Synthesis and Performance of LiFe1-xMnxPO4 in Lithium-ion Battery

NASA Astrophysics Data System (ADS)

Bazzi, Khadije; Nazri, Maryam; Vaishnava, Prem; Naik, Vaman; Nazri, Gholam-Abbas; Naik, Ratna

2013-03-01

Olivine-type lithium transition metal phosphates (i.e. LiFePO4) have been intensively investigated as promising electrode materials for rechargeable lithium-ion batteries. There have been attempts to improve energy density and voltage quality of phosphate based electrode. In this study, we have partially substituted FeII/FeIII redox center with MnII/MnIII in LiFePO4 that provides over 600 mV higher voltage. We prepared various compositions of LiFe1-xMnxPO4 (x =0, 0.2, 0.4, 0.6, 0.8 and 1) between the two end members (LiFePO4 - LiMnPO4) . Due to intrinsic low electronic conductivity of lithium transition metal phosphates, we coat these materials with a uniform conductive carbon through a unique sol-gel process developed in our laboratory. In addition, we made a composite of the carbon coated phosphate with carbon nano-tubes to develop a highly conductive matrix electrode. We report the materials structure, morphology, electrical conductivity and electrochemical performances of LiFe1-xMnxPO4 using XRD, Raman spectroscopy, SEM, TEM, XPS, electrical conductivity and galvanostatic charge/discharge measurements.

Optical Properties and Electrochemical Performance of LiFePO4 Thin Films Deposited on Transparent Current Collectors.

PubMed

Lee, HyunSeok; Yim, Haena; Kim, Kwang-Bum; Choi, Ji-Won

2015-11-01

LiFePO4 thin film cathodes are deposited on various transparent conducting oxide thin films on glass, which are used as cathode current collectors. The XRD patterns show that the thin films have the phase of LiFePO4 with an ordered olivine structure indexed to the orthorhombic Pmna space group. LiFePO4 thin film deposited on various TCO glass substrates exhibits transmittance of about 53%. The initial specific discharge capacities of LiFePO4 thin films are 25.0 μAh/cm2 x μm on FTO, 33.0 μAh/cm2 x μm on ITO, and 13.0 μAh/cm2 x μm on AZO coated glass substrates. Interestingly, the retention capacities of LiFePO4 thin films are 76.0% on FTO, 31.2% on ITO, and 37.7% on AZO coated glass substrates at 20th cycle. The initial specific discharge capacity of the LiFePO4/FTO electrode is slightly lower, but the discharge capacities of the LiFePO4/FTO electrode relatively decrease less than those of the others such as LiFePO4/ITO and LiFePO4/AZO with cycling. The results reported here provide the high transparency of LiFePO4 thin films cathode materials and the good candidate as FTO current collector of the LiFePO4 thin film cathode of transparent thin film rechargeable batteries due to its high transparency and cyclic retention.

Relaxation-Induced Memory Effect of LiFePO4 Electrodes in Li-Ion Batteries.

PubMed

Jia, Jianfeng; Tan, Chuhao; Liu, Mengchuang; Li, De; Chen, Yong

2017-07-26

In Li-ion batteries, memory effect has been found in several commercial two-phase materials as a voltage bump and a step in the (dis)charging plateau, which delays the two-phase transition and influences the estimation of the state of charge. Although memory effect has been first discovered in olivine LiFePO 4 , the origination and dependence are still not clear and are critical for regulating the memory effect of LiFePO 4 . Herein, LiFePO 4 has been synthesized by a home-built spray drying instrument, of which the memory effect has been investigated in Li-ion batteries. For as-synthesized LiFePO 4 , the memory effect is significantly dependent on the relaxation time after phase transition. Besides, the voltage bump of memory effect is actually a delayed voltage overshooting that is overlaid at the edge of stepped (dis)charging plateau. Furthermore, we studied the kinetics of LiFePO 4 electrode with electrochemical impedance spectroscopy (EIS), which shows that the memory effect is related to the electrochemical kinetics. Thereby, the underlying mechanism has been revealed in memory effect, which would guide us to optimize two-phase electrode materials and improve Li-ion battery management systems.

Facile Synthesis of Bowl-Like LiFePO4/C Composite with High Rate-Performance

NASA Astrophysics Data System (ADS)

Jing, Peng; Yao, Lei; Xiang, Mingwu; Wang, Yan; Wu, Jinhua; Wang, Boya; Zhang, Yun; Wu, Hao; Liu, Heng

2018-07-01

Olivine-structured LiFePO4/C composites with high rate-performance were synthesized via an industrial spray-drying technique using a low cost Fe3O4 as iron source. The as-obtained LiFePO4/C exhibits a unique bowl-like morphology with a particle size of 2-5 μm in diameter. A continuous uniform carbon coating layer on the surface of LiFePO4/C cathodes promotes fast electron transport, whilst it guarantees the favorable electrochemical reaction. Especially the formation of porous structure leads to an average pore volume of 0.127 cm3 g-1 and a high specific surface area of 34.46 m2 g-1, which is conducive to facilitating the penetration of electrolyte and providing the more contact area of electrolyte with LiFePO4/C. As a result, the as-prepared LiFePO4/C cathode material delivers an outstanding discharge capacity of 102.1 mAh g-1, 94.2% of the initial capacity (108.3 mAh g-1), after 1000 cycles at 10 C. Even at an ultrahigh current rate of 50 C, it still shows an initial discharge capacity of 58 mAh g-1.

Facile Synthesis of Bowl-Like LiFePO4/C Composite with High Rate-Performance

NASA Astrophysics Data System (ADS)

Jing, Peng; Yao, Lei; Xiang, Mingwu; Wang, Yan; Wu, Jinhua; Wang, Boya; Zhang, Yun; Wu, Hao; Liu, Heng

2018-03-01

Olivine-structured LiFePO4/C composites with high rate-performance were synthesized via an industrial spray-drying technique using a low cost Fe3O4 as iron source. The as-obtained LiFePO4/C exhibits a unique bowl-like morphology with a particle size of 2-5 μm in diameter. A continuous uniform carbon coating layer on the surface of LiFePO4/C cathodes promotes fast electron transport, whilst it guarantees the favorable electrochemical reaction. Especially the formation of porous structure leads to an average pore volume of 0.127 cm3 g-1 and a high specific surface area of 34.46 m2 g-1, which is conducive to facilitating the penetration of electrolyte and providing the more contact area of electrolyte with LiFePO4/C. As a result, the as-prepared LiFePO4/C cathode material delivers an outstanding discharge capacity of 102.1 mAh g-1, 94.2% of the initial capacity (108.3 mAh g-1), after 1000 cycles at 10 C. Even at an ultrahigh current rate of 50 C, it still shows an initial discharge capacity of 58 mAh g-1.

Rapid Polyol-Assisted Microwave Synthesis of Nanocrystalline LiFePO4/C Cathode for Lithium-Ion Batteries.

PubMed

Paul, Baboo Joseph; Gim, Jihyeon; Baek, Sora; Kang, Jungwon; Song, Jinju; Kim, Sungjin; Kim, Jaekook

2015-08-01

Nanocrystalline LiFePO4/C has been synthesized under a very short period of time (90 sec) using a polyol-assisted microwave heating synthesis technique. The X-ray diffraction (XRD) data indicates that the rapidly synthesized materials correspond to phase pure olivine. Post-annealing of the as-prepared sample at 600 °C in argon atmosphere yields highly crystalline LiFePO4/C. The morphology of the samples studied using scanning electron microscopy (SEM) reveals the presence of secondary particles formed from aggregation of primary particles in the range of 30-50 nm. Transmission electron microscopy (TEM) images reveal a thin carbon layer coating on the surface of the primary particle. The charge/discharge studies indicate that the as-prepared and annealed LiFePO4/C samples delivered initial discharge capacities of 126 and 160 mA h g-1, respectively, with good capacity retentions at 0.05 mA cm-2 current densities. The post-annealing process indeed improves the crystallinity of the LiFePO4 nanocrystals, which enhances the electrode performance of LiFePO4/C.

Self-assembled LiFePO4 nanowires with high rate capability for Li-ion batteries.

PubMed

Peng, Lele; Zhao, Yu; Ding, Yu; Yu, Guihua

2014-08-28

Controlling the dimensions in the nanometer scale of olivine-type LiFePO4 has been regarded as one of the most effective strategies to improve its electrochemical performance for Li-ion batteries. In this communication, we demonstrate a novel LiFePO4 nanoarchitecture, which is composed of self-assembled single-crystalline nanowires and exhibits good rate capability with a reversible capacity of ∼110 mA h g(-1) at a current rate of 30 C, and a stable capacity retention of ∼86% after 1000 cycles at a current rate of 10 C.

Microwave synthesis of molybdenum doped LiFePO4/C and its electrochemical studies.

PubMed

Naik, Amol; P, Sajan C

2016-05-10

A Mo-doped LiFePO4 composite was prepared successfully from an iron carbonyl complex by adopting a facile and rapid microwave assisted solid state method. The evolution of gases from the iron precursor produces a highly porous product. The formation and substitution of Mo in LiFePO4 were confirmed by X-ray diffraction; surface analysis was carried out by scanning electron microscopy, field emission scanning electron microscopy, and transmission electron microscopy. The electrochemical properties of the substituted LiFePO4 were examined by cyclic voltammetry, electrochemical impedance spectroscopy and by recording charge-discharge cycles. It was observed that the as prepared composites consisted of a single phase orthorhombic olivine-type structure, where Mo(6+) was successfully introduced into the M2(Fe) sites. Incorporation of supervalent Mo(6+) introduced Li(+) ion vacancies in LiFePO4. The synthesized material facilitated lithium ion diffusion during charging/discharging due to the charge compensation effect and porosity. The battery performance studies showed that LiMo0.05Fe0.095PO4 exhibited a maximum capacity of 169.7 mA h g(-1) at 0.1 C current density, with admirable stability retention. Even at higher current densities, the retention of the specific capacity was exceptional.

Enhanced thermal safety and high power performance of carbon-coated LiFePO4 olivine cathode for Li-ion batteries

NASA Astrophysics Data System (ADS)

Zaghib, K.; Dubé, J.; Dallaire, A.; Galoustov, K.; Guerfi, A.; Ramanathan, M.; Benmayza, A.; Prakash, J.; Mauger, A.; Julien, C. M.

2012-12-01

The carbon-coated LiFePO4 Li-ion oxide cathode was studied for its electrochemical, thermal, and safety performance. This electrode exhibited a reversible capacity corresponding to more than 89% of the theoretical capacity when cycled between 2.5 and 4.0 V. Cylindrical 18,650 cells with carbon-coated LiFePO4 also showed good capacity retention at higher discharge rates up to 5C rate with 99.3% coulombic efficiency, implying that the carbon coating improves the electronic conductivity. Hybrid Pulse Power Characterization (HPPC) test performed on LiFePO4 18,650 cell indicated the suitability of this carbon-coated LiFePO4 for high power HEV applications. The heat generation during charge and discharge at 0.5C rate, studied using an Isothermal Microcalorimeter (IMC), indicated cell temperature is maintained in near ambient conditions in the absence of external cooling. Thermal studies were also investigated by Differential Scanning Calorimeter (DSC) and Accelerating Rate Calorimeter (ARC), which showed that LiFePO4 is safer, upon thermal and electrochemical abuse, than the commonly used lithium metal oxide cathodes with layered and spinel structures. Safety tests, such as nail penetration and crush test, were performed on LiFePO4 and LiCoO2 cathode based cells, to investigate on the safety hazards of the cells upon severe physical abuse and damage.

High-capacity cathodes for lithium-ion batteries from nanostructured LiFePO4 synthesized by highly-flexible and scalable flame spray pyrolysis

NASA Astrophysics Data System (ADS)

Hamid, N. A.; Wennig, S.; Hardt, S.; Heinzel, A.; Schulz, C.; Wiggers, H.

2012-10-01

Olivine, LiFePO4 is a promising cathode material for lithium-ion batteries due to its low cost, environmental acceptability and high stability. Its low electric conductivity prevented it for a long time from being used in large-scale applications. Decreasing its particle size along with carbon coating significantly improves electronic conductivity and lithium diffusion. With respect to the controlled formation of very small particles with large specific surface, gas-phase synthesis opens an economic and flexible route towards high-quality battery materials. Amorphous FePO4 was synthesized as precursor material for LiFePO4 by flame spray pyrolysis of a solution of iron acetylacetonate and tributyl phosphate in toluene. The pristine FePO4 with a specific surface from 126-218 m2 g-1 was post-processed to LiFePO4/C composite material via a solid-state reaction using Li2CO3 and glucose. The final olivine LiFePO4/C particles still showed a large specific surface of 24 m2 g-1 and were characterized using X-ray diffraction (XRD), electron microscopy, X-ray photoelectron spectrocopy (XPS) and elemental analysis. Electrochemical investigations of the final LiFePO4/C composites show reversible capacities of more than 145 mAh g-1 (about 115 mAh g-1 with respect to the total coating mass). The material supports high drain rates at 16 C while delivering 40 mAh g-1 and causes excellent cycle stability.

In situ Electrochemical-AFM Study of LiFePO4 Thin Film in Aqueous Electrolyte.

PubMed

Wu, Jiaxiong; Cai, Wei; Shang, Guangyi

2016-12-01

Lithium-ion (Li-ion) batteries have been widely used in various kinds of electronic devices in our daily life. The use of aqueous electrolyte in Li-ion battery would be an alternative way to develop low cost and environmentally friendly batteries. In this paper, the lithium iron phosphate (LiFePO4) thin film cathode for the aqueous rechargeable Li-ion battery is prepared by radio frequency magnetron sputtering deposition method. The XRD, SEM, and AFM results show that the film is composed of LiFePO4 grains with olivine structure and the average size of 100 nm. Charge-discharge measurements at current density of 10 μAh cm(-2) between 0 and 1 V show that the LiFePO4 thin film electrode is able to deliver an initial discharge capacity of 113 mAh g(-1). Specially, the morphological changes of the LiFePO4 film electrode during charge and discharge processes were investigated in aqueous environment by in situ EC-AFM, which is combined AFM with chronopotentiometry method. The changes in grain area are measured, and the results show that the size of the grains decreases and increases during the charge and discharge, respectively; the relevant mechanism is discussed.

Rate-induced solubility and suppression of the first-order phase transition in olivine LiFePO4.

PubMed

Zhang, Xiaoyu; van Hulzen, Martijn; Singh, Deepak P; Brownrigg, Alex; Wright, Jonathan P; van Dijk, Niels H; Wagemaker, Marnix

2014-05-14

The impact of ultrahigh (dis)charge rates on the phase transition mechanism in LiFePO4 Li-ion electrodes is revealed by in situ synchrotron diffraction. At high rates the solubility limits in both phases increase dramatically, causing a fraction of the electrode to bypass the first-order phase transition. The small transforming fraction demonstrates that nucleation rates are consequently not limiting the transformation rate. In combination with the small fraction of the electrode that transforms at high rates, this indicates that higher performances may be achieved by further optimizing the ionic/electronic transport in LiFePO4 electrodes.

Rate-dependent, Li-ion insertion/deinsertion behavior of LiFePO4 cathodes in commercial 18650 LiFePO4 cells.

PubMed

Liu, Qi; He, Hao; Li, Zhe-Fei; Liu, Yadong; Ren, Yang; Lu, Wenquan; Lu, Jun; Stach, Eric A; Xie, Jian

2014-03-12

We have performed operando synchrotron high-energy X-ray diffraction (XRD) to obtain nonintrusive, real-time monitoring of the dynamic chemical and structural changes in commercial 18650 LiFePO4/C cells under realistic cycling conditions. The results indicate a nonequilibrium lithium insertion and extraction in the LiFePO4 cathode, with neither the LiFePO4 phase nor the FePO4 phase maintaining a static composition during lithium insertion/extraction. On the basis of our observations, we propose that the LiFePO4 cathode simultaneously experiences both a two-phase reaction mechanism and a dual-phase solid-solution reaction mechanism over the entire range of the flat voltage plateau, with this dual-phase solid-solution behavior being strongly dependent on charge/discharge rates. The proposed dual-phase solid-solution mechanism may explain the remarkable rate capability of LiFePO4 in commercial cells.

Electrochemical performances of LiMnPO4 synthesized from non-stoichiometric Li/Mn ratio.

PubMed

Xiao, Jie; Chernova, Natasha A; Upreti, Shailesh; Chen, Xilin; Li, Zheng; Deng, Zhiqun; Choi, Daiwon; Xu, Wu; Nie, Zimin; Graff, Gordon L; Liu, Jun; Whittingham, M Stanley; Zhang, Ji-Guang

2011-10-28

In this paper, the influences of the lithium content in the starting materials on the final performances of as-prepared Li(x)MnPO(4) (x hereafter represents the starting Li content in the synthesis step which does not necessarily mean that Li(x)MnPO(4) is a single phase solid solution in this work.) are systematically investigated. It has been revealed that Mn(2)P(2)O(7) is the main impurity when Li < 1.0 while Li(3)PO(4) begins to form once x > 1.0. The interactions between Mn(2)P(2)O(7) or Li(3)PO(4) impurities and LiMnPO(4) are studied in terms of the structural, electrochemical, and magnetic properties. At a slow rate of C/50, the reversible capacity of both Li(0.5)MnPO(4) and Li(0.8)MnPO(4) increases with cycling. This indicates a gradual activation of more sites to accommodate a reversible diffusion of Li(+) ions that may be related to the interaction between Mn(2)P(2)O(7) and LiMnPO(4) nanoparticles. Among all of the different compositions, Li(1.1)MnPO(4) exhibits the most stable cycling ability probably because of the existence of a trace amount of Li(3)PO(4) impurity that functions as a solid-state electrolyte on the surface. The magnetic properties and X-ray absorption spectroscopy (XAS) of the MnPO(4)·H(2)O precursor, pure and carbon-coated Li(x)MnPO(4) are also investigated to identify the key steps involved in preparing a high-performance LiMnPO(4). This journal is © the Owner Societies 2011

Aqueous synthesis of LiFePO4 with Fractal Granularity.

PubMed

Cabán-Huertas, Zahilia; Ayyad, Omar; Dubal, Deepak P; Gómez-Romero, Pedro

2016-06-03

Lithium iron phosphate (LiFePO4) electrodes with fractal granularity are reported. They were made from a starting material prepared in water by a low cost, easy and environmentally friendly hydrothermal method, thus avoiding the use of organic solvents. Our method leads to pure olivine phase, free of the impurities commonly found after other water-based syntheses. The fractal structures consisted of nanoparticles grown into larger micro-sized formations which in turn agglomerate leading to high tap density electrodes, which is beneficial for energy density. These intricate structures could be easily and effectively coated with a thin and uniform carbon layer for increased conductivity, as it is well established for simpler microstructures. Materials and electrodes were studied by means of XRD, SEM, TEM, SAED, XPS, Raman and TGA. Last but not least, lithium transport through fractal LiFePO4 electrodes was investigated based upon fractal theory. These water-made fractal electrodes lead to high-performance lithium cells (even at high rates) tested by CV and galvanostatic charge-discharge, their performance is comparable to state of the art (but less environmentally friendly) electrodes.

Aqueous synthesis of LiFePO4 with Fractal Granularity

PubMed Central

Cabán-Huertas, Zahilia; Ayyad, Omar; Dubal, Deepak P.; Gómez-Romero, Pedro

2016-01-01

Lithium iron phosphate (LiFePO4) electrodes with fractal granularity are reported. They were made from a starting material prepared in water by a low cost, easy and environmentally friendly hydrothermal method, thus avoiding the use of organic solvents. Our method leads to pure olivine phase, free of the impurities commonly found after other water-based syntheses. The fractal structures consisted of nanoparticles grown into larger micro-sized formations which in turn agglomerate leading to high tap density electrodes, which is beneficial for energy density. These intricate structures could be easily and effectively coated with a thin and uniform carbon layer for increased conductivity, as it is well established for simpler microstructures. Materials and electrodes were studied by means of XRD, SEM, TEM, SAED, XPS, Raman and TGA. Last but not least, lithium transport through fractal LiFePO4 electrodes was investigated based upon fractal theory. These water-made fractal electrodes lead to high-performance lithium cells (even at high rates) tested by CV and galvanostatic charge-discharge, their performance is comparable to state of the art (but less environmentally friendly) electrodes. PMID:27256504

Aqueous synthesis of LiFePO4 with Fractal Granularity

NASA Astrophysics Data System (ADS)

Cabán-Huertas, Zahilia; Ayyad, Omar; Dubal, Deepak P.; Gómez-Romero, Pedro

2016-06-01

Lithium iron phosphate (LiFePO4) electrodes with fractal granularity are reported. They were made from a starting material prepared in water by a low cost, easy and environmentally friendly hydrothermal method, thus avoiding the use of organic solvents. Our method leads to pure olivine phase, free of the impurities commonly found after other water-based syntheses. The fractal structures consisted of nanoparticles grown into larger micro-sized formations which in turn agglomerate leading to high tap density electrodes, which is beneficial for energy density. These intricate structures could be easily and effectively coated with a thin and uniform carbon layer for increased conductivity, as it is well established for simpler microstructures. Materials and electrodes were studied by means of XRD, SEM, TEM, SAED, XPS, Raman and TGA. Last but not least, lithium transport through fractal LiFePO4 electrodes was investigated based upon fractal theory. These water-made fractal electrodes lead to high-performance lithium cells (even at high rates) tested by CV and galvanostatic charge-discharge, their performance is comparable to state of the art (but less environmentally friendly) electrodes.

