipitates on the electrochemical cycling stability of LiCoO2 cathodes at a high voltage

Borong Wu,Yonghuan Ren,Daobin Mu,Xiaojiang Liu,Guchang Yang,Feng Wu

An electrolyte (LiPF6–EC/PC/DEC) containing a lithium carbonate (Li2CO3) additive is used to enable the high cycling stability of a lithium cobalt oxide (LiCoO2) cathode which is charged to 4.5 V for a higher capacity. A capacity as high as 162.8 mA h g−1 (1 C) is maintained after 116 cycles, which is twice as high as the capacity of 88.5 mA h g−1 which was achieved in the Li2CO3 free instance. The interface properties of the electrode are investigated by cyclic voltammetry, electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy. It is found that the solid electrolyte interphase (SEI) film tends to be thin and steady, and that the electrolyte decomposition is suppressed with the addition of Li2CO3. A possible mechanism is proposed according to the DFT calculation. The results indicate that the Co4+…CO32− coordination may decrease the oxidizability of Co4+ on the electrode surface so that the electrolyte decomposition could be suppressed.

CAS / MDL: 554-13-2
研究领域: 材料科学 · 电化学
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HYDROMETALLURGY · 2020 · IF 3.338

Novel process for the extraction of lithium carbonate from spent lithium-containing aluminum electrolytes by leaching with aluminum nitrate and nitric acid

Shaohua Wu,Wenju Tao,Yanchen Zheng,Youjian Yang,Jiangyu Yu,Jingbo Cui,Yu Lu,Zhongning Shi,Zhaowen Wang

A hydrometallurgical process was developed to extract lithium from a spent lithium-containing aluminum electrolyte, reduce the stacking of spent aluminum electrolyte, and recover the valuable elements. In this study, we extracted lithium from an electrolyte using the following three steps: 1) leaching with HNO 3  − Al(NO 3 ) 3 , 2) neutralizing the leachate obtained in the first step, and 3) precipitating the lithium carbonate. A lithium extraction efficiency of 88.0% could be achieved after a leaching time of 6 h, at a leaching temperature of 80 °C and an Al/F molar ratio of 1:6. During the process of neutralization, Al 3+ and F − was precipitated as Al 2 ((OH) 0.46 F 0.54 ) 6 (H 2 O). The obtained Li 2 CO 3 with a high purity of 98.8%.

CAS / MDL: 1310-73-2 497-19-8
研究领域: 冶金学 · 材料科学 · 环境工程
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JOURNAL OF ENVIRONMENTAL MANAGEMENT · 2017 · IF 4.01

Recovery of lithium from the effluent obtained in the process of spent lithium-ion batteries recycling

Xueyi Guo,Xiao Cao,Guoyong Huang,Qinghua Tian,Hongyu Sun

A novel process of lithium recovery as lithium ion sieve from the effluent obtained in the process of spent lithium-ion batteries recycling is developed. Through a two-stage precipitation process using Na 2 CO 3 and Na 3 PO 4 as precipitants , lithium is recovered as raw Li 2 CO 3 and pure Li 3 PO 4 , respectively. Under the best reaction condition (both the amounts of Na 2 CO 3 and Li 3 PO 4 vs . the theoretical ones are about 1.1), the corresponding recovery rates of lithium (calculated based on the concentration of the previous stage) are 74.72% and 92.21%, respectively. The raw Li 2 CO 3 containing the impurity of Na 2 CO 3 is used to prepare LiMn 2 O 4 as lithium ion sieve, and the tolerant level of sodium on its property is studied through batch tests of adsorption capacity and corrosion resistance . When the weight percentage of Na 2 CO 3 in raw Li 2 CO 3 is controlled less than 10%, the Mn corrosion percentage of LiMn 2 O 4 decreases to 21.07%, and the adsorption capacity can still keep at 40.08 mg g −1 . The results reveal that the conventional separation sodium from lithium may be avoided through the application of the raw Li 2 CO 3 in the field of lithium ion sieve.