Effect of synthesizing method on the properties of LiFePO4/C composite for rechargeable lithium-ion batteries

NASA Astrophysics Data System (ADS)

Yoon, Man-Soon; Islam, Mobinul; Park, Young Min; Ur, Soon-Chul

2013-03-01

Olivine-type LiFePO4/C cathode materials are fabricated with FePO4 powders that are pre-synthesized by two different processes from iron chloride solution. Process I is a modified precipitation method which is implemented by the pH control of a solution using NH4OH to form FePO4 precipitates at room temperature. Process II is a conventional precipitation method, of which H3PO4 (85%) solution is gradually added to a FeCl3 solution during the process to maintain a designated mole ratio. The solution is subsequently aged at 90°C in a water bath until FePO4 precipitates appear. In order to synthesize LiFePO4/C composites, each batch of FePO4 powders is then mixed with pre-milled lithium carbonate and glucose (8 wt. %) as a carbon source in a ball-mill. The structural characteristics of both LiFePO4/C composites fabricated using iron phospates from two different routes have been examined employing XRD and SEM. The modified precipitation process is considered to be a relatively simple and effective process for the preparation of LiFePO4/C composites owing to their excellent electrochemical properties and rate capabilities.

Lithium-ions diffusion kinetic in LiFePO4/carbon nanoparticles synthesized by microwave plasma chemical vapor deposition for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Gao, Chao; Zhou, Jian; Liu, Guizhen; Wang, Lin

2018-03-01

Olivine structure LiFePO4/carbon nanoparticles are synthesized successfully using a microwave plasma chemical vapor deposition (MPCVD) method. Microwave is an effective method to synthesize nanomaterials, the LiFePO4/carbon nanoparticles with high crystallinity can shorten diffusion routes for ionic transfer and electron tunneling. Meanwhile, a high quality, complete and homogenous carbon layer with appropriate thickness coating on the surface of LiFePO4 particles during in situ chemical vapor deposition process, which can ensure that electrons are able to transfer fast enough from all sides. Electrochemical impedance spectroscopy (EIS) is carried out to collect information about the kinetic behavior of lithium diffusion in LiFePO4/carbon nanoparticles during the charging and discharging processes. The chemical diffusion coefficients of lithium ions, DLi, are calculated in the range of 10-15-10-9 cm2s-1. Nanoscale LiFePO4/carbon particles show the longer regions of the faster solid-solution diffusion, and corresponding to the narrower region of the slower two-phase diffusion during the insertion/exaction of lithium ions. The CV and galvanostatic charge-discharge measurements show that the LiFePO4/carbon nanoparticles perform an excellent electrochemical performance, especially the high rate capacity and cycle life.

Preparation and characterization of core-shell structured LiFePO4/C composite using a novel carbon source for lithium-ion battery cathode

NASA Astrophysics Data System (ADS)

Huang, Zan; Luo, Peifang; Wang, Daxiang

2017-03-01

Core-shell structured LiFePO4/C1 cathode material is synthesized via a rapid microwave irradiation route using ethylene diamine tetraacetic acid (EDTA) as the novel carbon source. XRD results reveal that all the patterns can be indexed as the olivine-type structured LiFePO4 with the space group of Pnma. TEM images show that the obtained carbon is an amorphous layer with a thickness of about 3-4 nm. When the LiFePO4/C1 used as cathode material for lithium-ion battery, it delivers an initial discharge capacity of 163.1 mAh g-1 at 0.1 C which is about 96% of the theoretical capacity. Moreover, it also shows excellent rate performance and good cycle stability due to the enhanced electronic conductivity as proved by the electrochemical impedance spectroscopy (EIS). Thus, this carbon decorated LiFePO4 composite synthesized via the rapid microwave irradiation method is a promising cathode material for high-performance lithium-ion battery.

Ab initio identification of the Li-rich phase in LiFePO4.

PubMed

Zeng, Hua; Gu, Yue; Teng, Gaofeng; Liu, Yimeng; Zheng, Jiaxin; Pan, Feng

2018-06-27

A recent discovery of anionic redox activity in Li-rich layered compounds opens a new direction for the design of high-capacity cathode materials for lithium-ion batteries. Here using extensive ab initio calculations, the thermodynamic existence of the Li-rich phase in LiFePO4 to form Li1+xFe1-xPO4 with x not exceeding 12.5% has been proved. Anionic redox activity and structural stability during delithiation are further investigated. Interestingly, it is found that Li1+xFe1-xPO4 cannot be delithiated completely and thus cannot achieve extra capacity by anionic redox activity, because the local oxygen-ion redox will cause the fracture of the rigid framework formed by phosphate tetrahedral polyanions. Although an extra capacity cannot be realized, the excess Li-ions at Fe sites can enhance the Li-ion diffusivity along the adjacent [010] channel and contribute to the shift from 1D to 2D/3D diffusion. This study provides a fresh perspective on olivine-type LiFePO4 and offers some important clues on designing Li-rich cathode materials with high energy density.

Role of PO4 tetrahedron in LiFePO4 and FePO4 system.

PubMed

Zeng, Yuewu

2015-06-01

Using high resolution transmission electron microscopy with image simulation and Fourier analysis, the Li1- x FePO4 (x < 0.01), Li1- x FePO4 (x ∼ 0.5), and FePO4 particles, prepared by charging or discharging the 053048 electrochemical cells (thickness: 5 mm, width: 30 mm, height: 48 mm) and dismantled inside an Ar-filled dry box, were investigated. The high resolution images reveal: (1) the solid solution of Li1- x FePO4 (x < 0.01) contains some missing Li ions leading PO4 group distorted around M1 tunnel of the unit cell; (2) the texture of the particles of Li1- x FePO4 (x ∼0.5) has homogeneously distributed compositional domains of LiFePO4 and FePO4 resulting from spinodal decomposition which promote Li ion easily getting into the particle due to uphill diffusion, (3) the particles of FePO4 formed in charging have heavily distorted lattice and contain some isolated LiFePO4 , (4) interface between LiFePO4 and FePO4 and between amorphous and crystal region provides the lattice distortion of small polarons. © 2015 Wiley Periodicals, Inc.

Anode property of carbon coated LiFePO4 nanocrystals

NASA Astrophysics Data System (ADS)

Ni, Jiangfeng; Jiang, Jiaxing; Savilov, S. V.; Aldoshin, S. M.

2016-10-01

Nanostructured LiFePO4 is appealing cathode material for rechargeable lithium batteries. Herein, however, we report the intriguing anode properties of carbon coated LiFePO4 nanocrystals. In the potential range of 0-3.0 V, the LiFePO4 nanocrystal electrodes afford high reversible capacity of 373 mAhg-1 at a current rate of 0.05 Ag-1 and retains 239 mAhg-1 at a much higher rate of 1.25 Ag-1. In addition, it is capable of sustaining 1000 cycles at 1.25 Ag-1 without any capacity fading. Such superior properties indicate that nanostructured LiFePO4 could also be promising anode for rechargeable battery applications.

Unlocking the energy capabilities of micron-sized LiFePO4.

PubMed

Guo, Limin; Zhang, Yelong; Wang, Jiawei; Ma, Lipo; Ma, Shunchao; Zhang, Yantao; Wang, Erkang; Bi, Yujing; Wang, Deyu; McKee, William C; Xu, Ye; Chen, Jitao; Zhang, Qinghua; Nan, Cewen; Gu, Lin; Bruce, Peter G; Peng, Zhangquan

2015-08-03

Utilization of LiFePO4 as a cathode material for Li-ion batteries often requires size nanonization coupled with calcination-based carbon coating to improve its electrochemical performance, which, however, is usually at the expense of tap density and may be environmentally problematic. Here we report the utilization of micron-sized LiFePO4, which has a higher tap density than its nano-sized siblings, by forming a conducting polymer coating on its surface with a greener diazonium chemistry. Specifically, micron-sized LiFePO4 particles have been uniformly coated with a thin polyphenylene film via the spontaneous reaction between LiFePO4 and an aromatic diazonium salt of benzenediazonium tetrafluoroborate. The coated micron-sized LiFePO4, compared with its pristine counterpart, has shown improved electrical conductivity, high rate capability and excellent cyclability when used as a 'carbon additive free' cathode material for rechargeable Li-ion batteries. The bonding mechanism of polyphenylene to LiFePO4/FePO4 has been understood with density functional theory calculations.

Unlocking the energy capabilities of micron-sized LiFePO4

PubMed Central

Guo, Limin; Zhang, Yelong; Wang, Jiawei; Ma, Lipo; Ma, Shunchao; Zhang, Yantao; Wang, Erkang; Bi, Yujing; Wang, Deyu; McKee, William C.; Xu, Ye; Chen, Jitao; Zhang, Qinghua; Nan, Cewen; Gu, Lin; Bruce, Peter G.; Peng, Zhangquan

2015-01-01

Utilization of LiFePO4 as a cathode material for Li-ion batteries often requires size nanonization coupled with calcination-based carbon coating to improve its electrochemical performance, which, however, is usually at the expense of tap density and may be environmentally problematic. Here we report the utilization of micron-sized LiFePO4, which has a higher tap density than its nano-sized siblings, by forming a conducting polymer coating on its surface with a greener diazonium chemistry. Specifically, micron-sized LiFePO4 particles have been uniformly coated with a thin polyphenylene film via the spontaneous reaction between LiFePO4 and an aromatic diazonium salt of benzenediazonium tetrafluoroborate. The coated micron-sized LiFePO4, compared with its pristine counterpart, has shown improved electrical conductivity, high rate capability and excellent cyclability when used as a ‘carbon additive free' cathode material for rechargeable Li-ion batteries. The bonding mechanism of polyphenylene to LiFePO4/FePO4 has been understood with density functional theory calculations. PMID:26235395

Unlocking the energy capabilities of micron-sized LiFePO4

NASA Astrophysics Data System (ADS)

Guo, Limin; Zhang, Yelong; Wang, Jiawei; Ma, Lipo; Ma, Shunchao; Zhang, Yantao; Wang, Erkang; Bi, Yujing; Wang, Deyu; McKee, William C.; Xu, Ye; Chen, Jitao; Zhang, Qinghua; Nan, Cewen; Gu, Lin; Bruce, Peter G.; Peng, Zhangquan

2015-08-01

Utilization of LiFePO4 as a cathode material for Li-ion batteries often requires size nanonization coupled with calcination-based carbon coating to improve its electrochemical performance, which, however, is usually at the expense of tap density and may be environmentally problematic. Here we report the utilization of micron-sized LiFePO4, which has a higher tap density than its nano-sized siblings, by forming a conducting polymer coating on its surface with a greener diazonium chemistry. Specifically, micron-sized LiFePO4 particles have been uniformly coated with a thin polyphenylene film via the spontaneous reaction between LiFePO4 and an aromatic diazonium salt of benzenediazonium tetrafluoroborate. The coated micron-sized LiFePO4, compared with its pristine counterpart, has shown improved electrical conductivity, high rate capability and excellent cyclability when used as a `carbon additive free' cathode material for rechargeable Li-ion batteries. The bonding mechanism of polyphenylene to LiFePO4/FePO4 has been understood with density functional theory calculations.

Relevance of LiPF6 as Etching Agent of LiMnPO4 Colloidal Nanocrystals for High Rate Performing Li-ion Battery Cathodes.

PubMed

Chen, Lin; Dilena, Enrico; Paolella, Andrea; Bertoni, Giovanni; Ansaldo, Alberto; Colombo, Massimo; Marras, Sergio; Scrosati, Bruno; Manna, Liberato; Monaco, Simone

2016-02-17

LiMnPO4 is an attractive cathode material for the next-generation high power Li-ion batteries, due to its high theoretical specific capacity (170 mA h g(-1)) and working voltage (4.1 V vs Li(+)/Li). However, two main drawbacks prevent the practical use of LiMnPO4: its low electronic conductivity and the limited lithium diffusion rate, which are responsible for the poor rate capability of the cathode. The electronic resistance is usually lowered by coating the particles with carbon, while the use of nanosize particles can alleviate the issues associated with poor ionic conductivity. It is therefore of primary importance to develop a synthetic route to LiMnPO4 nanocrystals (NCs) with controlled size and coated with a highly conductive carbon layer. We report here an effective surface etching process (using LiPF6) on colloidally synthesized LiMnPO4 NCs that makes the NCs dispersible in the aqueous glucose solution used as carbon source for the carbon coating step. Also, it is likely that the improved exposure of the NC surface to glucose facilitates the formation of a conductive carbon layer that is in intimate contact with the inorganic core, resulting in a high electronic conductivity of the electrode, as observed by us. The carbon coated etched LiMnPO4-based electrode exhibited a specific capacity of 118 mA h g(-1) at 1C, with a stable cycling performance and a capacity retention of 92% after 120 cycles at different C-rates. The delivered capacities were higher than those of electrodes based on not etched carbon coated NCs, which never exceeded 30 mA h g(-1). The rate capability here reported for the carbon coated etched LiMnPO4 nanocrystals represents an important result, taking into account that in the electrode formulation 80% wt is made of the active material and the adopted charge protocol is based on reasonable fast charge times.

Nanocomposite Electrodes for Advanced Lithium Batteries: The LiFePO4 Cathode

DTIC Science & Technology

2001-11-01

The LiFePO4 Cathode DISTRIBUTION: Approved for public release, distribution unlimited This paper is part of the following report: TITLE: Nanophase and...Nanocomposite Electrodes for Advanced Lithium Batteries: The LiFePO4 Cathode Shoufeng Yang, Yanning Song, Peter Y. Zavalij and M. Stanley Whittingham...Institute for Materials Research, Binghamton University, Binghamton, NY 13902-1600, U.S.A. ABSTRACT LiFePO4 was successfully synthesized by high temperature

Virtual synthesis of crystals using ab initio MD: Case study on LiFePO4

NASA Astrophysics Data System (ADS)

Mishra, S. B.; Nanda, B. R. K.

2017-05-01

Molecular dynamics simulation technique is fairly successful in studying the structural aspects and dynamics of fluids. Here we study the ability of ab initio molecular dynamics (ab initio MD) to carry out virtual experiments to synthesize new crystalline materials and to predict their structures. For this purpose the olivine phosphate LiFePO4 (LFPO) is used as an example. As transition metal oxides in general are stabilized with layered geometry, we carried out ab initio MD simulations over a hypothetical layered configuration consisting of alternate LiPO2 and FeO2 layers. With intermittent steps of electron minimization, the resulted equilibrium lattice consist of PO4 tetrahedra and distorted Fe-O complexes similar to the one observed in the experimental lattice.

Chemically grafted carbon-coated LiFePO4 using diazonium chemistry

NASA Astrophysics Data System (ADS)

Delaporte, Nicolas; Perea, Alexis; Amin, Ruhul; Zaghib, Karim; Bélanger, Daniel

2015-04-01

The effect of surface functionalization of aminophenyl and bromophenyl groups on carbon-coated LiFePO4 and the electrochemical properties of composite electrode containing these materials are reported. The functionalization was performed by spontaneous reduction of the corresponding in situ generated diazonium ions. The resulting chemically grafted LiFePO4/C materials were characterized by energy-dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) to confirm the presence of the surface organic species. XRD analyses indicated the cathode material was partially oxidized. Thermogravimetric and elemental analyses revealed the loading of grafted molecules was between 0.2 and 1.1 wt.% depending on the reaction conditions. Interestingly, the electrochemical performances of the modified LiFePO4/C are not adversely affected by the presence of either aminophenyl and bromophenyl groups at the carbon surface, and in fact the grafted LiFePO4/C displayed slightly superior discharge capacity at the highest C rate investigated for a low loading of organic molecules.

Assembly of LiMnPO4 Nanoplates into Microclusters as a High-Performance Cathode in Lithium-Ion Batteries.

PubMed

Wang, Chao; Li, Shiheng; Han, Yuyao; Lu, Zhenda

2017-08-23

A novel structure of a carbon-coated LiMnPO 4 microcluster through emulsion-based self-assembly has been fabricated to yield a high-performance battery cathode. In this rational design, nanosized LiMnPO 4 plates are assembled into microclusters to achieve a dense packing and robust interparticle contact. In addition, the conductive carbon framework wrapping around these clusters functions as a fast electron highway, ensuring the high utilization of the active materials. The designed structure demonstrates enhanced specific capacity and cycling stability in lithium-ion batteries, delivering a discharge capacity of 120 mAh g -1 after 200 cycles at 0.2 C. It also shows a superior rate capability with discharge capacities of 139.7 mAh g -1 at 0.05 C, 131.7 mAh g -1 at 0.1 C, and 99.2 mAh g -1 at 1 C at room temperature.

Unraveling the Complex Delithiation Mechanisms of Olivine-Type Cathode Materials, LiFe x Co 1–x PO 4

DOE Office of Scientific and Technical Information (OSTI.GOV)

Strobridge, Fiona C.; Liu, Hao; Leskes, Michal

2016-06-14

The delithiation mechanisms occurring within the olivine-type class of cathode materials for Li-ion batteries have received considerable attention owing to the good capacity retention at high rates for LiFePO4. A comprehensive mechanistic study of the (de)lithiation reactions that occur when the substituted olivine-type cathode materials LiFexCo1-xPO4 (x = 0, 0.05, 0.125, 0.25, 0.5, 0.75, 0.875, 0.95 and 1) are electrochemically cycled is reported here, using in situ X-ray diffraction (XRD) data. On the first charge, two intermediate phases are observed and identified: Li1-x(Fe3+)x(Co2+)1- xPO4 for 0 < x < 1 (i.e. after oxidation of Fe2+ => Fe3+) and Li2/3FexCo1-xPO4 formore » 0 ≤ x ≤ 0.5 (i.e. the Co-majority materials). For the Fe-rich materials, we study how nonequilibrium, single-phase mechanisms that occur discretely in single particles, as observed for LiFePO4 at high rates, is affected by Co substitution. In the Co-majority materials, a two-phase mechanism with a coherent interface is observed, as was seen in LiCoPO4, and we discuss how it is manifested in the XRD patterns. We then compare the nonequilibrium, single-phase mechanism with the bulk single-phase and the coherent interface two-phase mechanisms. Despite the apparent differences between these mechanisms, we discuss how they are related and interconverted as a function of Fe/Co substitution and the potential implications for the electrochemistry of this system.« less

Single-crystalline LiFePO4 nanosheets for high-rate Li-ion batteries.

PubMed

Zhao, Yu; Peng, Lele; Liu, Borui; Yu, Guihua

2014-05-14

The lithiation/delithiation in LiFePO4 is highly anisotropic with lithium-ion diffusion being mainly confined to channels along the b-axis. Controlling the orientation of LiFePO4 crystals therefore plays an important role for efficient mass transport within this material. We report here the preparation of single crystalline LiFePO4 nanosheets with a large percentage of highly oriented {010} facets, which provide the highest pore density for lithium-ion insertion/extraction. The LiFePO4 nanosheets show a high specific capacity at low charge/discharge rates and retain significant capacities at high C-rates, which may benefit the development of lithium batteries with both favorable energy and power density.

The effect of heat preservation time on the electrochemical properties of LiFePO4

NASA Astrophysics Data System (ADS)

He, Rui; Zhang, Lihui; Bai, Xue; Liu, Zhenfa

2017-12-01

LiFePO4 was prepared via high temperature solid-state method at different heat preservation time. XRD and SEM was used to test the structure and morphology of LiFePO4. Land 2001 was used to test the electrochemical performance of LiFePO4. The results illustrated that well-crystallized LiFePO4 composite with homogeneous small particles was obtained by XRD and SEM. And the optimum heat preservation time was 4 hour. From charge/discharge test, it can be seen that at 0.2C, LiFePO4 has initial discharge capacities of 159.1mAh/g at the heat preservation time 4 hour. From the rate capacity, it can be seen that the discharge capacity was of optimum sample remains above 99% after 200 cycles.

Three-Dimensional Honeycomb-Structural LiAlO2-Modified LiMnPO4 Composite with Superior High Rate Capability as Li-Ion Battery Cathodes.

PubMed

Li, Junzhe; Luo, Shaohua; Ding, Xueyong; Wang, Qing; He, Ping

2018-04-04

In the efforts toward the rapidly increasing demands for high-power application, cathode materials with three-dimensional (3D) architectures have been proposed. Here, we report the construction of the 3D LiAlO 2 -LiMnPO 4 /C cathode materials for lithium-ion batteries in an innovation way. The as-prepared 3D active materials LiMnPO 4 /C and the honeycomb-like Li-ion conductor LiAlO 2 framework are used as working electrode directly without additional usage of polymeric binder. The electrochemical performance has been improved significantly due to the special designed core-shell architectures of LiMnPO 4 /C@LiAlO 2 . The 3D binder-free electrode exhibits high rate capability as well as superior cycling stability with a capability of ∼105 mAh g -1 and 98.4% capacity retention after 100 cycles at a high discharge rate of 10 C. Such synthesis method adopted in our work can be further extended to other promising candidates and would also inspire new avenues of development of 3D materials for lithium-ion batteries.

Magnetism in olivine-type LiCo(1-x)Fe(x)PO4 cathode materials: bridging theory and experiment.

PubMed

Singh, Vijay; Gershinsky, Yelena; Kosa, Monica; Dixit, Mudit; Zitoun, David; Major, Dan Thomas

2015-12-14

In the current paper, we present a non-aqueous sol-gel synthesis of olivine type LiCo1-xFexPO4 compounds (x = 0.00, 0.25, 0.50, 0.75, 1.00). The magnetic properties of the olivines are measured experimentally and calculated using first-principles theory. Specifically, the electronic and magnetic properties are studied in detail with standard density functional theory (DFT), as well as by including spin-orbit coupling (SOC), which couples the spin to the crystal structure. We find that the Co(2+) ions exhibit strong orbital moment in the pure LiCoPO4 system, which is partially quenched upon substitution of Co(2+) by Fe(2+). Interestingly, we also observe a non-negligible orbital moment on the Fe(2+) ion. We underscore that the inclusion of SOC in the calculations is essential to obtain qualitative agreement with the observed effective magnetic moments. Additionally, Wannier functions were used to understand the experimentally observed rising trend in the Néel temperature, which is directly related to the magnetic exchange interaction paths in the materials. We suggest that out of layer M-O-P-O-M magnetic interactions (J⊥) are present in the studied materials. The current findings shed light on important differences observed in the electrochemistry of the cathode material LiCoPO4 compared to the already mature olivine material LiFePO4.

Evolution of LiFePO4 thin films interphase with electrolyte

NASA Astrophysics Data System (ADS)

Dupré, N.; Cuisinier, M.; Zheng, Y.; Fernandez, V.; Hamon, J.; Hirayama, M.; Kanno, R.; Guyomard, D.

2018-04-01

Many parameters may control the growth and the characteristics of the interphase, such as surface structure and morphology, structural defects, grain boundaries, surface reactions, etc. However, polycrystalline surfaces contain these parameters simultaneously, resulting in a quite complicated system to study. Working with model electrode surfaces using crystallographically oriented crystalline thin films appears as a novel and unique approach to understand contributions of preferential orientation and rugosity of the surface. In order to rebuild the interphase architecture along electrochemical cycling, LiFePO4 epitaxial films offering ideal 2D (100) interfaces are here investigated through the use of non-destructive depth profiling by Angular Resolved X-ray Photoelectron Spectroscopy (ARXPS). The composition and structure of the interphase is then monitored upon cycling for samples stopped at the end of charge and discharge for various numbers of cycles, and discussed in the light of combined XPS and X-ray reflectivity (XRR) measurements. Such an approach allows describing the interphase evolution on a specific model LiFePO4 crystallographic orientation and helps understanding the nature and evolution of the LiFePO4/electrolyte interphase forming on the surface of LiFePO4 poly-crystalline powder.

Mechanistic insights of Li+ diffusion within doped LiFePO4 from Muon Spectroscopy.

PubMed

Johnson, Ian D; Ashton, Thomas E; Blagovidova, Ekaterina; Smales, Glen J; Lübke, Mechthild; Baker, Peter J; Corr, Serena A; Darr, Jawwad A

2018-03-07

The Li + ion diffusion characteristics of V- and Nb-doped LiFePO 4 were examined with respect to undoped LiFePO 4 using muon spectroscopy (µSR) as a local probe. As little difference in diffusion coefficient between the pure and doped samples was observed, offering D Li values in the range 1.8-2.3 × 10 -10  cm 2 s -1 , this implied the improvement in electrochemical performance observed within doped LiFePO 4 was not a result of increased local Li + diffusion. This unexpected observation was made possible with the µSR technique, which can measure Li + self-diffusion within LiFePO 4 , and therefore negated the effect of the LiFePO 4 two-phase delithiation mechanism, which has previously prevented accurate Li + diffusion comparison between the doped and undoped materials. Therefore, the authors suggest that µSR is an excellent technique for analysing materials on a local scale to elucidate the effects of dopants on solid-state diffusion behaviour.

Dynamic study of sub-micro sized LiFePO4 cathodes by in-situ tender X-ray absorption near edge structure

NASA Astrophysics Data System (ADS)

Wang, Dongniu; Wang, Huixin; Yang, Jinli; Zhou, Jigang; Hu, Yongfeng; Xiao, Qunfeng; Fang, Haitao; Sham, Tsun-Kong

2016-01-01

Olivine-type phosphates (LiMPO4, M = Fe, Mn, Co) are promising cathode materials for lithium-ion batteries that are generally accepted to follow first order equilibrium phase transformations. Herein, the phase transformation dynamics of sub-micro sized LiFePO4 particles with limited rate capability at a low current density of 0.14 C was investigated. An in-situ X-ray Absorption Near Edge Structure (XANES) measurement was conducted at the Fe and P K-edge for the dynamic studies upon lithiation and delithiation. Fe K-edge XANES spectra demonstrate that not only lithium-rich intermediate phase LixFePO4 (x = 0.6-0.75), but also lithium-poor intermediate phase LiyFePO4 (y = 0.1-0.25) exist during the charge and discharge, respectively. Furthermore, during charge and discharge, a fluctuation of the FePO4 and LiFePO4 fractions obtained by liner combination fitting around the imaginary phase fractions followed Faraday's law and the equilibrium first-order two-phase transformation versus reaction time is present, respectively. The charging and discharging process has a reversible phase transformation dynamics with symmetric structural evolution routes. P K-edge XANES spectra reveal an enrichment of PF6-1 anions at the surface of the electrode during charging.

Kinetic Monte Carlo Study of Li Intercalation in LiFePO4.

PubMed

Xiao, Penghao; Henkelman, Graeme

2018-01-23

Even as a commercial cathode material, LiFePO 4 remains of tremendous research interest for understanding Li intercalation dynamics. The partially lithiated material spontaneously separates into Li-poor and Li-rich phases at equilibrium. Phase segregation is a surprising property of LiFePO 4 given its high measured rate capability. Previous theoretical studies, aiming to describe Li intercalation in LiFePO 4 , include both atomic-scale density functional theory (DFT) calculations of static Li distributions and entire-particle-scale phase field models, based upon empirical parameters, studying the dynamics of the phase separation. Little effort has been made to bridge the gap between these two scales. In this work, DFT calculations are used to fit a cluster expansion for the basis of kinetic Monte Carlo calculations, which enables long time scale simulations with accurate atomic interactions. This atomistic model shows how the phases evolve in Li x FePO 4 without parameters from experiments. Our simulations reveal that an ordered Li 0.5 FePO4 phase with alternating Li-rich and Li-poor planes along the ac direction forms between the LiFePO 4 and FePO 4 phases, which is consistent with recent X-ray diffraction experiments showing peaks associated with an intermediate-Li phase. The calculations also help to explain a recent puzzling experiment showing that LiFePO 4 particles with high aspect ratios that are narrower along the [100] direction, perpendicular to the [010] Li diffusion channels, actually have better rate capabilities. Our calculations show that lateral surfaces parallel to the Li diffusion channels, as well as other preexisting sites that bind Li weakly, are important for phase nucleation and rapid cycling performance.

Study on SOC wavelet analysis for LiFePO4 battery

NASA Astrophysics Data System (ADS)

Liu, Xuepeng; Zhao, Dongmei

2017-08-01

Improving the prediction accuracy of SOC can reduce the complexity of the conservative and control strategy of the strategy such as the scheduling, optimization and planning of LiFePO4 battery system. Based on the analysis of the relationship between the SOC historical data and the external stress factors, the SOC Estimation-Correction Prediction Model based on wavelet analysis is established. Using wavelet neural network prediction model is of high precision to achieve forecast link, external stress measured data is used to update parameters estimation in the model, implement correction link, makes the forecast model can adapt to the LiFePO4 battery under rated condition of charge and discharge the operating point of the variable operation area. The test results show that the method can obtain higher precision prediction model when the input and output of LiFePO4 battery are changed frequently.

Synthesisofc-lifepo4 composite by solid state reaction method

NASA Astrophysics Data System (ADS)

Rahayu, I.; Hidayat, S.; Noviyanti, A. R.; Rakhmawaty, D.; Ernawati, E.

2017-02-01

In this research, the enhancement of LiFePO4 conductivity was conducted by doping method with carbon materials. Carbon-based materials were obtained from the mixture of sucrose, and the precursor of LiH2PO4 and α-Fe2O3 was synthesized by solid state reaction. Sintering temperature was varied at 700°C, 800°C, 900°C and 1,000°C. The result showed that C-LiFePO4 could be synthesized by using solid state reaction method. Based on the XRD and FTIR spectrums, C-LiFePO4 can be identified as the type of crystal, characterized by the appearance of sharp signal on (011), (211) and typical peak of LiFePO4 materials. The result of conductivity measurement from C-LiFePO4 at sintering temperature of 900°C and 1,000°C was 2×10-4 S/cm and 4×10-4S/cm, respectively. The conductivity value at sintering temperature of 700°C and 800°C was very small (<10-6 S/cm), which cannot be measured by the existing equipment.

[100]-Oriented LiFePO4 Nanoflakes toward High Rate Li-Ion Battery Cathode.

PubMed

Li, Zhaojin; Peng, Zhenzhen; Zhang, Hui; Hu, Tao; Hu, Minmin; Zhu, Kongjun; Wang, Xiaohui

2016-01-13

[100] is believed to be a tough diffusion direction for Li(+) in LiFePO4, leading to the belief that the rate performance of [100]-oriented LiFePO4 is poor. Here we report the fabrication of 12 nm-thick [100]-oriented LiFePO4 nanoflakes by a simple one-pot solvothermal method. The nanoflakes exhibit unexpectedly excellent electrochemical performance, in stark contrast to what was previously believed. Such an exceptional result is attributed to a decreased thermodynamic transformation barrier height (Δμb) associated with increased active population.

A facile method of preparing LiMnPO4/reduced graphene oxide aerogel as cathodic material for aqueous lithium-ion hybrid supercapacitors

NASA Astrophysics Data System (ADS)

Xu, Lin; Wang, Senlin; Zhang, Xiao; He, Taobin; Lu, Fengxia; Li, Huichang; Ye, Junhui

2018-01-01

A facile method of preparing LiMnPO4/reduced graphene oxide aerogel (LMP/rGO) as cathodic material was reported here. LiMnPO4 nano-particles were prepared using a facile polyvinyl pyrrolidone-assisted solvothermal route. Then LMP/rGO aerogel was prepared using the accessible restacking method. The influence of the cathodic electrode composition (ratio of rGO to LiMnPO4) on the performance of the LMP/rGO was evaluated by constant-current discharge tests. When compared with 217C g-1 for the pristine LMP, the best LMP/rGO (the content of rGO is 27.3 wt%) exhibits a higher capacity of 464.5C g-1 (at 0.5 A g-1), which presenting the capacity enhance of 114%. Moreover, a lithium-ion hybrid supercapacitor (LIHS) was successfully assembled by using LMP/rGO aerogel as the cathodic electrode and rGO aerogel as the anodic electrode. The LMP/rGO//rGO device achieves excellent specific energy of 16.46 W h kg-1 at a power density of 0.38 kW kg-1, even under the higher specific power of 4.52 kW kg-1, there still holds the specific energy of 11.79 W h kg-1. The LMP/rGO//rGO device maintains 91.2% of the initial capacity after 10,000 cycles (at 2 A g-1), which displays high rate performance and long cycle life. The 3D LMP/rGO aerogel could be a promising candidate material for the lithium-ion hybrid supercapacitors.

Synthesis and magnetic properties of LiFePO4 substitution magnesium

NASA Astrophysics Data System (ADS)

Choi, Hyunkyung; Kim, Min Ji; Hahn, Eun Joo; Kim, Sam Jin; Kim, Chul Sung

2017-06-01

LiFe0.9Mg0.1PO4 sample was prepared by using a solid-state reaction method, and the temperature-dependent magnetic properties of the sample were studied. The X-ray diffraction (XRD) pattern showed an olivine-type orthorhombic structure with space group Pnma based on Rietveld refinement method. The effect of Mg substitution in antiferromagnetic LiFe0.9Mg0.1PO4 was investigated using a vibrating sample magnetometer (VSM) and Mössbauer spectroscopy. The temperature-dependence of the magnetization curves of LiFe0.9Mg0.1PO4 shows abnormal antiferromagnetic behavior with ordering temperature. Sudden changes in both the magnetic hyperfine field (Hhf) and its slope below 15 K suggest that magnetic phase transition associated to the abrupt occurrence of spin-reorientation. The Néel temperature (TN) and spin-reorientation temperature (TS) of LiFe0.9Mg0.1PO4 are lower than those of pure LiFePO4 (TN = 51 K, TS = 23 K). This is due to the Fe-O-Fe superexchange interaction being larger than that of the Fe-O-Mg link. Also, we have confirmed a change in the electric quadrupole splitting (ΔEQ) by the spin-orbit coupling effect and the shape of Mössbauer spectrum has provided the evidence for TS and a strong crystalline field. We have found that Mg ions in LiFe0.9Mg0.1PO4 induce an asymmetric charge density due to the presence of Mg2+ ions at the FeO6 octahedral sites.

Superior lithium-ion insertion/extraction properties of a novel LiFePO4/C/graphene material used as a cathode in aqueous solution.

PubMed

Duan, Wenyuan; Zhao, Mingshu; Shen, Junfang; Zhao, Suixin; Song, Xiaoping

2017-09-28

Herein, olivine LiFePO 4 covered with graphene and carbon layers is prepared via a sol-gel method, followed by calcination, and the resultant composite is used as a cathode material in aqueous rechargeable lithium-ion batteries (ARLBs). The phase structure and morphology of the composite are characterized via X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM) and specific surface area analysis (BET). The ARLB system is fabricated using LiFePO 4 /C/graphene as the cathode and a zinc anode in 1 mol L -1 ZnSO 4 ·7H 2 O and saturated LiNO 3 aqueous solution without dissolved oxygen, which delivers a capacity of 153 mA h g -1 at 0.5C rate. Even at a 50C rate, it maintains a capacity of 95 mA h g -1 after 200 cycles. The excellent rate capabilities show that this cathode material exhibits good electrochemical performance and this novel ARLB has great potential in the fields of energy storage and high power sources.

Preparation and characterization of SnO2 and Carbon Co-coated LiFePO4 cathode materials.

PubMed

Wang, Haibin; Liu, Shuxin; Huang, Yongmao

2014-04-01

The SnO2 and carbon co-coated LiFePO4 cathode materials were successfully synthesized by solid state method. The microstructure and morphology of LiFePO4 composites were characterized by X-ray diffraction, Raman spectroscopy, scanning electron microscopy and transmission electron microscope. The results showed that the SnO2 and carbon co-coated LiFePO4 cathode materials exhibited more uniform particle size distribution. Compared with the uncoated LiFePO4/C, the structure of LiFePO4 with SnO2 and carbon coating had no change. The existence of SnO2 and carbon coating layer effectively enhanced the initial discharge capacity. Among the investigated samples, the one with DBTDL:LiFePO4 molar ratios of 7:100 exhibited the best electrochemical performance.

A chemically activated graphene-encapsulated LiFePO4 composite for high-performance lithium ion batteries.

PubMed

Ha, Jeonghyun; Park, Seung-Keun; Yu, Seung-Ho; Jin, Aihua; Jang, Byungchul; Bong, Sungyool; Kim, In; Sung, Yung-Eun; Piao, Yuanzhe

2013-09-21

A composite of modified graphene and LiFePO4 has been developed to improve the speed of charging-discharging and the cycling stability of lithium ion batteries using LiFePO4 as a cathode material. Chemically activated graphene (CA-graphene) has been successfully synthesized via activation by KOH. The as-prepared CA-graphene was mixed with LiFePO4 to prepare the composite. Microscopic observation and nitrogen sorption analysis have revealed the surface morphologies of CA-graphene and the CA-graphene/LiFePO4 composite. Electrochemical properties have also been investigated after assembling coin cells with the CA-graphene/LiFePO4 composite as a cathode active material. Interestingly, the CA-graphene/LiFePO4 composite has exhibited better electrochemical properties than the conventional graphene/LiFePO4 composite as well as bare LiFePO4, including exceptional speed of charging-discharging and excellent cycle stability. That is because the CA-graphene in the composite provides abundant porous channels for the diffusion of lithium ions. Moreover, it acts as a conducting network for easy charge transfer and as a divider, preventing the aggregation of LiFePO4 particles. Owing to these properties of CA-graphene, LiFePO4 could demonstrate enhanced and stably long-lasting electrochemical performance.

Surface Modification of the LiFePO4 Cathode for the Aqueous Rechargeable Lithium Ion Battery.

PubMed

Tron, Artur; Jo, Yong Nam; Oh, Si Hyoung; Park, Yeong Don; Mun, Junyoung

2017-04-12

The LiFePO 4 surface is coated with AlF 3 via a simple chemical precipitation for aqueous rechargeable lithium ion batteries (ARLBs). During electrochemical cycling, the unfavorable side reactions between LiFePO 4 and the aqueous electrolyte (1 M Li 2 SO 4 in water) leave a highly resistant passivation film, which causes a deterioration in the electrochemical performance. The coated LiFePO 4 by 1 wt % AlF 3 has a high discharge capacity of 132 mAh g -1 and a highly improved cycle life, which shows 93% capacity retention even after 100 cycles, whereas the pristine LiFePO 4 has a specific capacity of 123 mAh g -1 and a poor capacity retention of 82%. The surface analysis results, which include X-ray photoelectron spectroscopy and transmission electron microscopy results, show that the AlF 3 coating material is highly effective for reducing the detrimental surface passivation by relieving the electrochemical side reactions of the fragile aqueous electrolyte. The AlF 3 coating material has good compatibility with the LiFePO 4 cathode material, which mitigates the surface diffusion obstacles, reduces the charge-transfer resistances and improves the electrochemical performance and surface stability of the LiFePO 4 material in aqueous electrolyte solutions.

Hydrothermal synthesis of cathode materials

NASA Astrophysics Data System (ADS)

Chen, Jiajun; Wang, Shijun; Whittingham, M. Stanley

A number of cathodes are being considered for the next generation of lithium ion batteries to replace the expensive LiCoO 2 presently used. Besides the layered oxides, such as LiNi yMn yCo 1-2 yO 2, a leading candidate is lithium iron phosphate with the olivine structure. Although this material is inherently low cost, a manufacturing process that produces electrochemically active LiFePO 4 at a low cost is also required. Hydrothermal reactions are one such possibility. A number of pure phosphates have been prepared using this technique, including LiFePO 4, LiMnPO 4 and LiCoPO 4; this method has also successfully produced mixed metal phosphates, such as LiFe 0.33Mn 0.33Co 0.33PO 4. Ascorbic acid was found to be better than hydrazine or sugar at preventing the formation of ferric ions in aqueous media. When conductive carbons are added to the reaction medium excellent electrochemical behavior is observed.

Accelerated Removal of Fe-Antisite Defects while Nanosizing Hydrothermal LiFePO4 with Ca(2).

PubMed

Paolella, Andrea; Turner, Stuart; Bertoni, Giovanni; Hovington, Pierre; Flacau, Roxana; Boyer, Chad; Feng, Zimin; Colombo, Massimo; Marras, Sergio; Prato, Mirko; Manna, Liberato; Guerfi, Abdelbast; Demopoulos, George P; Armand, Michel; Zaghib, Karim

2016-04-13

Based on neutron powder diffraction (NPD) and high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), we show that calcium ions help eliminate the Fe-antisite defects by controlling the nucleation and evolution of the LiFePO4 particles during their hydrothermal synthesis. This Ca-regulated formation of LiFePO4 particles has an overwhelming impact on the removal of their iron antisite defects during the subsequent carbon-coating step since (i) almost all the Fe-antisite defects aggregate at the surface of the LiFePO4 crystal when the crystals are small enough and (ii) the concomitant increase of the surface area, which further exposes the Fe-antisite defects. Our results not only justify a low-cost, efficient and reliable hydrothermal synthesis method for LiFePO4 but also provide a promising alternative viewpoint on the mechanism controlling the nanosizing of LiFePO4, which leads to improved electrochemical performances.

LiFePO4 Nanostructures Fabricated from Iron(III) Phosphate (FePO4 x 2H2O) by Hydrothermal Method.

PubMed

Saji, Viswanathan S; Song, Hyun-Kon

2015-01-01

Electrode materials having nanometer scale dimensions are expected to have property enhancements due to enhanced surface area and mass/charge transport kinetics. This is particularly relevant to intrinsically low electronically conductive materials such as lithium iron phosphate (LiFePO4), which is of recent research interest as a high performance intercalation electrode material for Li-ion batteries. Many of the reported works on LiFePO4 synthesis are unattractive either due to the high cost of raw materials or due to the complex synthesis technique. In this direction, synthesis of LiFePO4 directly from inexpensive FePO4 shows promise.The present study reports LiFePO4 nanostructures prepared from iron (III) phosphate (FePO4 x 2H2O) by precipitation-hydrothermal method. The sintered powder was characterized by X-ray diffractometry (XRD), X-ray photoelectron spectroscopy (XPS), Inductive coupled plasma-optical emission spectroscopy (ICP-OES), and Electron microscopy (SEM and TEM). Two synthesis methods, viz. bulk synthesis and anodized aluminum oxide (AAO) template-assisted synthesis are reported. By bulk synthesis, micro-sized particles having peculiar surface nanostructuring were formed at precipitation pH of 6.0 to 7.5 whereas typical nanosized LiFePO4 resulted at pH ≥ 8.0. An in-situ precipitation strategy inside the pores of AAO utilizing the spin coating was utilized for the AAO-template-assisted synthesis. The template with pores filled with the precipitate was subsequently subjected to hydrothermal process and high temperature sintering to fabricate compact rod-like structures.

Hierarchical LiFePO4 with a controllable growth of the (010) facet for lithium-ion batteries.