研究领域: 环境科学 · 材料科学
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Particuology · 2024 · IF 4.1

Influence of stearic acid surface modification on flowability and agglomeration of battery grade Li2CO3 powder

Ming Zhou

This work investigates the flow and agglomeration behaviors of battery grade Li 2 CO 3 powder and the influence of stearic acid surface modification. The degree of agglomeration is directly related to the uniformity of Li 2 CO 3 and its powder mixtures. According to the Chinese National Nonferrous Metal Industry Standard, battery grade Li 2 CO 3 powder has D 50 equal to 3–8 μm which belongs to a micron-sized superfine powder. Therefore, with the extension of storage time, the serious agglomeration phenomenon occurs due to the large specific surface area and rough and irregular powder particles. The Hausner ratio (HR) of the unmodified sample increases from 1.14 to 1.41, and the corresponding flowability is classified as good to poor. Instead, among samples with doping stearic acid, the optimum amount of it is 0.10 wt% which exhibits an extremely stable HR value from 1.14 to 1.16. Meanwhile, after 156 days, the repose angle (AR) obtained for samples without surface modification and using 0.10 wt% stearic acid are calculated to be 49° and 28°, respectively. Based on the values of HR and AR, the flowability of the unmodified sample is poor while the sample modified with 0.10 wt% of stearic acid still maintain excellent powder flow property. Moreover, The LiMn 2 O 4 cathode material synthesized from modified Li 2 CO 3 powder with a stearic acid content of 0.10 wt% exhibits good crystallinity and comparable electrochemical performance to that prepared by commercial Li 2 CO 3 . These results indicate that stearic acid has the potential to be an ideal modifier for battery grade Li 2 CO 3 powder that needs to be kept for a long time.

CAS / MDL: 57-11-4
研究领域: 材料科学 · 电化学
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Nature Communications · 2020 ·Vol. 11 ·期 1 ·1-10 · IF 12.121

On-surface lithium donor reaction enables decarbonated lithium garnets and compatible interfaces within cathodes

Yang Ya-Nan,Li Ying-Xiang,Li Yi-Qiu,Zhang Tao

Lithium garnets have been widely studied as promising electrolytes that could enable the next-generation all-solid-state lithium batteries. However, upon exposure to atmospheric moisture and carbon dioxide, insulating lithium carbonate forms on the surface and deteriorates the interfaces within electrodes. Here, we report a scalable solid sintering method, defined by lithium donor reaction that allows for complete decarbonation of Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) and yields an active LiCoO 2 layer for each garnet particle. The obtained LiCoO 2 coated garnets composite is stable against air without any Li 2 CO 3 . Once working in a solid-state lithium battery, the LiCoO 2 -LLZTO@LiCoO 2 composite cathode maintains 81% of the initial capacity after 180 cycles at 0.1 C. Eliminating CO 2 evolution above 4.0 V is confirmed experimentally after transforming Li 2 CO 3 into LiCoO 2 . These results indicate that Li 2 CO 3 is no longer an obstacle, but a trigger of the intimate solid-solid interface. This strategy has been extended to develop a series of LLZTO@active layer materials.

研究领域: 材料科学 · 能源存储
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ChemistrySelect · 2024 ·Vol. 9 ·期 1 ·e202304480 · IF 1.9

Extraction of Lithium and Synthesis of Kaolinite from α-Spodumene via Alkali Calcination