PubMed

Guo, Binbin; Ruan, Hongcheng; Zheng, Cheng; Fei, Hailong; Wei, Mingdeng

2013-09-27

Hierarchically structured LiFePO4 was successfully synthesized by ionic liquid solvothermal method. These hierarchically structured LiFePO4 samples were constructed from nanostructured platelets with their (010) facets mainly exposed. To the best of our knowledge, facet control of a hierarchical LiFePO4 crystal has not been reported yet. Based on a series of experimental results, a tentative mechanism for the formation of these hierarchical structures was proposed. After these hierarchically structured LiFePO4 samples were coated with a thin carbon layer and used as cathode materials for lithium-ion batteries, they exhibited excellent high-rate discharge capability and cycling stability. For instance, a capacity of 95% can be maintained for the LiFePO4 sample at a rate as high as 20 C, even after 1000 cycles.

A hydrothermally synthesized LiFePO4/C composite with superior low-temperature performance and cycle life

NASA Astrophysics Data System (ADS)

Wu, Guan; Liu, Na; Gao, Xuguang; Tian, Xiaohui; Zhu, Yanbin; Zhou, Yingke; Zhu, Qingyou

2018-03-01

The LiFePO4/C composites have been successfully synthesized by a hydrothermal process, with the combined carbon sources of fructose and calcium lignosulfonate. The morphology and microstructure of LiFePO4/C were investigated by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and Fourier transform infrared spectroscopy. The electrochemical properties were evaluated by the constant-current charge/discharge tests, cyclic voltammetry and electrochemical impedance spectroscopy. The uniform carbon coating layer derived from calcium lignosulfonate can effectively improve the electronic conductivity, lithium-ion diffusivity and surface stability of the LiFePO4/C composites and prevent the side reactions between the LiFePO4 particles and electrolytes. The LiFePO4/C composites display excellent rate capability, superior cycle life and outstanding low temperature performance, which are promising for lithium-ion battery applications in electrical vehicles and electrical energy storage systems.

In-situ synthesis of monodisperse micro-nanospherical LiFePO4/carbon cathode composites for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Gong, Hao; Xue, Hairong; Wang, Tao; He, Jianping

2016-06-01

The LiFePO4 is recognized as the promising cathode material, due to its high specific capacity, excellent, structural stability and environmental benignity. However, it is blamed for the low tap density and poor rate performance when served as the cathode materials for a long time. Here, the microspheric LiFePO4/C composites are successfully synthesized through a one-step in-situ solvothermal method combined with carbothermic reduction. These LiFePO4/C microspheres are assembled by LiFePO4 nanoparticles (∼100 nm) and uniformly coated by the carbon, which show a narrow diameter distribution of 4 μm. As a cathode material for lithium ion batteries, the LiFePO4/C composites can deliver an initiate charge capacity of 155 mAh g-1 and retain 90% of initial capacity after 200 cycles at 0.1 C. When cycled at high current densities up to 20 C, it shows a discharge capacity of ∼60 mAh g-1, exhibiting superior rate performance. The significantly improved electrochemical performance of LiFePO4/C composites material can be attributed to its special micro-nano hierarchical structure. Microspheric LiFePO4/C composites exhibit a high tap density about 1.3 g cm-3. What's more, the well-coated carbon insures the high electrical conductivity and the nano-sized LiFePO4/C particles shorten lithium ion transport, thus exhibiting the high specific capacity, high cycling stability and good rate performance.

Structural and Electrical Properties of Lithium-Ion Rechargeable Battery Using the LiFePO4/Carbon Cathode Material.

PubMed

Kim, Young-Sung; Jeoung, Tae-Hoon; Nam, Sung-Pill; Lee, Seung-Hwan; Kim, Jea-Chul; Lee, Sung-Gap

2015-03-01

LiFePO4/C composite powder as cathode material and graphite powder as anode material for Li-ion batteries were synthesized by using the sol-gel method. An electrochemical improvement of LiFePO4 materials has been achieved by adding polyvinyl alcohol as a carbon source into as-prepared materials. The samples were characterized by elemental analysis (EA), X-ray diffraction (XRD), and field emission scanning electron microscopy (FE-EM). The chemical composition of LiFePO4/C powders was in a good agreement with that of the starting solution. The capacity loss after 500 cycles of LiFePO4/C cell is 11.1% in room temperature. These superior electrochemical properties show that LiFePO4/C composite materials are promising candidates as cathode materials.

Synthesis of LiFePO4/Li2SiO3/reduced Graphene Oxide (rGO) Composite via Hydrothermal Method

NASA Astrophysics Data System (ADS)

Arifin, M.; Iskandar, F.; Aimon, A. H.; Munir, M. M.; Nuryadin, B. W.

2016-08-01

LiFePO4 is a type of cathode active material used for lithium ion batteries. It has a high electrochemical performance. However, it suffers from certain disadvantages such as a very low intrinsic electronic conductivity and low ionic diffusion. This study was conducted to increase the conductivity of LiFePO4. We have investigated the addition of Li2SiO3 and reduced graphene oxide (rGO) to LiFePO4. The objective of this research was to synthesize LiFePO4/Li2SiO3/rGO via hydrothermal method. Fourier transform infrared spectroscopy (FTIR) measurement showed that the peaks corresponded to the vibration of LiFePO4/Li2SiO3. Further, X-ray diffraction (XRD) measurement confirmed a single phase of LiFePO4. Finally, scanning electron microscopy (SEM) images showed that rGO was distributed on the LiFePO4/Li2SiO3 structure.

Synthesis and characterization of LiFePO4/C cathode materials by sol-gel method.

PubMed

Liu, Shuxin; Yin, Hengbo; Wang, Haibin; Wang, Hong

2014-09-01

The carbon coated LiFePO4 cathode materials (LiFePO4/C) were successfully synthesized by sol-gel method with glucose, citric acid and PEG-4000 as dispersant and carbon source, respectively. The microstructure and grain size of LiFePO4/C composite were characterized by X-ray diffraction, Raman spectroscopy, transmission electron microscopy. The results showed that the carbon source and calcination temperature had important effect on the graphitization degree of carbon; the carbon decomposed by citric acid had higher graphitization degree; with calcination temperature rising, the graphitization degree of carbon increased and the particles size increased. The graphitization degree and grain size were very important for improving the electrochemical performance of LiFePO4 cathode materials, according to the experimental results, the sample LFP-700 (LFP-C) which was synthesized with citric acid as dispersant at 700 degree C had lower polarization and larger discharge capacity.

Enhancement of the Rate Capability of LiFePO4 by a New Highly Graphitic Carbon-Coating Method.

PubMed

Song, Jianjun; Sun, Bing; Liu, Hao; Ma, Zhipeng; Chen, Zhouhao; Shao, Guangjie; Wang, Guoxiu

2016-06-22

Low lithium ion diffusivity and poor electronic conductivity are two major drawbacks for the wide application of LiFePO4 in high-power lithium ion batteries. In this work, we report a facile and efficient carbon-coating method to prepare LiFePO4/graphitic carbon composites by in situ carbonization of perylene-3,4,9,10-tetracarboxylic dianhydride during calcination. Perylene-3,4,9,10-tetracarboxylic dianhydride containing naphthalene rings can be easily converted to highly graphitic carbon during thermal treatment. The ultrathin layer of highly graphitic carbon coating drastically increased the electronic conductivity of LiFePO4. The short pathway along the [010] direction of LiFePO4 nanoplates could decrease the Li(+) ion diffusion path. In favor of the high electronic conductivity and short lithium ion diffusion distance, the LiFePO4/graphitic carbon composites exhibit an excellent cycling stability at high current rates at room temperature and superior performance at low temperature (-20 °C).

Improved Electrochemical Performance of LiFePO4@N-Doped Carbon Nanocomposites Using Polybenzoxazine as Nitrogen and Carbon Sources.

PubMed

Wang, Ping; Zhang, Geng; Li, Zhichen; Sheng, Wangjian; Zhang, Yichi; Gu, Jiangjiang; Zheng, Xinsheng; Cao, Feifei

2016-10-03

Polybenzoxazine is used as a novel carbon and nitrogen source for coating LiFePO 4 to obtain LiFePO 4 @nitrogen-doped carbon (LFP@NC) nanocomposites. The nitrogen-doped graphene-like carbon that is in situ coated on nanometer-sized LiFePO 4 particles can effectively enhance the electrical conductivity and provide fast Li + transport paths. When used as a cathode material for lithium-ion batteries, the LFP@NC nanocomposite (88.4 wt % of LiFePO 4 ) exhibits a favorable rate performance and stable cycling performance.

Mesoporous carbon-coated LiFePO4 nanocrystals co-modified with graphene and Mg2+ doping as superior cathode materials for lithium ion batteries.

PubMed

Wang, Bo; Xu, Binghui; Liu, Tiefeng; Liu, Peng; Guo, Chenfeng; Wang, Shuo; Wang, Qiuming; Xiong, Zhigang; Wang, Dianlong; Zhao, X S

2014-01-21

In this work, mesoporous carbon-coated LiFePO4 nanocrystals further co-modified with graphene and Mg(2+) doping (G/LFMP) were synthesized by a modified rheological phase method to improve the speed of lithium storage as well as cycling stability. The mesoporous structure of LiFePO4 nanocrystals was designed and realized by introducing the bead milling technique, which assisted in forming sucrose-pyrolytic carbon nanoparticles as the template for generating mesopores. For comparison purposes, samples modified only with graphene (G/LFP) or Mg(2+) doping (LFMP) as well as pure LiFePO4 (LFP) were also prepared and investigated. Microscopic observation and nitrogen sorption analysis have revealed the mesoporous morphologies of the as-prepared composites. X-ray diffraction (XRD) and Rietveld refinement data demonstrated that the Mg-doped LiFePO4 is a single olivine-type phase and well crystallized with shortened Fe-O and P-O bonds and a lengthened Li-O bond, resulting in an enhanced Li(+) diffusion velocity. Electrochemical properties have also been investigated after assembling coin cells with the as-prepared composites as the cathode active materials. Remarkably, the G/LFMP composite has exhibited the best electrochemical properties, including fast lithium storage performance and excellent cycle stability. That is because the modification of graphene provided active sites for nuclei, restricted the in situ crystallite growth, increased the electronic conductivity and reduced the interface reaction current density, while, Mg(2+) doping improved the intrinsically electronic and ionic transfer properties of LFP crystals. Moreover, in the G/LFMP composite, the graphene component plays the role of "cushion" as it could quickly realize capacity response, buffering the impact to LFMP under the conditions of high-rate charging or discharging, which results in a pre-eminent rate capability and cycling stability.

Thin film rechargeable electrodes based on conductive blends of nanostructured olivine LiFePO4 and sucrose derived nanocarbons for lithium ion batteries.

PubMed

Praveen, P; Jyothsna, U; Nair, Priya; Ravi, Soumya; Balakrishnan, A; Subramanian, K R V; Nair, A Sreekumaran; Nair, V Shantikumar; Sivakumar, N

2013-08-01

The present study provides the first reports of a novel approach of electrophoretic co-deposition technique by which titanium foils are coated with LiFePO4-carbon nanocomposites synthesized by sol gel route and processed into high-surface area cathodes for lithium ion batteries. The study elucidates how sucrose additions as carbon source can affect the surface morphology and the redox reaction behaviors underlying these cathodes and thereby enhance the battery performance. The phase and morphological analysis were done using XRD and XPS where the LiFePO4 formed was confirmed to be a high purity orthorhombic system. From the analysis of the relevant electrochemical parameters using cyclic voltammetry and electrochemical impedance spectroscopy, a 20% increment and 90% decrement in capacity and impedance values were observed respectively. The composite electrodes also exhibited a specific capacity of 130 mA h/g. It has been shown that cathodes based on such composite systems can allow significant room for improvement in the cycling performance at the electrode/electrolyte interface.

In situ carbon coated LiFePO4/C microrods with improved lithium intercalation behavior.

PubMed

Bhuvaneswari, D; Kalaiselvi, N

2014-01-28

LiFePO4/C microrods consisting of building blocks of interconnected nanoparticles surrounded by a thin and amorphous coating of carbon have been prepared by a customized hydrothermal method. Appreciable discharge capacity values of 168 mA h g(-1) at 0.1 C and 130 mA h g(-1) at 5 C rates have been exhibited by the currently synthesized LiFePO4/C cathode. The study enumerates the feasibility of exploiting the hydrothermal method to prepare an in situ carbon coated LiFePO4/C compound with tunable morphological properties and desirable electrochemical properties observed for up to 100 cycles at a 5 C rate.

LiFePO4 nanoparticles encapsulated in graphene nanoshells for high-performance lithium-ion battery cathodes.

PubMed

Fei, Huilong; Peng, Zhiwei; Yang, Yang; Li, Lei; Raji, Abdul-Rahman O; Samuel, Errol L G; Tour, James M

2014-07-11

LiFePO4 encapsulated in graphene nanoshells (LiFePO4@GNS) nanoparticles were synthesized by solid state reaction between graphene-coated Fe nanoparticles and LiH2PO4. The resulting nanocomposite was demonstrated to be a superior lithium-ion battery cathode with improved cycle and rate performances.

Tailored surface structure of LiFePO4/C nanofibers by phosphidation and their electrochemical superiority for lithium rechargeable batteries.

PubMed

Lee, Yoon Cheol; Han, Dong-Wook; Park, Mihui; Jo, Mi Ru; Kang, Seung Ho; Lee, Ju Kyung; Kang, Yong-Mook

2014-06-25

We offer a brand new strategy for enhancing Li ion transport at the surface of LiFePO4/C nanofibers through noble Li ion conducting pathways built along reduced carbon webs by phosphorus. Pristine LiFePO4/C nanofibers composed of 1-dimensional (1D) LiFePO4 nanofibers with thick carbon coating layers on the surfaces of the nanofibers were prepared by the electrospinning technique. These dense and thick carbon layers prevented not only electrolyte penetration into the inner LiFePO4 nanofibers but also facile Li ion transport at the electrode/electrolyte interface. In contrast, the existing strong interactions between the carbon and oxygen atoms on the surface of the pristine LiFePO4/C nanofibers were weakened or partly broken by the adhesion of phosphorus, thereby improving Li ion migration through the thick carbon layers on the surfaces of the LiFePO4 nanofibers. As a result, the phosphidated LiFePO4/C nanofibers have a higher initial discharge capacity and a greatly improved rate capability when compared with pristine LiFePO4/C nanofibers. Our findings of high Li ion transport induced by phosphidation can be widely applied to other carbon-coated electrode materials.

Stabilization of Lithium Transition Metal Silicates in the Olivine Structure

DOE PAGES

Sun, Xiaoqi; Tripathi, Rajesh; Popov, Guerman; ...

2017-07-28

While olivine LiFePO 4 shows amongst the best electrochemical properties of Li-ion positive electrodes with respect to rate behavior owing to facile Li + migration pathways in the framework, replacing the [PO 4] 3- polyanion with a silicate [SO 4] 4- moitie in olivine is desirable. This would allow additional balancing alkali content and hence electron transfer, and increase the capacity. We demonstrate the first stabilization of a lithium transition-metal silicate (as a pure silicate) in the olivine structure type. Using LiInSiO 4 and LiScSiO 4 as the parent materials, transition metal (Mn, Fe, Co) substitutions on the In/Sc sitemore » were investigated by computational modelling via atomic scale simulation. Transition metal substitution was found to be only favourable for Co, a finding confirmed by the successful solid state synthesis of olivine LixInyCo 2-x-ySiO 4. Finally, the stabilization of the structure was achieved by entropy provided by cation disorder.« less

Improved battery performance using Pd nanoparticles synthesized on the surface of LiFePO4/C by ultrasound irradiation

NASA Astrophysics Data System (ADS)

Saliman, Muhammad Ali; Okawa, Hirokazu; Takai, Misaki; Ono, Yuki; Kato, Takahiro; Sugawara, Katsuyasu; Sato, Mineo

2016-07-01

LiFePO4 has been attracting interest as a cathode material for Li-ion batteries due to its high energy density, low cost, and eco-friendliness. The electrochemical performance of LiFePO4 is limited because it exhibits low Li-ion diffusivity and low electronic conductivity. Numerous solutions have been considered, such as carbon coating, which is widely known to improve the electronic conductivity of LiFePO4. The deposition of metal nanoparticles (NPs) on the surface of carbon-coated LiFePO4 further enhances the electronic conductivity. In this study, we deposited Pd NPs onto the surface of LiFePO4/C and investigated the resulting electrochemical performance. Sonochemical synthesis was used to prepare the metal NPs; the procedure did not require any surfactants and the reaction was rapid.

Development of surface functionalized ZnO-doped LiFePO4/C composites as alternative cathode material for lithium ion batteries

NASA Astrophysics Data System (ADS)

Saroha, Rakesh; Panwar, Amrish K.; Sharma, Yogesh; Tyagi, Pawan K.; Ghosh, Sudipto

2017-02-01

Surface modified olivine-type LiFePO4/C-ZnO doped samples were synthesized using sol-gel assisted ball-milling route. In this work, the influence of ZnO-doping on the physiochemical, electrochemical and surface properties such as charge separation at solid-liquid interphase, surface force gradient, surface/ionic conductivity of pristine LiFePO4/C (LFP) has been investigated thoroughly. Synthesized samples were characterized using X-ray diffraction, scanning electron microscopy, atomic force microscopy, and transmission electron microscopy. All the synthesized samples were indexed to the orthorhombic phase with Pnma space group. Pristine LiFePO4 retain its structure for higher ZnO concentrations (i.e. 2.5 and 5.0 wt.% of LFP). Surface topography and surface force gradient measurements by EFM revealed that the kinetics of charge carriers, e-/Li+ is more in ZnO-doped LFP samples, which may be attributed to diffusion or conduction process of the charges present at the surface. Among all the synthesized samples LFP/C with 2.5 wt.% of ZnO (LFPZ2.5) displays the highest discharge capacity at all C-rates and exhibit excellent rate performance. LFPZ2.5 delivers a specific discharge capacity of 164 (±3) mAh g-1 at 0.1C rate. LFPZ2.5 shows best cycling performance as it provides a discharge capacity of 135 (±3) mAh g-1 at 1C rate and shows almost 95% capacity retention after 50 charge/discharge cycles. Energy density plot shows that LFPZ2.5 offers high energy and power density measured at high discharge rates (5C), proving its usability for hybrid vehicles application.

Thermal annealing dynamics of carbon-coated LiFePO4 nanoparticles studied by in-situ analysis

NASA Astrophysics Data System (ADS)

Krumeich, Frank; Waser, Oliver; Pratsinis, Sotiris E.

2016-10-01

The thermal behavior of core-shell carbon-coated lithium iron phosphate (LiFePO4-C) nanoparticles made by flame spray pyrolysis (FSP) during annealing was investigated by in-situ transmission electron microscopy (TEM), in-situ X-ray powder diffraction (XRD) as well as ex-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Crystallization of the initially glassy LiFePO4-C nanoparticles starts at quite low temperatures (T=400 °C), forming single crystals inside the confinement of the carbon shell. Upon increasing the temperature to T≥700 °C, LiFePO4 starts to diffuse through the carbon shell resulting in cavities inside the mostly intact carbon shell. By increasing the temperature further to T≥800 °C, the initial core-shell morphology converts into open carbon shells (flakes and cenospheres) and bulky LiFePO4 particles (diameter in the range 300-400 nm), in agreement with ex-situ experiments.

Structural, Transport and Electrochemical Properties of LiFePO4 Substituted in Lithium and Iron Sublattices (Al, Zr, W, Mn, Co and Ni)

PubMed Central

Molenda, Janina; Kulka, Andrzej; Milewska, Anna; Zając, Wojciech; Świerczek, Konrad

2013-01-01

LiFePO4 is considered to be one of the most promising cathode materials for lithium ion batteries for electric vehicle (EV) application. However, there are still a number of unsolved issues regarding the influence of Li and Fe-site substitution on the physicochemical properties of LiFePO4. This is a review-type article, presenting results of our group, related to the possibility of the chemical modification of phosphoolivine by introduction of cation dopants in Li and Fe sublattices. Along with a synthetic review of previous papers, a large number of new results are included. The possibility of substitution of Li+ by Al3+, Zr4+, W6+ and its influence on the physicochemical properties of LiFePO4 was investigated by means of XRD, SEM/EDS, electrical conductivity and Seebeck coefficient measurements. The range of solid solution formation in Li1−3xAlxFePO4, Li1−4xZrxFePO4 and Li1−6xWxFePO4 materials was found to be very narrow. Transport properties of the synthesized materials were found to be rather weakly dependent on the chemical composition. The battery performance of selected olivines was tested by cyclic voltammetry (CV). In the case of LiFe1−yMyPO4 (M = Mn, Co and Ni), solid solution formation was observed over a large range of y (0 < y ≤ 1). An increase of electrical conductivity for the substitution level y = 0.25 was observed. Electrons of 3d metals other than iron do not contribute to the electrical properties of LiFe1−yMyPO4, and substitution level y > 0.25 leads to considerably lower values of σ. The activated character of electrical conductivity with a rather weak temperature dependence of the Seebeck coefficient suggests a small polaron-type conduction mechanism. The electrochemical properties of LiFe1−yMyPO4 strongly depend on the Fe substitution level. PMID:28809235

Synthesis and performances of 2LiFePO4·Li3V2(PO4)3/C cathode materials via spray drying method with double carbon sources

NASA Astrophysics Data System (ADS)

Zhang, Jia-feng; Shen, Chao; Zhang, Bao; Zheng, Jun-chao; Peng, Chun-li; Wang, Xiao-wei; Yuan, Xin-bo; Li, Hui; Chen, Guo-min

2014-12-01

The 2LiFePO4·Li3V2(PO4)3/C samples are synthesized through spray drying method. Glucose and oxalic acid are used as collaborative carbon sources to improve the electrochemical performance of 2LiFePO4·Li3V2(PO4)3/C composites. XRD results reveal the LiFePO4·Li3V2(PO4)3/C samples are composed of orthorhombic LiFePO4 and monoclinic Li3V2(PO4)3 phases. SEM results reveal that the nano-spherical Fe4(VO4)4·5H2O are about 80 nm and the 2LiFePO4·Li3V2(PO4)3/C composites possess a micro-nano spherical morphology with carbon coating layer. The samples show the best electrochemical performance when the mass ration of glucose and oxalic is 6:4, it can deliver a capacity of 147.6 mAh g-1, 145.0 mAh g-1, 134.1 mAh g-1 and 123.0 mAh g-1 at the rates of 0.1C, 1C, 5C and 10C, respectively.

Study on feed forward neural network convex optimization for LiFePO4 battery parameters

NASA Astrophysics Data System (ADS)

Liu, Xuepeng; Zhao, Dongmei

2017-08-01

Based on the modern facility agriculture automatic walking equipment LiFePO4 Battery, the parameter identification of LiFePO4 Battery is analyzed. An improved method for the process model of li battery is proposed, and the on-line estimation algorithm is presented. The parameters of the battery are identified using feed forward network neural convex optimization algorithm.

Preparation of V-Doped LiFePO4/C as the Optimized Cathode Material for Lithium Ion Batteries.

PubMed

Sun, Pingping; Zhang, Haiyang; Shen, Kai; Fan, Qi; Xu, Qingyu

2015-04-01

LiFe1-x,Vx,PO4/C composites were synthesized by solid state reaction. The effect of carbon coating and V doping on the performance of LiFePO4 has been systematically investigated by X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), transmission electron microscope (TEM), charge/discharge and cyclic voltammetry (CV) measurement. The results show that carbon coating and proper amount of V incorporation do not significantly change the host crystal structure of LiFePO4, while the electrochemical performance of LiFePO4 can be significantly improved. Particularly, the LiFe0.96V0.04PO4/C exhibits the best performance with a specific discharge capacity of 105.5 mA h/g at 5.0 C, 90.3 mA h/g at 10 C and 66.7 mA h/g at 30 C with stable cycle performance, which is significantly improved compared with the pure LiFePO4/C. The cyclic voltammograms result reveals that V doping could decrease the resistance of LiFePO4/C composite electrode drastically and improve its reversibility.

Synthesis, characterization and electrochemical performances of LiFePO4/graphene cathode material for high power lithium-ion batteries

NASA Astrophysics Data System (ADS)

Shang, Weili; Kong, Lingyong; Ji, Xuewen

2014-12-01

LiFePO4/graphene (LiFePO4/G) cathode with exciting electrochemical performance was successfully synthesized by liquid phase method. LiFePO4 nanoparticles wrapped with multi-layered grapheme can be fabricated in a short time. This method did not need external heating source. Heat generated by chemical reaction conduct the process and removed the solvent simultaneously. The LiFePO4/G were analyzed by X-ray diffraction (XRD) analysis, scanning electron microscope (SEM), transmission electron microscopy (TEM), magnetic properties analysis and electrochemical performance tests. The LiFePO4/G delivered a capacity of 160 mAh g-1 at 0.1C and could tolerate various dis-charge currents with a capacity retention rate of 99.8%, 99.2%, 99.0%, 98.6%, 97.3% and 95.0% after stepwise under 5C, 10C, 15C, 20C, 25C and 30C, respectively.

Controllable synthesis, morphology evolution and electrochemical properties of LiFePO4 cathode materials for Li-ion batteries.

PubMed

Song, Jianjun; Wang, Lin; Shao, Guangjie; Shi, Meiwu; Ma, Zhipeng; Wang, Guiling; Song, Wei; Liu, Shuang; Wang, Caixia

2014-05-07

Monodispersed LiFePO4 nanocrystals with diverse morphologies were successfully synthesized via a mild and controllable solvothermal approach with a mixture of ethylene glycol and oleic acid as the solvent. Morphology evolution of LiFePO4 nanoparticles from nanoplates to nanorods can be simply realized by varying the volume ratio of oleic acid to ethylene glycol. Moreover, the mechanism of competitive adsorption between ethylene glycol and oleic acid was proposed for the formation of different morphologies. Electrochemical measurements show that the LiFePO4/C nanorods have an initial discharge capacity of 155 mA h g(-1) at 0.5 C with a capacity retention of 80% at a high rate of 5 C, which confirms that LiFePO4/C nanorods exhibit excellent rate capability and cycling stability.

Composited reduced graphene oxide into LiFePO4/Li2SiO3 and its electrochemical impedance spectroscopy properties

NASA Astrophysics Data System (ADS)

Arifin, M.; Rus, Y. B.; Aimon, A. H.; Iskandar, F.; Winata, T.; Abdullah, M.; Khairurrijal, K.

2017-03-01

LiFePO4 is commonly used as cathode material for Li-ion batteries due to its stable operational voltage and high specific capacity. However, it suffers from certain disadvantages such as low intrinsic electronic conductivity and low ionic diffusion. This study was conducted to analyse the effect of reduced graphene oxide (rGO) on the electrochemical properties of LiFePO4/Li2SiO3 composite. This composite was synthesized by a hydrothermal method. Fourier transform infrared spectroscopy measurement identified the O-P-O, Fe-O, P-O, and O-Si-O- bands in the LiFePO4/Li2SiO3 composite. X-ray diffraction measurement confirmed the formation of LiFePO4. Meanwhile, Raman spectroscopy confirmed the number of rGO layers. Further, scanning electron microscopy images showed that rGO was distributed around the LiFePO4/Li2SiO3 particles. Finally, the electrochemical impedance spectroscopy results showed that the addition of 1 wt% of rGO to the LiFePO4/Li2SiO3 composite reduced charge transfer resistance. It may be concluded that the addition of 1 wt% rGO to LiFePO4/Li2SiO3 composite can enhance its electrochemical performance as a cathode material.

Direct regeneration of recycled cathode material mixture from scrapped LiFePO4 batteries

NASA Astrophysics Data System (ADS)

Li, Xuelei; Zhang, Jin; Song, Dawei; Song, Jishun; Zhang, Lianqi

2017-03-01

A new green recycling process (named as direct regeneration process) of cathode material mixture from scrapped LiFePO4 batteries is designed for the first time. Through this direct regeneration process, high purity cathode material mixture (LiFePO4 + acetylene black), anode material mixture (graphite + acetylene black) and other by-products (shell, Al foil, Cu foil and electrolyte solvent, etc.) are recycled from scrapped LiFePO4 batteries with high yield. Subsequently, recycled cathode material mixture without acid leaching is further directly regenerated with Li2CO3. Direct regeneration procedure of recycled cathode material mixture from 600 to 800 °C is investigated in detail. Cathode material mixture regenerated at 650 °C display excellent physical, chemical and electrochemical performances, which meet the reuse requirement for middle-end Li-ion batteries. The results indicate the green direct regeneration process with low-cost and high added-value is feasible.

MW-assisted synthesis of LiFePO 4 for high power applications

NASA Astrophysics Data System (ADS)

Beninati, Sabina; Damen, Libero; Mastragostino, Marina

LiFePO 4/C was prepared by solid-state reaction from Li 3PO 4, Fe 3(PO 4) 2·8H 2O, carbon and glucose in a few minutes in a scientific MW (microwave) oven with temperature and power control. The material was characterized by X-ray diffraction, scanning electron microscopy and by TGA analysis to evaluate carbon content. The electrochemical characterization as positive electrode in EC (ethylene carbonate)-DMC (dimethylcarbonate) 1 M LiPF 6 was performed by galvanostatic charge-discharge cycles at C/10 to evaluate specific capacity and by sequences of 10 s discharge-charge pulses, at different high C-rates (5-45C) to evaluate pulse-specific power in simulate operative conditions for full-HEV application. The maximum pulse-specific power and, particularly, pulse efficiency values are quite high and make MW synthesis a very promising route for mass production of LiFePO 4/C for full-HEV batteries at low energy costs.

Recycling bacteria for the synthesis of LiMPO4 (M = Fe, Mn) nanostructures for high-power lithium batteries.

PubMed

Zhou, Yanping; Yang, Dan; Zeng, Yi; Zhou, Yan; Ng, Wun Jern; Yan, Qingyu; Fong, Eileen

2014-10-15

In this work, a novel waste-to-resource strategy to convert waste bacteria into a useful class of cathode materials, lithium metal phosphate (LiMPO4; M = Fe, Mn), is presented. Escherichia coli (E. coli) bacteria used for removing phosphorus contamination from wastewater are harvested and used as precursors for the synthesis of LiMPO4. After annealing, LiFePO4 and LiMnPO4 nanoparticles with dimensions around 20 nm are obtained. These particles are found to be enveloped in a carbon layer with a thickness around 3-5 nm, generated through the decomposition of the organic matter from the bacterial cell cytoplasm. The battery performance for the LiFePO4 is evaluated. A high discharge capacity of 140 mAh g(-1) at 0.1 C with a flat plateau located at around 3.5 V is obtained. In addition, the synthesized particles display excellent stability and rate capabilities. Even under a high C rate of 10 C, a stable discharge capacity of 75.4 mAh g(-1) can still be achieved. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Boron and Nitrogen Codoped Carbon Layers of LiFePO4 Improve the High-Rate Electrochemical Performance for Lithium Ion Batteries.

PubMed

Zhang, Jinli; Nie, Ning; Liu, Yuanyuan; Wang, Jiao; Yu, Feng; Gu, Junjie; Li, Wei

2015-09-16

An evolutionary composite of LiFePO4 with nitrogen and boron codoped carbon layers was prepared by processing hydrothermal-synthesized LiFePO4. This novel codoping method is successfully applied to LiFePO4 for commercial use, and it achieved excellent electrochemical performance. The electrochemical performance can be improved through single nitrogen doping (LiFePO4/C-N) or boron doping (LiFePO4/C-B). When modifying the LiFePO4/C-B with nitrogen (to synthesis LiFePO4/C-B+N) the undesired nonconducting N-B configurations (190.1 and 397.9 eV) are generated. This decreases the electronic conductivity from 2.56×10(-2) to 1.30×10(-2) S cm(-1) resulting in weak electrochemical performance. Nevertheless, using the opposite order to decorate LiFePO4/C-N with boron (to obtain LiFePO4/C-N+B) not only eliminates the nonconducting N-B impurity, but also promotes the conductive C-N (398.3, 400.3, and 401.1 eV) and C-B (189.5 eV) configurations-this markedly improves the electronic conductivity to 1.36×10(-1) S cm(-1). Meanwhile the positive doping strategy leads to synergistic electrochemical activity distinctly compared with single N- or B-doped materials (even much better than their sum capacity at 20 C). Moreover, due to the electron and hole-type carriers donated by nitrogen and boron atoms, the N+B codoped carbon coating tremendously enhances the electrochemical property: at the rate of 20 C, the codoped sample can elevate the discharge capacity of LFP/C from 101.1 mAh g(-1) to 121.6 mAh g(-1), and the codoped product based on commercial LiFePO4/C shows a discharge capacity of 78.4 mAh g(-1) rather than 48.1 mAh g(-1). Nevertheless, the B+N codoped sample decreases the discharge capacity of LFP/C from 101.1 mAh g(-1) to 95.4 mAh g(-1), while the commercial LFP/C changes from 48.1 mAh g(-1) to 40.6 mAh g(-1).

Outstanding Li-storage performance of LiFePO4@MWCNTs cathode material with 3D network structure for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Sun, Xiaodong; Zhang, Le

2018-05-01

In this work, the MWCNTs-decorated LiFePO4 microspheres (LiFePO4@MWCNTs) with a 3D network structure have been synthesized by a facile and efficient spray-drying approach followed by solid-state reaction in a reduction atmosphere. In the as-prepared composite, the MWCNTs around LiFePO4 nanoparticles can provide 3D conductive networks which greatly facilitate the transport of Li+-ion and electron during the electrochemical reaction. Compared to the pure LiFePO4 material, the LiFePO4@MWCNTs composite as cathode for lithium-ion batteries exhibits significantly improved Li-storage performance in terms of rate capability and cyclic stability. Therefore, we can speculate that the spray-drying approach is a promising route to prepare the high-performance electrode materials with 3D network structure for electrochemical energy storage.

Mesoscale phase distribution in single particles of LiFePO4 following lithium deintercalation

PubMed Central

Boesenberg, Ulrike; Meirer, Florian; Liu, Yijin; Shukla, Alpesh K.; Dell’Anna, Rossana; Tyliszczak, Tolek; Chen, Guoying; Andrews, Joy C.; Richardson, Thomas J.; Kostecki, Robert; Cabana, Jordi

2013-01-01

The chemical phase distribution in hydrothermally grown micrometric single crystals LiFePO4 following partial chemical delithiation was investigated. Full field and scanning X-ray microscopy were combined with X-ray absorption spectroscopy at the Fe K- and O K-edges, respectively, to produce maps with high chemical and spatial resolution. The resulting information was compared to morphological insight into the mechanics of the transformation by scanning transmission electron microscopy. This study revealed the interplay at the mesocale between microstructure and phase distribution during the redox process, as morphological defects were found to kinetically determine the progress of the reaction. Lithium deintercalation was also found to induce severe mechanical damage in the crystals, presumably due to the lattice mismatch between LiFePO4 and FePO4. Our results lead to the conclusion that rational design of intercalation-based electrode materials, such as LiFePO4, with optimized utilization and life requires the tailoring of particles that minimize kinetic barriers and mechanical strain. Coupling TXM-XANES with TEM can provide unique insight into the behavior of electrode materials during operation, at scales spanning from nanoparticles to ensembles and complex architectures. PMID:23745016

Identifying compatibility of lithium salts with LiFePO4 cathode using a symmetric cell

NASA Astrophysics Data System (ADS)

Tong, Bo; Wang, Jiawei; Liu, Zhenjie; Ma, Lipo; Zhou, Zhibin; Peng, Zhangquan

2018-04-01

The electrochemical performance of lithium-ion batteries is dominated by the interphase electrochemistry between the electrolyte and electrode materials. A multitude of efforts have been dedicated to the solid electrolyte interphase (SEI) formed on the anode. However, the interphase on the cathode, namely the cathode electrolyte interphase (CEI), is left aside, partially due to the fact that it is hard to single out the CEI considering the complicated anode-cathode inter-talk. Herein, a partially delithiated lithium iron phosphate (Li0.25FePO4) electrode is used as the anode. Owing to a high voltage plateau (≈3.45 V vs. Li/Li+), negligible reduction reactions of electrolyte occur on the L0.25FePO4 anode. Therefore, the CEI can be investigated exclusively. Using a LiFePO4|Li0.25FePO4 symmetric cell configuration, we scrutinize the compatibility of the electrolytes containing a wide spectrum of lithium salts, Li[(FSO2)(Cm F2m+1SO2)N] (m = 0, 1, 2, 4), with the LiFePO4, in both cycling and calendar tests. It is found that the Li[(FSO2)(n-C4F9SO2)N] (LiFNFSI)-based electrolyte exhibits the highest compatibility with LiFePO4.

Improving cylinder-type LiFePO4 battery performance via control of internal resistance

NASA Astrophysics Data System (ADS)

Purwanto, Agus; Jumari, Arif; Nizam, Muhammad; Widiyandari, Hendri; Sudaryanto; Deswita; Azmin Mohamad, Ahmad

2018-04-01

Strategies for controlling the internal resistance to improve battery performance were systematically investigated. Electrode densification of LiFePO4 cathodes significantly reduced the internal resistance of the prepared batteries. Densification by reduction to 31.25% of initial thickness resulted in optimal electrochemical performance of the prepared LiFePO4 batteries. The addition of KS 6 graphite material improved the conductivity of the cathodes, which was indicated by a lowering of the internal resistance. The internal resistance was decreased from 73 to 54 when the KS6/AB ratio was varied from 3 to 1. Another factor in controlling the internal resistance was the location of a welded aluminum tab in the cathode. The welding of an aluminum tab in a small gap in the cathode significantly reduced the internal resistance. Thus, three main factors can be performed during fabrication to reduce the internal resistance of a LiFePO4 battery: cathode densification, KS-6 graphite addition, and the arrangement of an aluminum tab welded to the cathode. By optimizing these factors, high-performance LFP batteries were produced.

Enhancement of Electrical Conductivity of LiFePO4 by Controlled Solution Combustion Synthesis

NASA Astrophysics Data System (ADS)

Rajoba, S. J.; Jadhav, L. D.; Patil, P. S.; Tyagi, D. K.; Varma, S.; Wani, B. N.

2017-03-01

LiFePO4 has been synthesized by a solution combustion method at different oxidant-to-fuel ratios. At stoichiometric oxidant-to-fuel ratio (1:2), Fe2O3 formed in addition to LiFePO4 during combustion. Hence, reducing atmosphere was generated by increasing the ratio from stoichiometric to 1:4 and 1:8, named as 1-LFP, 2-LFP, and 4-LFP, respectively. Furthermore, as-prepared powders were calcined in inert atmosphere to avoid oxidation of LiFePO4 to Fe2O3 and Li3PO4, as confirmed by x-ray diffraction (XRD) and thermogravimetric and differential thermal analyses. The calcined powders were characterized by XRD analysis, Raman spectroscopy, scanning electron microscopy, and energy-dispersive x-ray spectroscopy. X-ray photoelectron spectroscopy ascertained oxidation state of +2 and +5 for Fe and P, respectively. With increasing oxidant-to-fuel ratio, the binding energies of 2 p 3/2 and 2 p 1/2 levels of Fe shifted downwards and showed increased splitting. According to Raman spectroscopy results, the residual carbon is amorphous with sp 2 C-C bond. The conductivity of 1-LFP, 2-LFP, and 4-LFP measured at 313 K was 0.15 × 10-6 S/cm, 8.46 × 10-6 S/cm, and 1.21 × 10-3 S/cm, respectively. The enhanced conductivity of 4-LFP is due to presence of residual carbon and Fe2P.

Fast‐Rate Capable Electrode Material with Higher Energy Density than LiFePO4: 4.2V LiVPO4F Synthesized by Scalable Single‐Step Solid‐State Reaction

PubMed Central

Kim, Minkyung; Lee, Seongsu

2015-01-01

Use of compounds that contain fluorine (F) as electrode materials in lithium ion batteries has been considered, but synthesizing single‐phase samples of these compounds is a difficult task. Here, it is demonstrated that a simple scalable single‐step solid‐state process with additional fluorine source can obtain highly pure LiVPO4F. The resulting material with submicron particles achieves very high rate capability ≈100 mAh g−1 at 60 C‐rate (1‐min discharge) and even at 200 C‐rate (18 s discharge). It retains superior capacity, ≈120 mAh g−1 at 10 C charge/10 C discharge rate (6‐min) for 500 cycles with >95% retention efficiency. Furthermore, LiVPO4F shows low polarization even at high rates leading to higher operating potential >3.45 V (≈3.6 V at 60 C‐rate), so it achieves high energy density. It is demonstrated for the first time that highly pure LiVPO4F can achieve high power capability comparable to LiFePO4 and much higher energy density (≈521 Wh g−1 at 20 C‐rate) than LiFePO4 even without nanostructured particles. LiVPO4F can be a real substitute of LiFePO4. PMID:27774395

Fast-Rate Capable Electrode Material with Higher Energy Density than LiFePO4: 4.2V LiVPO4F Synthesized by Scalable Single-Step Solid-State Reaction.

PubMed

Kim, Minkyung; Lee, Seongsu; Kang, Byoungwoo

2016-03-01

Use of compounds that contain fluorine (F) as electrode materials in lithium ion batteries has been considered, but synthesizing single-phase samples of these compounds is a difficult task. Here, it is demonstrated that a simple scalable single-step solid-state process with additional fluorine source can obtain highly pure LiVPO 4 F. The resulting material with submicron particles achieves very high rate capability ≈100 mAh g -1 at 60 C-rate (1-min discharge) and even at 200 C-rate (18 s discharge). It retains superior capacity, ≈120 mAh g -1 at 10 C charge/10 C discharge rate (6-min) for 500 cycles with >95% retention efficiency. Furthermore, LiVPO 4 F shows low polarization even at high rates leading to higher operating potential >3.45 V (≈3.6 V at 60 C-rate), so it achieves high energy density. It is demonstrated for the first time that highly pure LiVPO 4 F can achieve high power capability comparable to LiFePO 4 and much higher energy density (≈521 Wh g -1 at 20 C-rate) than LiFePO 4 even without nanostructured particles. LiVPO 4 F can be a real substitute of LiFePO 4.

Synthesis of cage-like LiFePO4/C microspheres for high performance lithium ion batteries

NASA Astrophysics Data System (ADS)

Deng, Honggui; Jin, Shuangling; Zhan, Liang; Wang, Yanli; Qiao, Wenming; Ling, Licheng

2012-12-01

Cage-like LiFePO4 microspheres are synthesized by a solvothermal reaction-calcination process, using Fe(NO3)3·9H2O as iron source and ethylene glycol/water as co-solvent medium. The microsphere is the assembly of LiFePO4 nanoparticles with an open porous structure, thus the carbon coating can be easily introduced on the surface of the nanoparticles by the chemical vapor deposition of C2H4 during calcination process. When used as the cathode materials for the lithium-ion batteries, the resultant cage-like LiFePO4/C microsphere shows high capacity and good cycle stability (160 mAh g-1 at 0.1 C over 300 cycles), as well as good rate capability (120 mAh g-1 at 10 C). The desirable electrochemical performance can be attributed to high rate of ionic/electronic conduction and the high structural stability arising from the interconnected open pores, carbon-coated nanoparticles and microsized structure.