Lu Xiong,Haisheng Hu,Meitang Liu,Lun Zhuang,Yunfei Li

Graphical The graphical summary shows the preparation of lithium carbonate from α -lithium pyroxene using an alkaline roasting process in a low-energy method. This new method achieves the full utilization of spodumene with lower energy consumption and demonstrates great potential for industrial applications. Extracting lithium from spodumene by sulfuric acid roasting is the largest commercialized way at present, which not only consumes a large amount of energy but also produces massive waste residue that will cause environmental problems. In this work, a new process for extracting lithium by directly decomposing α -spodumene through alkali calcination is designed. The reaction of α -spodumene with Na 2 CO 3 at 750 °C for 2 h can decompose it and form nepheline and lithium silicate/sodium silicate. The nepheline and soluble lithium silicate/sodium silicate are separated by water leaching, and 93.9 % of lithium can be leached under optimal conditions. In addition, the synthesis of nano-kaolinite is investigated with nitric acid solutions. Conversions of 98.7 % were obtained with 0.4 M nitric acid at 250 °C and an L/S ratio of 17.5 L/kg. The water leachate can precipitate Li 2 CO 3 with a purity of 99.0 % by CO 2 after desilicated by CaO. The final yields of Li 2 CO 3 and kaolinite relative to the Li and Si content of the starting minerals are 91.4 % and 48.5 %, respectively. This new method achieves the full utilization of spodumene with lower energy consumption and demonstrates great potential for industrial applications.

研究领域: 材料科学 · 环境科学 · 化学工程
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SEPARATION AND PURIFICATION TECHNOLOGY · 2024 · IF 8.1

Clean and efficient lithium recovery from waste electrolytes via an environmentally short process

Jiaxin Yang,Wenju Tao,Jiaming Li,Lingyu Kong,Shaohua Wu,Jingui He,Zhaoshun Liu,Yu Sun,Chao Fan,Zhaowen Wang

Low-cost and environmentally friendly recycling methods can incorporate strategic elements from discarded lithium-containing aluminum electrolytes (LiAE), which is crucial for alleviating resource shortages and environmental footprint. This study aims to develop a method for the comprehensive utilization of LiAE through low-temperature leaching of calcification. Unlike traditional high-temperature acidification roasting/ transformation processes (320–850 °C), the calcification leaching method only involves one-step leaching and avoids high heat energy consumption. Besides, this low-temperature calcification method chemically destroys the crystal structure of metal fluorides (Li, Na, K, etc.), ensuring a high leaching rate while ensuring an alkaline environment for lithium extraction from the leaching solution without additional alkaline neutralization. The lithium extraction rate exceeds 96 %, with high-purity Li 2 CO 3 and NaOH prepared. The CaCO 3 produced by decalcification has the potential for recycling (in the form of CaO after calcination). Meanwhile, the effects of operating temperature, mass ratio of CaO to LiAE, liquid–solid ratio, and leaching time on the calcium leaching reaction were systematically studied. The economic benefits and creative evaluation of the process were evaluated. Finally, the regenerated LCO prepared from recycled Li 2 CO 3 has been proven to have good electrochemical performance compared to commercial LCO, demonstrating the feasibility of energy storage application. In summary, the comprehensive utilization of LiAE by the calcium leaching method has been proven to be feasible.

研究领域: 环境科学 · 材料科学
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ACS Nano · 2024 · IF 15.8

Zn and Cl Coregulated MXene Catalyst Enhances Li-CO2 Battery Reversibility

Xue Tian,Huan Liu,Bin Cao,Peng Zhang,Yanze Li,Yanchao Ou,Haonan Cui,Mengyao Xu,Bin Xu

MXenes are promising cathodes for Li–CO2 batteries owing to their high electrical conductivity and efficient CO2 activation function. However, the effects of adsorption and electronic structures of MXene on the full life cycle of Li–CO2 batteries have been rarely investigated. Here, we employ a coregulation approach to enhance the adsorption–decomposition of lithium carbonate (Li2CO3) by introducing Zn and Cl surface groups onto the Ti3C2 MXene (Zn–Ti3C2Cl2) catalyst. The incorporation of Cl surface groups enhances Li2CO3 adsorption on the MXene catalyst surface, resulting in the formation of small-sized and uniform Li2CO3. Additionally, the introduction of Zn shifts the d-band centers of titanium and promotes CO2 evolution reaction (CO2ER) activity, thereby facilitating the decomposition of discharge products. As a result, the Li–CO2 battery based on the Zn–Ti3C2Cl2 catalyst exhibits an ultralow overpotential (0.72 V) at 200 mA g–1 and stable cycling for up to 1500 h. This work validates the efficacy of promoting reversibility in Li–CO2 batteries by adjusting the adsorption-decomposition process.

研究领域: 材料科学 · 电化学
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