LiFePO4 nanoparticles enveloped in freestanding sandwich-like graphitized carbon sheets as enhanced remarkable lithium-ion battery cathode.

PubMed

Zhang, Yan; Zhang, Huijuan; Li, Xiao; Xu, Haitao; Wang, Yu

2016-04-15

A novel nanostructure where LiFePO4 nanoparticles are enveloped in sandwich-like carbon sheets as an enhanced cathode in lithium-ion batteries has successfully been synthesized for the first time. Compared to previous carbon-based nanocomposites, the achieved sandwich-like LiFePO4 nanocomposites exhibit totally different architecture, in which LiFePO4 nanoparticles are tightly entrapped between two carbon layers, instead of being anchored on the carbon sheet surfaces. In other words, the achieved sandwich-like LiFePO4 nanocomposite carbon layers are actually freestanding and can be operated and separated from each other. This is a great breakthrough in the design and synthesis of carbon-based functional materials. The obtained sandwich-like LiFePO4 nanocomposites present excellent electrochemical performance, which is rationally ascribed to the superb and unique structure and architecture. Of particular note is that the freestanding sandwich-like LiFePO4 nanocomposites exhibit enhanced cyclability and rate capability. At a high current density of 0.1 A g(-1), a stable specific capacity of approximately 168.5 mAh g(-1) can be delivered over 1000 cycles, and when the charge-discharge rates increase to 0.6, 2, 5 and 10 A g(-1), the specific capacities still survive at 149, 129, 114 and 91 mAh g(-1), respectively. Meanwhile, the sandwiched nanocomposite demonstrates a significantly improved low-temperature electrochemical energy storage performance. With respect to the excellent Li storage performance, and facility and reliability of production, the freestanding sandwich-like LiFePO4 nanocomposites are reasonably believed to have a great potential for multiple electrochemical energy storage applications.

Magnetic phase investigations on fluorine (F) doped LiFePO4

NASA Astrophysics Data System (ADS)

Radhamani, A. V.

2018-03-01

LiFePO4 (LFP) is a very promising cathode material for Li-ion batteries due to its high thermal stability, less toxicity and high theoretical capacity (170 mAh g-1). Anion doping, especially fluorine (F) at the oxygen site is one way to improve the low electronic conductivity of the material. In this line, fluorine doped LFP was prepared at different fluorine concentrations (1 to 40 mol%) to study the structural, spectroscopic and magnetic properties in view of the material property optimization for battery applications. The investigation of the magnetic properties was found to be successful for the determination of small amounts of magnetic impurities which were not noticeably observed from structural characterizations. Determination of conducting magnetic impurities has its own relevance in the current scenario of Li-ion based battery applications. Systematic characterization studies along with the implications of magnetic phases on the material activity of fluorine doped LiFePO4 nanoparticles will be discussed in detail.

Effect of carbon source on the morphology and electrochemical performances of LiFePO4/C nanocomposites.

PubMed

Liu, Shuxin; Wang, Haibin; Yin, Hengbo; Wang, Hong; He, Jichuan

2014-03-01

The carbon coated LiFePO4 (LiFePO4/C) nanocomposites materials were successfully synthesized by sol-gel method. The microstructure and morphology of LiFePO4/C nanocomposites were characterized by X-ray diffraction, Raman spectroscopy and scanning electron microscopy. The results showed that the carbon layers decomposed by different dispersant and carbon source had different graphitization degree, and the sugar could decompose to form more graphite-like structure carbon. The carbon source and heat-treatment temperature had some effect on the particle size and morphology, the sample LFP-S700 synthesized by adding sugar as carbon source at 700 degrees C had smaller particle size, uniform size distribution and spherical shape. The electrochemical behavior of LiFePO4/C nanocomposites was analyzed using galvanostatic measurements and cyclic voltammetry (CV). The results showed that the sample LFP-S700 had higher discharge specific capacities, higher apparent lithium ion diffusion coefficient and lower charge transfer resistance. The excellent electrochemical performance of sample LFP-S700 could be attributed to its high graphitization degree of carbon, smaller particle size and uniform size distribution.

Improvement on high rate performance of LiFePO4 cathodes using graphene as a conductive agent

NASA Astrophysics Data System (ADS)

Wei, Xufang; Guan, Yibiao; Zheng, Xiaohui; Zhu, Qizhen; Shen, Jinran; Qiao, Ning; Zhou, Shuqin; Xu, Bin

2018-05-01

In this work, the electrochemical properties of the LiFePO4 cathode using graphene as a conductive agent were revealed. Compared to the conventional LiFePO4 electrodes with carbon black as a conductive agent, the graphene sheets can establish a more effective conductive framework due to their layered structure and excellent electronic conductivity, leading to better electrochemical rate performance. Furthermore, the obverse of increasing graphene content is continued gains in high-rate performance of the LiFePO4 electrodes. The electrodes with 30 wt% graphene show high capacities up to 103.1 mA h g-1 and 68 mA h g-1 during discharging with extremely high rates of 30 C and 50 C, respectively. Besides, good cycling performance at high rate is also achieved. The electrodes with 30 wt% graphene display a capacity retention higher than 80% after 1000 cycles at 30 C. These results not only indicate that the graphene could be a promising candidate as a conductive agent, but also provide a new insight for designing LiFePO4 electrodes with brilliant high-rate performance via a simple method.

Unconventional Magnetism and Band Gap Formation in LiFePO4: Consequence of Polyanion Induced Non-planarity.

PubMed

Jena, Ajit; Nanda, B R K

2016-01-21

Oxygen plays a critical role in strongly correlated transition metal oxides as crystal field effect is one of the key factors that determine the degree of localization of the valence d/f states. Based on the localization, a set of conventional mechanisms such as Mott-Hubbard, Charge-transfer and Slater were formulated to explain the antiferromagnetic and insulating (AFI) phenomena in many of these correlated systems. From the case study on LiFePO4, through density-functional calculations, we demonstrate that none of these mechanisms are strictly applicable to explain the AFI behavior when the transition metal oxides have polyanions such as (PO4)(3-). The symmetry-lowering of the metal-oxygen complex, to stabilize the polyanion, creates an asymmetric crystal field for d/f states. In LiFePO4 this field creates completely non-degenerate Fe-d states which, with negligible p-d and d-d covalent interactions, become atomically localized to ensure a gap at the Fermi level. Due to large exchange splitting, high spin state is favored and an antiferromagnetic configuration is stabilized. For the prototype LiFePO4, independent electron approximation is good enough to obtain the AFI ground state. Inclusion of additional correlation measures like Hubbard U simply amplifies the gap and therefore LiFePO4 can be preferably called as weakly coupled Mott insulator.

Unconventional Magnetism and Band Gap Formation in LiFePO4: Consequence of Polyanion Induced Non-planarity

PubMed Central

Jena, Ajit; Nanda, B. R. K.

2016-01-01

Oxygen plays a critical role in strongly correlated transition metal oxides as crystal field effect is one of the key factors that determine the degree of localization of the valence d/f states. Based on the localization, a set of conventional mechanisms such as Mott-Hubbard, Charge-transfer and Slater were formulated to explain the antiferromagnetic and insulating (AFI) phenomena in many of these correlated systems. From the case study on LiFePO4, through density-functional calculations, we demonstrate that none of these mechanisms are strictly applicable to explain the AFI behavior when the transition metal oxides have polyanions such as (PO4)3−. The symmetry-lowering of the metal-oxygen complex, to stabilize the polyanion, creates an asymmetric crystal field for d/f states. In LiFePO4 this field creates completely non-degenerate Fe-d states which, with negligible p-d and d-d covalent interactions, become atomically localized to ensure a gap at the Fermi level. Due to large exchange splitting, high spin state is favored and an antiferromagnetic configuration is stabilized. For the prototype LiFePO4, independent electron approximation is good enough to obtain the AFI ground state. Inclusion of additional correlation measures like Hubbard U simply amplifies the gap and therefore LiFePO4 can be preferably called as weakly coupled Mott insulator. PMID:26791249

Effect of complexing agents on the electrochemical performance of LiFePO4/C prepared by sol-gel method

PubMed Central

2012-01-01

LiFePO4/C is synthesized via sol-gel method using Fe3+ as iron sources and different complexing agents, followed by sintering at high temperature for crystallization. The amount of carbon in these composites is less than 6.8 wt.%, and the X-ray diffraction experiment confirms that all samples are pure single phase indexed with the orthorhombic Pnma space group. The particle size of the LiFePO4/C synthesized by acetic acid as a complexing agent is very fine with a size of 200 nm. The electrochemical performance of this material, including reversible capacity, cycle number, and charge-discharge characteristics, is better than those of LiFePO4/C synthesized by other complexing agents. The cell of this sample can deliver a discharge capacity of 161.1 mAh g-1 at the first cycle. After 30 cycles, the capacity decreases to 157.5 mAh g-1, and the capacity fading rate is 2.2%. The mechanism is studied to explain the effect of a complexing agent on the synthesis of LiFePO4/C by sol-gel method. The results show that the complexing agent with a low stability constant may be proper for the synthetic process of LiFePO4/C via sol-gel method. PMID:22221711

Effect of complexing agents on the electrochemical performance of LiFePO4/C prepared by sol-gel method

NASA Astrophysics Data System (ADS)

Yang, Rong; Kang, Erwei; Jiang, Bailing; Ahn, Jou-Hyeon

2012-01-01

LiFePO4/C is synthesized via sol-gel method using Fe3+ as iron sources and different complexing agents, followed by sintering at high temperature for crystallization. The amount of carbon in these composites is less than 6.8 wt.%, and the X-ray diffraction experiment confirms that all samples are pure single phase indexed with the orthorhombic Pnma space group. The particle size of the LiFePO4/C synthesized by acetic acid as a complexing agent is very fine with a size of 200 nm. The electrochemical performance of this material, including reversible capacity, cycle number, and charge-discharge characteristics, is better than those of LiFePO4/C synthesized by other complexing agents. The cell of this sample can deliver a discharge capacity of 161.1 mAh g-1 at the first cycle. After 30 cycles, the capacity decreases to 157.5 mAh g-1, and the capacity fading rate is 2.2%. The mechanism is studied to explain the effect of a complexing agent on the synthesis of LiFePO4/C by sol-gel method. The results show that the complexing agent with a low stability constant may be proper for the synthetic process of LiFePO4/C via sol-gel method.

Ab-initio Calculation of the XANES of Lithium Phosphates and LiFePO4

NASA Astrophysics Data System (ADS)

Yiu, Y. M.; Yang, Songlan; Wang, Dongniu; Sun, Xueliang; Sham, T. K.

2013-04-01

Lithium iron phosphate has been regarded as a promising cathode material for the next generation lithium ion batteries due to its high specific capacity, superior thermal and cyclic stability [1]. In this study, the XANES (X-ray Absorption Near Edge Structure) spectra of lithium iron phosphate and lithium phosphates of various compositions at the Li K, P L3,2, Fe M3,2 and O K-edges have been simulated self-consistently using ab-initio calculations based on multiple scattering theory (the FEFF9 code) and DFT (Density Functional Theory, the Wien2k code). The lithium phosphates under investigation include LiFePO4, γ-Li3PO4, Li4P2O7 and LiPO3. The calculated spectra are compared to the experimental XANES recorded in total electron yield (TEY) and fluorescence yield (FLY). This work was carried out to assess the XANES of possible phases presented in LiFePO4 based Li ion battery applications [2].

Investigation of sodium insertion–extraction in olivine Na x FePO 4 (0 ≤ x ≤ 1) using first-principles calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saracibar, A.; Carrasco, J.; Saurel, D.

Olivine NaFePO4 has recently attracted the attention of the scientific community as a promising cathode material for Na-ion batteries. In this work we combine density functional theory (DFT) calculations and high resolution synchrotron X-ray diffraction (HRXRD) experiments to study the phase stability of NaxFePO4 along the whole range of sodium compositions (0 ≤ x ≤ 1). DFT calculations reveal the existence of two intermediate structures governing the phase stability at x = 2/3 and x = 5/6. This is in contrast to isostructural LiFePO4, which is a broadly used cathode in Li-ion batteries. Na2/3FePO4 and Na5/6FePO4 ground states both alignmore » vacancies diagonally within the ab plane, coupled to a Fe2+/Fe3+ alignment. HRXRD data for NaxFePO4 (2/3 < x < 1) materials show common superstructure reflections up to x = 5/6 within the studied compositions. The computed intercalation voltage profile shows a voltage difference of 0.16 V between NaFePO4 and Na2/3FePO4 in agreement with the voltage discontinuity observed experimentally during electrochemical insertion.« less

Carbon nanostructures modified LiFePO4 cathodes for lithium ion battery applications: optimized porosity and composition

NASA Astrophysics Data System (ADS)

Mahmoud, Lama; Singh Lalia, Boor; Hashaikeh, Raed

2016-12-01

Lithium iron phosphate (LiFePO4) battery cathode was fabricated without using any metallic current collector and polymeric binder. Carbon nanostructures (CNS) were used as microbinders for LiFePO4 particles and at the same time as a 3D current collector. A facile and cost effective method of fabricating composite cathodes of CNS and LiFePO4 was developed. Thick electrodes with high loading of active material (20-25 mg cm-2) were obtained that are almost 2-3 folds higher than commercial electrodes. SEM images confirm that the 3D CNS conductive network encapsulated the LiFePO4 particles homogenously facilitating the charge transfer at the electrode-CNS interface. The composition, scan rate and porosity of the paper-like cathode were sequentially varied and their influence was systematically monitored by means of linear sweep cyclic voltammetry and AC electrochemical impedance spectroscopy. Addition of CNS improved the electrode’s bulk electronic conductivity, mechanical integrity, surface area and double layer capacitance, yet compromised the charge transfer resistance at the electrode-electrolyte interface. Based on a range of the tested binder-free electrodes, this study proposes that electrodes with 20 wt% CNS having 49 ± 2.5% porosity had realized best improvements of two folds and four folds in the electronic conductivity and diffusion coefficient, respectively.

Influence of memory effect on the state-of-charge estimation of large-format Li-ion batteries based on LiFePO4 cathode

NASA Astrophysics Data System (ADS)

Shi, Wei; Wang, Jiulin; Zheng, Jianming; Jiang, Jiuchun; Viswanathan, Vilayanur; Zhang, Ji-Guang

2016-04-01

In this work, we systematically investigated the influence of the memory effect of LiFePO4 cathodes in large-format full batteries. The electrochemical performance of the electrodes used in these batteries was also investigated separately in half-cells to reveal their intrinsic properties. We noticed that the memory effect of LiFePO4/graphite cells depends not only on the maximum state of charge reached during the memory writing process, but is also affected by the depth of discharge reached during the memory writing process. In addition, the voltage deviation in a LiFePO4/graphite full battery is more complex than in a LiFePO4/Li half-cell, especially for a large-format battery, which exhibits a significant current variation in the region near its terminals. Therefore, the memory effect should be taken into account in advanced battery management systems to further extend the long-term cycling stabilities of Li-ion batteries using LiFePO4 cathodes.

Self-Assembly of Antisite Defectless nano-LiFePO4 @C/Reduced Graphene Oxide Microspheres for High-Performance Lithium-Ion Batteries.

PubMed

Wang, Hongbin; Liu, Lijia; Wang, Runwei; Yan, Xiao; Wang, Ziqi; Hu, Jiangtao; Chen, Haibiao; Jiang, Shang; Ni, Ling; Qiu, Hailong; Tang, Haitong; Wei, Yingjin; Zhang, Zongtao; Qiu, Shilun; Pan, Feng

2018-05-18

LiFePO 4 @C/reduced graphene oxide (rGO) hierarchical microspheres with superior electrochemical activity and a high tap density were first synthesized by using a Fe 3+ -based single inorganic precursor (LiFePO 4 OH@RF/GO; RF=resorcinol-formaldehyde, GO=graphene oxide) obtained from a template-free self-assembly synthesis followed by direct calcination. The synthetic process requires no physical mixing step. The phase transformation pathway from tavorite LiFePO 4 OH to olivine LiFePO 4 upon calcination was determined by means of the in situ high-temperature XRD technique. Benefitting from the unique structure of the material, these microspheres can be densely packed together, giving a high tap density of 1.3 g cm -3 , and simultaneously, defectless LiFePO 4 primary nanocrystals modified with a highly conductive surface carbon layer and ultrathin rGO provide good electronic and ionic kinetics for fast electron/Li + ion transport. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of imbalanced currents on large-format LiFePO4/graphite batteries systems connected in parallel

NASA Astrophysics Data System (ADS)

Shi, Wei; Hu, Xiaosong; Jin, Chao; Jiang, Jiuchun; Zhang, Yanru; Yip, Tony

2016-05-01

With the development and popularization of electric vehicles, it is urgent and necessary to develop effective management and diagnosis technology for battery systems. In this work, we design a parallel battery model, according to equivalent circuits of parallel voltage and branch current, to study effects of imbalanced currents on parallel large-format LiFePO4/graphite battery systems. Taking a 60 Ah LiFePO4/graphite battery system manufactured by ATL (Amperex Technology Limited, China) as an example, causes of imbalanced currents in the parallel connection are analyzed using our model, and the associated effect mechanisms on long-term stability of each single battery are examined. Theoretical and experimental results show that continuously increasing imbalanced currents during cycling are mainly responsible for the capacity fade of LiFePO4/graphite parallel batteries. It is thus a good way to avoid fast performance fade of parallel battery systems by suppressing variations of branch currents.

Electrochemical and XPS study of LiFePO4 cathode nanocomposite with PPy/PEG conductive network

NASA Astrophysics Data System (ADS)

Fedorková, A.; Oriňáková, R.; Oriňák, A.; Kupková, M.; Wiemhöfer, H.-D.; Audinot, J. N.; Guillot, J.

2012-08-01

High performance PPy/PEG-LiFePO4 nanocomposites as cathode materials were synthesized by solvothermal method and simple chemical oxidative polymerization of pyrrole (Py) monomer on the surface of LiFePO4 particles. The samples were characterized by scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectrometry (XPS) and charge-discharge tests. PPyPEG hybrid layers decrease particle to particle contact resistance while the impedance measurements confirmed that the coating of PPy-PEG significantly decreases the charge transfer resistance of the electrode material. The initial discharge capacities of this sample at C/5 and 1C are 150 and 128 mAh/g, respectively. The results show that PPy/PEGLiFePO4 composites are more effective than bare LiFePO4 as cathode material.

Optimization of multicomponent aqueous suspensions of lithium iron phosphate (LiFePO4) nanoparticles and carbon black for lithium-ion battery cathodes.

PubMed

Li, Jianlin; Armstrong, Beth L; Daniel, Claus; Kiggans, Jim; Wood, David L

2013-09-01

Addition of polyethyleneimine (PEI) to aqueous LiFePO4 nanoparticle suspensions improves stability and reduces agglomerate size, which is beneficial to lithium-ion battery cathode manufacturing. This research examines the effect of both PEI concentration and molecular weight (MW) on dispersing LiFePO4 and Super P C45 in multicomponent aqueous suspensions. It is demonstrated that the optimal conditions for obtaining stable suspensions with minimal agglomerate size are 1.5 wt% PEI with MW=2000 g mol(-1) and 5.0 wt% PEI with MW=10,000 g mol(-1) for LiFePO4 and Super P C45, respectively. The mixing sequence also affects rheological properties of these suspensions. It is found that dispersing the LiFePO4 and Super P C45 separately yielded suspensions with superior properties (Newtonian rheological behavior, smaller agglomerate size, improved settling, etc.). In particular, dispersing the LiFePO4 prior to the Super P C45 when making the final multicomponent suspension is found to be beneficial, which was evidenced by higher half-cell discharge capacity. Copyright © 2013 Elsevier Inc. All rights reserved.

Effect of reducing agents on low-temperature synthesis of nanostructured LiFePO4

NASA Astrophysics Data System (ADS)

Kulka, Andrzej; Walczak, Katarzyna; Zając, Wojciech; Molenda, Janina

2017-09-01

Simple co-precipitation synthesis procedure yielding nanometric LiFePO4 with enhanced electrochemical properties without any post-synthesis heat treatment is presented. XRD, SEM and TEM analysis of the obtained powders revealed platelet crystallites and well crystalized bulk structure. Effective way of decreasing amount of Fe3+ containing phases by addition of reducing agents (KI, (NH4)2S2O3, glucose and the atmosphere of 5%H2-95%Ar) during low-temperature (107 °C) synthesis is described. The traditional analytical chemistry methods or the Mӧssbauer spectroscopy methods revealed that utilization of selected reducing agents diminished Fe3+ concentration from 25 to 12 at%. The constructed cells with optimized LiFePO4 as a cathode material showed superior electrochemical performances, including high reversible capacity up to 162 mAh/g at C/10 current discharge rate, flat voltage plateau with a value close to 3.45 V vs. Li0/+.

Why LiFePO4 is a safe battery electrode: Coulomb repulsion induced electron-state reshuffling upon lithiation.

PubMed

Liu, Xiaosong; Wang, Yung Jui; Barbiellini, Bernardo; Hafiz, Hasnain; Basak, Susmita; Liu, Jun; Richardson, Thomas; Shu, Guojiun; Chou, Fangcheng; Weng, Tsu-Chien; Nordlund, Dennis; Sokaras, Dimosthenis; Moritz, Brian; Devereaux, Thomas P; Qiao, Ruimin; Chuang, Yi-De; Bansil, Arun; Hussain, Zahid; Yang, Wanli

2015-10-21

LiFePO4 is a battery cathode material with high safety standards due to its unique electronic structure. We performed systematic experimental and theoretical studies based on soft X-ray emission, absorption, and hard X-ray Raman spectroscopy of LixFePO4 nanoparticles and single crystals. The results clearly show a non-rigid electron-state reconfiguration of both the occupied and unoccupied Fe-3d and O-2p states during the (de)lithiation process. We focus on the energy configurations of the occupied states of LiFePO4 and the unoccupied states of FePO4, which are the critical states where electrons are removed and injected during the charge and discharge process, respectively. In LiFePO4, the soft X-ray emission spectroscopy shows that, due to the Coulomb repulsion effect, the occupied Fe-3d states with the minority spin sit close to the Fermi level. In FePO4, the soft X-ray absorption and hard X-ray Raman spectroscopy show that the unoccupied Fe-3d states again sit close to the Fermi level. These critical 3d electron state configurations are consistent with the calculations based on modified Becke and Johnson potentials GGA+U (MBJGGA+U) framework, which improves the overall lineshape prediction compared with the conventionally used GGA+U method. The combined experimental and theoretical studies show that the non-rigid electron state reshuffling guarantees the stability of oxygen during the redox reaction throughout the charge and discharge process of LiFePO4 electrodes, leading to the intrinsic safe performance of the electrodes.

Encapsulation of LiFePO4 by in-situ graphitized carbon cage towards enhanced low temperature performance as cathode materials for lithium ion batteries

NASA Astrophysics Data System (ADS)

Yao, Bin; Ding, Zhaojun; Zhang, Jianxin; Feng, Xiaoyu; Yin, Longwei

2014-08-01

The severe capacity decay of LiFePO4 at low temperatures (≤0 °C) limits its wide applications as cathode materials for energy storage batteries. Creating comprehensive carbon network between particles with improved electronic conductivity is a well known solution to this problem. Here, a novel structured LiFePO4/C composite was prepared by a facile solid state route, in which nanosized LiFePO4 spheres were encapsulated by in-situ graphitized carbon cages. With the enhancement in electronic conductivity (2.15e-1 S cm-1), the composite presented excellent rate performance at room temperature and remarkable capacity retention at -40 °C, with charge transfer resistance much lower than commercial LiFePO4.

Combined operando X-ray diffraction-electrochemical impedance spectroscopy detecting solid solution reactions of LiFePO4 in batteries.

PubMed

Hess, Michael; Sasaki, Tsuyoshi; Villevieille, Claire; Novák, Petr

2015-09-08

Lithium-ion batteries are widely used for portable applications today; however, often suffer from limited recharge rates. One reason for such limitation can be a reduced active surface area during phase separation. Here we report a technique combining high-resolution operando synchrotron X-ray diffraction coupled with electrochemical impedance spectroscopy to directly track non-equilibrium intermediate phases in lithium-ion battery materials. LiFePO4, for example, is known to undergo phase separation when cycled under low-current-density conditions. However, operando X-ray diffraction under ultra-high-rate alternating current and direct current excitation reveal a continuous but current-dependent, solid solution reaction between LiFePO4 and FePO4 which is consistent with previous experiments and calculations. In addition, the formation of a preferred phase with a composition similar to the eutectoid composition, Li0.625FePO4, is evident. Even at a low rate of 0.1C, ∼20% of the X-ray diffractogram can be attributed to non-equilibrium phases, which changes our understanding of the intercalation dynamics in LiFePO4.

Quantum-Chemical Approach to NMR Chemical Shifts in Paramagnetic Solids Applied to LiFePO4 and LiCoPO4.

PubMed

Mondal, Arobendo; Kaupp, Martin

2018-04-05

A novel protocol to compute and analyze NMR chemical shifts for extended paramagnetic solids, accounting comprehensively for Fermi-contact (FC), pseudocontact (PC), and orbital shifts, is reported and applied to the important lithium ion battery cathode materials LiFePO 4 and LiCoPO 4 . Using an EPR-parameter-based ansatz, the approach combines periodic (hybrid) DFT computation of hyperfine and orbital-shielding tensors with an incremental cluster model for g- and zero-field-splitting (ZFS) D-tensors. The cluster model allows the use of advanced multireference wave function methods (such as CASSCF or NEVPT2). Application of this protocol shows that the 7 Li shifts in the high-voltage cathode material LiCoPO 4 are dominated by spin-orbit-induced PC contributions, in contrast with previous assumptions, fundamentally changing interpretations of the shifts in terms of covalency. PC contributions are smaller for the 7 Li shifts of the related LiFePO 4 , where FC and orbital shifts dominate. The 31 P shifts of both materials finally are almost pure FC shifts. Nevertheless, large ZFS contributions can give rise to non-Curie temperature dependences for both 7 Li and 31 P shifts.

In situ catalytic synthesis of high-graphitized carbon-coated LiFePO4 nanoplates for superior Li-ion battery cathodes.

PubMed

Ma, Zhipeng; Fan, Yuqian; Shao, Guangjie; Wang, Guiling; Song, Jianjun; Liu, Tingting

2015-02-04

The low electronic conductivity and one-dimensional diffusion channel along the b axis for Li ions are two major obstacles to achieving high power density of LiFePO4 material. Coating carbon with excellent conductivity on the tailored LiFePO4 nanoparticles therefore plays an important role for efficient charge and mass transport within this material. We report here the in situ catalytic synthesis of high-graphitized carbon-coated LiFePO4 nanoplates with highly oriented (010) facets by introducing ferrocene as a catalyst during thermal treatment. The as-obtained material exhibits superior performances for Li-ion batteries at high rate (100 C) and low temperature (-20 °C), mainly because of fast electron transport through the graphitic carbon layer and efficient Li(+)-ion diffusion through the thin nanoplates.

A facile route to modify ferrous phosphate and its use as an iron-containing resource for LiFePO4 via a polyol process.

PubMed

Li, Shaomin; Liu, Xichuan; Mi, Rui; Liu, Hao; Li, Yinchuan; Lau, Woon-min; Mei, Jun

2014-06-25

This study introduces an economical and environmentally friendly way of synthesizing LiFePO4/C to be used as cathode material in lithium ion batteries via two processes: (1) the synthesis of LiFePO4/C cathode material using a low cost divalent precursor ferrous phosphate, Fe3 (PO4)2·8H2O, as iron source in a polyol process and (2) the modification of the morphology of this precursor by varying the reaction time in a coprecipitation process. The study examines the effects of different structures and morphologies of the precursor on the structure and electrochemical performance of the as-synthesized LiFePO4/C. The LiFePO4/C shows an excellent rate capability and cycle performance, with initial discharge capacities of 153, 128, and 106 mA h g(-1) at 1 C, 5 C, and 10 C. The capacity retention is respectively 98.7%, 98.2%, and 98.7%, after 10 cycles at the corresponding rates. The capacity retention remains at 97% even after 300 cycles at the rate of 10 C. The outstanding electrochemical performance can be attributed to the improved rate of Li(+) diffusion and the excellent crystallinity of synthesized LiFePO4/C powders through the modified precursor. Therefore, this is an economical and environmentally friendly way of synthesizing LiFePO4/C to be used as cathode material in lithium ion batteries.

Capacity Fading Mechanism of the Commercial 18650 LiFePO4-Based Lithium-Ion Batteries: An in Situ Time-Resolved High-Energy Synchrotron XRD Study.

PubMed

Liu, Qi; Liu, Yadong; Yang, Fan; He, Hao; Xiao, Xianghui; Ren, Yang; Lu, Wenquan; Stach, Eric; Xie, Jian

2018-02-07

In situ high-energy synchrotron XRD studies were carried out on commercial 18650 LiFePO 4 cells at different cycles to track and investigate the dynamic, chemical, and structural changes in the course of long-term cycling to elucidate the capacity fading mechanism. The results indicate that the crystalline structural deterioration of the LiFePO 4 cathode and the graphite anode is unlikely to happen before capacity fades below 80% of the initial capacity. Rather, the loss of the active lithium source is the primary cause for the capacity fade, which leads to the appearance of inactive FePO 4 that is proportional to the absence of the lithium source. Our in situ HESXRD studies further show that the lithium-ion insertion and deinsertion behavior of LiFePO 4 continuously changed with cycling. For a fresh cell, the LiFePO 4 experienced a dual-phase solid-solution behavior, whereas with increasing cycle numbers, the dynamic change, which is characteristic of the continuous decay of solid solution behavior, is obvious. The unpredicted dynamic change may result from the morphology evolution of LiFePO 4 particles and the loss of the lithium source, which may be the cause of the decreased rate capability of LiFePO 4 cells after long-term cycling.

Desired crystal oriented LiFePO4 nanoplatelets in situ anchored on a graphene cross-linked conductive network for fast lithium storage.

PubMed

Wang, Bo; Liu, Anmin; Abdulla, Wael Al; Wang, Dianlong; Zhao, X S

2015-05-21

Electron transfer and lithium ion diffusion rates are the key factors limiting the lithium ion storage in anisotropic LiFePO4 electrodes. In this work, we employed a facile solvothermal method to synthesize a "platelet-on-sheet" LiFePO4/graphene composite (LFP@GNs), which is LiFePO4 nanoplatelets in situ grown on graphene sheets with highly oriented (010) facets of LiFePO4 crystals. Such a two-phase contact mode with graphene sheets cross-linked to form a three-dimensional porous network is favourable for both fast lithium ion and electron transports. As a result, the designed LFP@GNs displayed a high rate capability (∼56 mA h g(-1) at 60 C) and long life cycling stability (∼87% capacity retention over 1000 cycles at 10 C). For comparison purposes, samples ex situ modified with graphene (LFP/GNs) as well as pure LiFePO4 platelets (LFP) were also prepared and investigated. More importantly, the obtained LFP@GNs can be used as a basic unit for constructing more complex structures to further improve electrochemical performance, such as coating the exposed LFP surface with a thin layer of carbon to build a C@LFP@GN composite to further enhance its cycling stability (∼98% capacity retention over 1000 cycles at 10 C).

Synergistic effect in carbon coated LiFePO4 for high yield spontaneous grafting of diazonium salt. Structural examination at the grain agglomerate scale.

PubMed

Madec, Lénaïc; Robert, Donatien; Moreau, Philippe; Bayle-Guillemaud, Pascale; Guyomard, Dominique; Gaubicher, Joël

2013-08-07

Molecular grafting of p-nitrobenzene diazonium salt at the surface of (Li)FePO4-based materials was thoroughly investigated. The grafting yields obtained by FTIR, XPS, and elemental analysis for core shell LiFePO4-C are found to be much higher than the sum of those associated with either the LiFePO4 core or the carbon shell alone, thereby revealing a synergistic effect. Electrochemical, XRD, and EELS experiments demonstrate that this effect stems from the strong participation of the LiFePO4 core that delivers large amounts of electrons to the carbon substrate at a constant energy, above the Fermi level of the diazonium salt. Correspondingly large multilayer anisotropic structures that are associated with outstanding grafting yields could be observed from TEM experiments. Results therefore constitute strong evidence of a grafting mechanism where homolytic cleavage of the N2(+) species occurs together with the formation and grafting of radical nitro-aryl intermediates. Although the oxidation and concomitant Li deintercalation of LiFePO4 grains constitute the main driving force of the functionalization reaction, EFTEM EELS mapping shows a striking lack of spatial correlation between grafted grains and oxidized ones.

Monodisperse porous LiFePO4/C microspheres derived by microwave-assisted hydrothermal process combined with carbothermal reduction for high power lithium-ion batteries

NASA Astrophysics Data System (ADS)

Chen, Rongrong; Wu, Yixiong; Kong, Xiang Yang

2014-07-01

A microwave-assisted hydrothermal approach combined with carbothermal reduction has been developed to synthesize monodisperse porous LiFePO4/C microspheres, which possess the diameter range of 1.0-1.5 μm, high tap density of ∼1.3 g cm-3, and mesoporous characteristic with Brunauer-Emmett-Teller (BET) surface area of 30.6 m2 g-1. The obtained microspheres show meatball-like morphology aggregated by the carbon-coated LiFePO4 nanoparticles. The electrochemical impedance spectra (EIS) results indicate that carbon coating can effectively enhance both of the electronic and ionic conductivities for LiFePO4/C microspheres. The Li-ion diffusion coefficient of the LiFePO4/C microspheres calculated from the cyclic voltammetry (CV) curves is ∼6.25 × 10-9 cm2 s-1. The electrochemical performance can achieve about 100 and 90 mAh g-1 at 5C and 10C charge/discharge rates, respectively. As cathode material, the as-prepared LiFePO4/C microspheres show excellent rate capability and cycle stability, promising for high power lithium-ion batteries.

A simple route to improve rate performance of LiFePO4/reduced graphene oxide composite cathode by adding Mg2+ via mechanical mixing

NASA Astrophysics Data System (ADS)

Huang, Yuan; Liu, Hao; Gong, Li; Hou, Yanglong; Li, Quan

2017-04-01

Introducing Mg2+ to LiFePO4 and reduced graphene oxide composite via mechanical mixing and annealing leads to largely improved rate performance of the cathode (e.g. ∼78 mA h g-1 at 20 C for LiFePO4 and reduced graphene oxide composite with Mg2+ introduction vs. ∼37 mA h g-1 at 20 C for LiFePO4 and reduced graphene oxide composite). X-ray photoelectron spectroscopy unravels that the enhanced reduction of Fe2+ to Fe0 occurs in the simultaneous presence of Mg2+ and reduced graphene oxide, which is beneficial for the rate capability of cathode. The simple fabrication process provides a simple and effective means to improve the rate performance of the LiFePO4 and reduced graphene oxide composite cathode.

Study of imbalanced internal resistance on drop voltage of LiFePO4 battery system connected in parallel

NASA Astrophysics Data System (ADS)

Adie Perdana, Fengky; Supriyanto, Agus; Purwanto, Agus; Jamaluddin, Anif

2017-01-01

The purpose of this research focuses on the effect of imbalanced internal resistance for the drop voltage of LiFePO4 18650 battery system connected in parallel. The battery pack has been assembled consist of two cell battery LiFePO4 18650 that has difference combination of internal resistance. Battery pack was tested with 1/C constant current charging, 3,65V per group sel, 3,65V constant voltage charging, 5 minutes of rest time between charge and discharge process, 1/2C Constant current discharge until 2,2V, 26 cycle of measurement test, and 4320 minutes rest time after the last charge cycle. We can conclude that the difference combination of internal resistance on the battery pack seriously influence the drop voltage of a battery. Theoretical and experimental result show that the imbalance of internal resistance during cycling are mainly responsible for the drop voltage of LiFePO4 parallel batteries. It is thus a good way to avoid drop voltage fade of parallel battery system by suppressing variations of internal resistance.

Combined operando X-ray diffraction–electrochemical impedance spectroscopy detecting solid solution reactions of LiFePO4 in batteries

PubMed Central

Hess, Michael; Sasaki, Tsuyoshi; Villevieille, Claire; Novák, Petr

2015-01-01

Lithium-ion batteries are widely used for portable applications today; however, often suffer from limited recharge rates. One reason for such limitation can be a reduced active surface area during phase separation. Here we report a technique combining high-resolution operando synchrotron X-ray diffraction coupled with electrochemical impedance spectroscopy to directly track non-equilibrium intermediate phases in lithium-ion battery materials. LiFePO4, for example, is known to undergo phase separation when cycled under low-current-density conditions. However, operando X-ray diffraction under ultra-high-rate alternating current and direct current excitation reveal a continuous but current-dependent, solid solution reaction between LiFePO4 and FePO4 which is consistent with previous experiments and calculations. In addition, the formation of a preferred phase with a composition similar to the eutectoid composition, Li0.625FePO4, is evident. Even at a low rate of 0.1C, ∼20% of the X-ray diffractogram can be attributed to non-equilibrium phases, which changes our understanding of the intercalation dynamics in LiFePO4. PMID:26345306

Degradation diagnosis of aged Li4Ti5O12/LiFePO4 batteries

NASA Astrophysics Data System (ADS)

Castaing, Rémi; Reynier, Yvan; Dupré, Nicolas; Schleich, Donald; Jouanneau Si Larbi, Séverine; Guyomard, Dominique; Moreau, Philippe

2014-12-01

Li4Ti5O12/LiFePO4 cells are cycled under 4 different conditions of discharge profile (galvanostatic or driving-based) and cycling rates (C/8 or 1C) during 4-5 months. All the cells exhibit capacity fade whose extent is not correlated with the aging condition. In order to understand aging phenomena, cells are disassembled at the end of cycle life and the recovered electrodes are analyzed using electrochemistry, electron microscopy, XRD and MAS-NMR. Positive and negative electrodes show no loss in active material and no change in electrochemical activity, active material structure and composite electrode structure. This rules out any irreversible electrode degradation. Lithium stoichiometry estimated by both XRD and electrochemistry is unexpectedly low in the positive electrode when the aging is stopped at full discharge. That indicates a loss of cyclable lithium or electrons leading to cell balancing evolution. That loss may have been caused by parasitic reactions occurring at both electrodes, in accordance with their rich surface chemistry as evidenced by MAS-NMR.

Investigating the stability of cathode materials for rechargeable lithium ion batteries

NASA Astrophysics Data System (ADS)

Huang, Yiqing

Lithium ion batteries are widely used in portable electronic devices and electric vehicles. However, safety is one of the most important issues for the Li-ion batteries' use. Some cathode materials, such as LiCoO 2, are thermally unstable in the charged state. Upon decomposition these cathode materials release O2, which could react with organic electrolyte, leading to a thermal runaway. Thus understanding the stability of the cathode materials is critical to the safety of lithium ion batteries. Olivine-type LiMnPO4 is a promising cathode material for lithium ion batteries because of its high energy density. We have revealed the critical role of carbon in the stability and thermal behaviour of olivine MnPO 4 obtained by chemical delithiation of LiMnPO4. (Li)MnPO 4 samples with various particle sizes and carbon contents were studied. Carbon-free LiMnPO4 obtained by solid state synthesis in O 2 becomes amorphous upon delithiation. Small amounts of carbon (0.3 wt.%) help to stabilize the olivine structure, so that completely delithiated crystalline olivine MnPO4 can be obtained. Larger amount of carbon (2 wt.%) prevents full delithiation. Heating in air, O2, or N 2 results in structural disorder (< 300 °C), formation of an intermediate sarcopside Mn3(PO4)2 phase (350 -- 450 °C), and complete decomposition to Mn2P2O 7 on extended heating at 400 °C. Carbon protects MnPO4 from reacting with environmental water, which is detrimental to its structural stability. We not only studied the crystalline olivine MnPO4, but also investigated the amorphous products obtained from carbon-free LiMnPO 4. We have revealed the Mn dissolution phenomenon during chemical delithiation of LiMnPO4, which causes the amorphization of olivine MnPO 4. Properties of crystalline-MnPO4 obtained from carbon-coated LiMnPO4 and of amorphous product resulting from the delithiation of pure LiMnPO4 were studied and compared. The P-rich amorphous phases in the latter are considered to be MnHP2O7 and MnH2P

Excellent temperature performance of spherical LiFePO4/C composites modified with composite carbon and metal oxides.

PubMed

Zhang, Bao; Zeng, Tao; Zhang, Jiafeng; Peng, Chunli; Zheng, Junchao; Chen, Guomin

2014-01-01

Nanosized spherical LiFePO4/C composite was synthesized from nanosized spherical FePO4 ·2H2O, Li2C2O4, aluminum oxide, titanium oxide, oxalic acid, and sucrose by binary sintering process. The phases and morphologies of LiFePO4/C were characterized using SEM, TEM, CV, EIS, EDS, and EDX as well as charging and discharging measurements. The results showed that the as-prepared LiFePO4/C composite with good conductive webs from nanosized spherical FePO4 ·2H2O exhibits excellent electrochemical performances, delivering an initial discharge capacity of 161.7 mAh·g(-1) at a 0.1 C rate, 152.4 mAh·g(-1) at a 1 C rate and 131.7 mAh·g(-1) at a 5 C rate, and the capacity retention of 99.1%, 98.7%, and 95.8%, respectively, after 50 cycles. Meanwhile, the high and low temperature performance is excellent for 18650 battery, maintaining capacity retention of 101.7%, 95.0%, 88.3%, and 79.3% at 55°C, 0°C, -10°C, and -20°C by comparison withthat of room temperature (25°C) at the 0.5 C rate over a voltage range of 2.2 V to 3.6 V, respectively.

In-situ growth of graphene decorations for high-performance LiFePO4 cathode through solid-state reaction

NASA Astrophysics Data System (ADS)

Li, Jing; Zhang, Li; Zhang, Longfei; Hao, Weiwei; Wang, Haibo; Qu, Qunting; Zheng, Honghe

2014-03-01

Graphene-decorated LiFePO4 composite is synthesized for the first time through in-situ pyrolysis and catalytic graphitization, in which glucose and a trace amount of FeSO4 are employed as the graphene source and catalyst precursor, respectively. Under Ar/H2 (95:5) atmosphere at 750 °C, FeSO4 is thermally reduced to Fe nano-particles (Fe NPs) and glucose is pyrolyzed to carbon fragments first, followed by the in-situ growth of graphene sheets directly on the LiFePO4 nano-particles (LFP NPs) surface through the realignment of carbon fragments under the catalytic effect of the Fe NPs. The graphene sheets not only form a compact and uniform coating layer throughout the LFP NPs, but also stretch out and cross-link into a conducting network around the LFP particles. The LiFePO4@graphene composite displays a high reversible specific capacity of 167.7 mAh g-1 at 0.1C rate, superb rate performance with discharge capacity of 94.3 mAh g-1 at 100C rate and much prolonged cycle life. The remarkable electrochemical improvement is attributed to both electric and ionic conductivity increase as a result of in-situ grown graphene coatings along the LFP surface and the graphene network intrinsically connecting to the LFP particles.

Quality monitoring methods of initial and terminal manufacture of LiFePO4 based lithium ion batteries by capillary electrophoresis.

PubMed

Xie, Xia; Yang, Yang; Zhou, Henghui; Li, Meixian; Zhu, Zhiwei

2018-03-01

Magnetic impurities of lithium ion battery degrade both the capacity and cycling rates, even jeopardize the safety of the battery. During the material manufacture of LiFePO 4 , two opposite and extreme cases (trace impurity Fe(II) with high content of Fe(III) background in FePO 4 of initial end and trace Fe(III) with high content of Fe(II) background in LiFePO 4 of terminal end) can result in the generation of magnetic impurities. Accurate determination of impurities and precise evaluation of raw material or product are necessary to ensure reliability, efficiency and economy in lithium ion battery manufacture. Herein, two kinds of rapid, simple, and sensitive capillary electrophoresis (CE) methods are proposed for quality monitoring of initial and terminal manufacture of LiFePO 4 based lithium ion batteries. The key to success includes the smart use of three common agents 1,10-phenanthroline (phen), EDTA and cetyltrimethyl ammonium bromide (CTAB) in sample solution or background electrolyte (BGE), as well as sample stacking technique of CE feature. Owing to the combination of field-enhanced sample injection (FESI) technique with high stacking efficiency, detection limits of 2.5nM for Fe(II) and 0.1μM for Fe(III) were obtained corresponding to high content of Fe(III) and Fe(II), respectively. The good recoveries and reliability demonstrate that the developed methods are accurate approaches for quality monitoring of LiFePO 4 manufacture. Copyright © 2017 Elsevier B.V. All rights reserved.

Engineering 3D bicontinuous hierarchically macro-mesoporous LiFePO4/C nanocomposite for lithium storage with high rate capability and long cycle stability

PubMed Central

Zhang, Qian; Huang, Shao-Zhuan; Jin, Jun; Liu, Jing; Li, Yu; Wang, Hong-En; Chen, Li-Hua; Wang, Bin-Jie; Su, Bao-Lian

2016-01-01

A highly crystalline three dimensional (3D) bicontinuous hierarchically macro-mesoporous LiFePO4/C nanocomposite constructed by nanoparticles in the range of 50~100 nm via a rapid microwave assisted solvothermal process followed by carbon coating have been synthesized as cathode material for high performance lithium-ion batteries. The abundant 3D macropores allow better penetration of electrolyte to promote Li+ diffusion, the mesopores provide more electrochemical reaction sites and the carbon layers outside LiFePO4 nanoparticles increase the electrical conductivity, thus ultimately facilitating reverse reaction of Fe3+ to Fe2+ and alleviating electrode polarization. In addition, the particle size in nanoscale can provide short diffusion lengths for the Li+ intercalation-deintercalation. As a result, the 3D macro-mesoporous nanosized LiFePO4/C electrode exhibits excellent rate capability (129.1 mA h/g at 2 C; 110.9 mA h/g at 10 C) and cycling stability (87.2% capacity retention at 2 C after 1000 cycles, 76.3% at 5 C after 500 cycles and 87.8% at 10 C after 500 cycles, respectively), which are much better than many reported LiFePO4/C structures. Our demonstration here offers the opportunity to develop nanoscaled hierarchically porous LiFePO4/C structures for high performance lithium-ion batteries through microwave assisted solvothermal method. PMID:27181195

Engineering 3D bicontinuous hierarchically macro-mesoporous LiFePO4/C nanocomposite for lithium storage with high rate capability and long cycle stability.

PubMed

Zhang, Qian; Huang, Shao-Zhuan; Jin, Jun; Liu, Jing; Li, Yu; Wang, Hong-En; Chen, Li-Hua; Wang, Bin-Jie; Su, Bao-Lian

2016-05-16

A highly crystalline three dimensional (3D) bicontinuous hierarchically macro-mesoporous LiFePO4/C nanocomposite constructed by nanoparticles in the range of 50~100 nm via a rapid microwave assisted solvothermal process followed by carbon coating have been synthesized as cathode material for high performance lithium-ion batteries. The abundant 3D macropores allow better penetration of electrolyte to promote Li(+) diffusion, the mesopores provide more electrochemical reaction sites and the carbon layers outside LiFePO4 nanoparticles increase the electrical conductivity, thus ultimately facilitating reverse reaction of Fe(3+) to Fe(2+) and alleviating electrode polarization. In addition, the particle size in nanoscale can provide short diffusion lengths for the Li(+) intercalation-deintercalation. As a result, the 3D macro-mesoporous nanosized LiFePO4/C electrode exhibits excellent rate capability (129.1 mA h/g at 2 C; 110.9 mA h/g at 10 C) and cycling stability (87.2% capacity retention at 2 C after 1000 cycles, 76.3% at 5 C after 500 cycles and 87.8% at 10 C after 500 cycles, respectively), which are much better than many reported LiFePO4/C structures. Our demonstration here offers the opportunity to develop nanoscaled hierarchically porous LiFePO4/C structures for high performance lithium-ion batteries through microwave assisted solvothermal method.

In situ Raman spectroscopy of LiFePO4: size and morphology dependence during charge and self-discharge.

PubMed

Wu, Jing; Dathar, Gopi Krishna Phani; Sun, Chunwen; Theivanayagam, Murali G; Applestone, Danielle; Dylla, Anthony G; Manthiram, Arumugam; Henkelman, Graeme; Goodenough, John B; Stevenson, Keith J

2013-10-25

Previous studies of the size dependent properties of LiFePO4 have focused on the diffusion rate or phase transformation pathways by bulk analysis techniques such as x-ray diffraction (XRD), neutron diffraction and electrochemistry. In this work, in situ Raman spectroscopy was used to study the surface phase change during charge and self-discharge on a more localized scale for three morphologies of LiFePO4: (1) 25 ± 6 nm width nanorods, (2) 225 ± 6 nm width nanorods and (3) ∼2 μm porous microspheres. Both the large nanorod and microsphere geometries showed incomplete delithiation at the end of charge, which was most likely caused by anti-site defects along the 1D diffusion channels in the bulk of the larger particles. Based on the in situ Raman measurements, all of the morphologies studied exhibited self-discharge with time. Among them, the smallest FePO4 particles self-discharged (lithiated) the fastest. While nanostructuring LiFePO4 can offer advantages in terms of lowering anti-site defects within particles, it also creates new problems due to high surface energies that allow self-discharge. The in situ Raman spectroscopy also showed that carbon coating did not provide significant improvement to the stability of the lithiated particles.

Effects of ionic liquid to water ratio as a composite medium for the synthesis of LiFePO4 for battery

NASA Astrophysics Data System (ADS)

Tith, Rany; Dutta, Jaydeep; Jung, Kichang; Martinez-Morales, Alfredo A.

2017-05-01

LiFePO4 is a highly researched cathode material that serves as an alternative material for traditional commercial lithiumion batteries such as LiCoO2. Currently, there are a number of different methods to synthesize LiFePO4 including: hydrothermal, solid state, spray pyrolysis, and coprecipitation. Our proposed method has the potential to provide an ecologically friendly and economically competitive way to synthesize LiFePO4 by utilizing ionic liquid and water, as a composite synthesis medium. The addition of water to ionic liquid can be beneficial as it can act as a mineralizer to bring insoluble precursors to form LiFePO4 seed crystals. Furthermore, this method provides the possibility of recycling the ionic liquid for repeated synthesis processes. In this work, we study the effects of ionic liquid to water ratio on the crystallinity and morphology of the synthesized material. Our group was able to conclude a reaction medium utilizing a ratio of equal parts of 1-ethyl-3-methyl imidazolium trifluoromethane sulfonate (EMIM Otf) and water, or a slightly favored ionic liquid ratio, increases the efficacy of the synthesis route. Crystallinity and purity was determined by X-ray diffraction (XRD), scanning electron microscopy (SEM) was used to determine morphology and crystal sizes, and energy dispersion spectroscopy (EDX) was used for elemental analysis.

Synthesis, Characterization, and Electrochemical Behavior of LiMnxFe(1−x)PO4 Composites Obtained from Phenylphosphonate-Based Organic-Inorganic Hybrids

PubMed Central

Dell’Era, Alessandro; Pasquali, Mauro; Bauer, Elvira Maria; Lupi, Carla

2017-01-01

The synthesis of organic-inorganic hybrid compounds based on phenylphosphonate and their use as precursors to form LiMnxFe(1−x)PO4 composites containing carbonaceous substances with sub-micrometric morphology are presented. The experimental procedure includes the preliminary synthesis of Fe2+ and/or Mn2+ phenylphosphonates with the general formula Fe(1−x)Mnx[(C6H5PO3)(H2O)] (with 0 < x < 1), which are then mixed at different molar ratios with lithium carbonate. In this way the carbon, obtained from in situ partial oxidation of the precursor organic part, coats the LiMnxFe(1−x)PO4 particles. After a structural and morphological characterization, the electrochemical behavior of lithium iron manganese phosphates has been compared to the one of pristine LiFePO4 and LiMnPO4, in order to evaluate the doping influence on the material. PMID:29301206

Relating the 3D electrode morphology to Li-ion battery performance; a case for LiFePO4

NASA Astrophysics Data System (ADS)

Liu, Zhao; Verhallen, Tomas W.; Singh, Deepak P.; Wang, Hongqian; Wagemaker, Marnix; Barnett, Scott

2016-08-01

One of the main goals in lithium ion battery electrode design is to increase the power density. This requires insight in the relation between the complex heterogeneous microstructure existing of active material, conductive additive and electrolyte providing the required electronic and Li-ion transport. FIB-SEM is used to determine the three phase 3D morphology, and Li-ion concentration profiles obtained with Neutron Depth Profiling (NDP) are compared for two cases, conventional LiFePO4 electrodes and better performing carbonate templated LiFePO4 electrodes. This provides detailed understanding of the impact of key parameters such as the tortuosity for electron and Li-ion transport though the electrodes. The created hierarchical pore network of the templated electrodes, containing micron sized pores, appears to be effective only at high rate charge where electrolyte depletion is hindering fast discharge. Surprisingly the carbonate templating method results in a better electronic conductive CB network, enhancing the activity of LiFePO4 near the electrolyte-electrode interface as directly observed with NDP, which in a large part is responsible for the improved rate performance both during charge and discharge. The results demonstrate that standard electrodes have a far from optimal charge transport network and that significantly improved electrode performance should be possible by engineering the microstructure.

Preparation of Ce- and La-Doped Li4Ti5O12 Nanosheets and Their Electrochemical Performance in Li Half Cell and Li4Ti5O12/LiFePO4 Full Cell Batteries

PubMed Central

Qin, Meng; Li, Yueming; Lv, Xiao-Jun

2017-01-01

This work reports on the synthesis of rare earth-doped Li4Ti5O12 nanosheets with high electrochemical performance as anode material both in Li half and Li4Ti5O12/LiFePO4 full cell batteries. Through the combination of decreasing the particle size and doping by rare earth atoms (Ce and La), Ce and La doped Li4Ti5O12 nanosheets show the excellent electrochemical performance in terms of high specific capacity, good cycling stability and excellent rate performance in half cells. Notably, the Ce-doped Li4Ti5O12 shows good electrochemical performance as anode in a full cell which LiFePO4 was used as cathode. The superior electrochemical performance can be attributed to doping as well as the nanosized particle, which facilitates transportation of the lithium ion and electron transportation. This research shows that the rare earth doped Li4Ti5O12 nanosheets can be suitable as a high rate performance anode material in lithium-ion batteries. PMID:28632167

The Synthesis of LiMnxFe1−xPO4/C Cathode Material through Solvothermal Jointed with Solid-State Reaction

PubMed Central

He, Xiangming; Wang, Jixian; Dai, Zhongjia; Wang, Li; Tian, Guangyu

2016-01-01

LiMnxFe1−xPO4/C material has been synthesized through a facile solid-state reaction under the condition of carbon coating, using solvothermal-prepared LiMnPO4 and LiFePO4 as precursors and sucrose as a carbon resource. XRD and element distribution analysis reveal completed solid-state reaction of precursors. LiMnxFe1−xPO4/C composites inherit the morphology of precursors after heat treatment without obvious agglomeration and size increase. LiMnxFe1−xPO4 solid solution forms at low temperature around 350 °C, and Mn2+/Fe2+ diffuse completely within 1 h at 650 °C. The LiMnxFe1−xPO4/C (x < 0.8) composite exhibits a high-discharge capacity of over 120 mAh·g−1 (500 Wh·kg−1) at low C-rates. This paves a way to synthesize the crystal-optimized LiMnxFe1−xPO4/C materials for high performance Li-ion batteries. PMID:28773887

Multiscale phase mapping of LiFePO4-based electrodes by transmission electron microscopy and electron forward scattering diffraction.

PubMed

Robert, Donatien; Douillard, Thierry; Boulineau, Adrien; Brunetti, Guillaume; Nowakowski, Pawel; Venet, Denis; Bayle-Guillemaud, Pascale; Cayron, Cyril

2013-12-23

LiFePO4 and FePO4 phase distributions of entire cross-sectioned electrodes with various Li content are investigated from nanoscale to mesoscale, by transmission electron microscopy and by the new electron forward scattering diffraction technique. The distributions of the fully delithiated (FePO4) or lithiated particles (LiFePO4) are mapped on large fields of view (>100 × 100 μm(2)). Heterogeneities in thin and thick electrodes are highlighted at different scales. At the nanoscale, the statistical analysis of 64 000 particles unambiguously shows that the small particles delithiate first. At the mesoscale, the phase maps reveal a core-shell mechanism at the scale of the agglomerates with a preferential pathway along the electrode porosities. At larger scale, lithiation occurs in thick electrodes "stratum by stratum" from the surface in contact with electrolyte toward the current collector.

High-rate and ultralong cycle-life LiFePO4 nanocrystals coated by boron-doped carbon as positive electrode for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Feng, Jinpeng; Wang, Youlan

2016-12-01

An evolutionary modification approach, boron-doped carbon coating, has been used to improve the electrochemical performances of positive electrodes for lithium-ion batteries, and demonstrates apparent and significant modification effects. In this study, the boron-doped carbon coating is firstly adopted and used to decorate the performance of LiFePO4. The obtained composite exhibits a unique core-shell structure with an average diameter of 140 nm and a 4 nm thick boron-doped carbon shell that uniformly encapsulates the core. Owing to the boron element which could induce high amount of defects in the carbon, the electronic conductivity of LiFePO4 is greatly ameliorated. Thus, the boron-doped composite shows superior rate capability and cycle stability than the undoped sample. For instance, the reversible specific capacity of LiFePO4@B0.4-C can reach 164.1 mAh g-1 at 0.1C, which is approximately 96.5% of the theoretical capacity (170 mAh g-1). Even at high rate of 10C, it still shows a high specific capacity of 126.8 mAh g-1 and can be maintained at 124.5 mAh g-1 after 100 cycles with capacity retention ratio of about 98.2%. This outstanding Li-storage property enable the present design strategy to open up the possibility of fabricating the LiFePO4@B-C composite for high-performance lithium-ion batteries.

In operando neutron diffraction study of the temperature and current rate-dependent phase evolution of LiFePO4 in a commercial battery

NASA Astrophysics Data System (ADS)

Sharma, N.; Yu, D. H.; Zhu, Y.; Wu, Y.; Peterson, V. K.

2017-02-01

In operando NPD data of electrodes in lithium-ion batteries reveal unusual LiFePO4 phase evolution after the application of a thermal step and at high current. At low current under ambient conditions the LiFePO4 to FePO4 two-phase reaction occurs during the charge process, however, following a thermal step and at higher current this reaction appears at the end of charge and continues into the next electrochemical step. The same behavior is observed for the FePO4 to LiFePO4 transition, occurring at the end of discharge and continuing into the following electrochemical step. This suggests that the bulk (or the majority of the) electrode transformation is dependent on the battery's history, current, or temperature. Such information concerning the non-equilibrium evolution of an electrode allows a direct link between the electrode's functional mechanism that underpins lithium-ion battery behavior and the real-life operating conditions of the battery, such as variable temperature and current, to be made.

Double Carbon Nano Coating of LiFePO4 Cathode Material for High Performance of Lithium Ion Batteries.

PubMed

Ding, Yan-Hong; Huang, Guo-Long; Li, Huan-Huan; Xie, Hai-Ming; Sun, Hai-Zhu; Zhang, Jing-Ping

2015-12-01

Double carbon-coated LiFePO4 (D-LiFePO4/C) composite with sphere-like structure was synthesized through combination of co-precipitation and solid-state methods. Cetyl-trimethyl-ammonium bromide (CTAB) and citric acid served as two kinds of carbon sources in sequence. SEM images demonstrated that double carbon coating had certain influence on the morphology. The thickness of carbon coating on D-LiFePO4/C was about 1.7 nm and the content of carbon was 2.48 wt%, according to HRTEM and TG analysis. The electrochemical impedance spectroscopy analysis indicated that the D-LiFePO4/C composite presented the charge-transfer resistance of 68 Ω and Li ion diffusion coefficient of 2.68 x 10(-13) cm2 S(-1), while the single carbon-coated LiFePO4 (S-LiFePO4/C) exhibited 135.5Ω and 4.03 x 10(-14) cm2 S(-1). Especially, the prepared D-LiFePO4/C electrode showed discharge capacities of 102.9 (10C) and 87.1 (20C) mA h g(-1), respectively, with almost no capacity lost after 400 cycles at 10C, which were much better than those of S-LiFePO4/C composite.

Core-shell LiFePO4 /carbon-coated reduced graphene oxide hybrids for high-power lithium-ion battery cathodes.

PubMed

Ha, Sung Hoon; Lee, Yun Jung

2015-01-26

Core-shell carbon-coated LiFePO4 nanoparticles were hybridized with reduced graphene (rGO) for high-power lithium-ion battery cathodes. Spontaneous aggregation of hydrophobic graphene in aqueous solutions during the formation of composite materials was precluded by employing hydrophilic graphene oxide (GO) as starting templates. The fabrication of true nanoscale carbon-coated LiFePO4 -rGO (LFP/C-rGO) hybrids were ascribed to three factors: 1) In-situ polymerization of polypyrrole for constrained nanoparticle synthesis of LiFePO4 , 2) enhanced dispersion of conducting 2D networks endowed by colloidal stability of GO, and 3) intimate contact between active materials and rGO. The importance of conducting template dispersion was demonstrated by contrasting LFP/C-rGO hybrids with LFP/C-rGO composites in which agglomerated rGO solution was used as the starting templates. The fabricated hybrid cathodes showed superior rate capability and cyclability with rates from 0.1 to 60 C. This study demonstrated the synergistic combination of nanosizing with efficient conducting templates to afford facile Li(+) ion and electron transport for high power applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A high performance hybrid battery based on aluminum anode and LiFePO4 cathode.

PubMed

Sun, Xiao-Guang; Bi, Zhonghe; Liu, Hansan; Fang, Youxing; Bridges, Craig A; Paranthaman, M Parans; Dai, Sheng; Brown, Gilbert M

2016-01-28

A novel hybrid battery utilizing an aluminum anode, a LiFePO4 cathode and an acidic ionic liquid electrolyte based on 1-ethyl-3-methylimidazolium chloride (EMImCl) and aluminum trichloride (AlCl3) (EMImCl-AlCl3, 1-1.1 in molar ratio) with or without LiAlCl4 is proposed. The hybrid ion battery delivers an initial high capacity of 160 mA h g(-1) at a current rate of C/5. It also shows good rate capability and cycling performance.

A high performance hybrid battery based on aluminum anode and LiFePO 4 cathode

DOE PAGES

Sun, Xiao-Guang; Bi, Zhonghe; Liu, Hansan; ...

2015-12-07

A unique battery hybrid utilizes an aluminum anode, a LiFePO 4 cathode and an acidic ionic liquid electrolyte based on 1-ethyl-3-methylimidazolium chloride (EMImCl) and aluminum trichloride (AlCl 3) (EMImCl-AlCl 3, 1-1.1 in molar ratio) with or without LiAlCl 4 is proposed. This hybrid ion battery delivers an initial high capacity of 160 mAh g -1 at a current rate of C/5. It also shows good rate capability and cycling performance.

Redirected charge transport arising from diazonium grafting of carbon coated LiFePO4.

PubMed

Madec, L; Seid, K A; Badot, J-C; Humbert, B; Moreau, P; Dubrunfaut, O; Lestriez, B; Guyomard, D; Gaubicher, J

2014-11-07

The morphological and the electrical properties of carbon coated LiFePO4 (LFPC) active material functionalized by 4-ethynylbenzene tetrafluoroboratediazonium salt were investigated. For this purpose, FTIR, Raman, XPS, High Resolution Transmission Electron Microscopy (HRTEM) and Broadband Dielectric Spectroscopy (BDS) were considered. Electronic conductivities of LFPC samples at room temperature were found to decrease in a large frequency range upon simple immersion in polar solvents and to decrease further upon functionalization. Due to their high dipole moment, strongly physisorbed molecules detected by XPS likely add barriers to electron hopping. Significant alteration of the carbon coating conductivity was only observed, however, upon functionalization. This effect is most presumably associated with an increase in the sp(3) content determined by Raman spectroscopy, which is a strong indication of the formation of a covalent bond between the organic layer and the carbon coating. In this case, the electron flux appears to be redirected and relayed by short-range (intra chain) and long-range (inter chain) electron transport through molecular oligomers anchored at the LFPC surface. The latter are controlled by tunnelling and slightly activated hopping, which enable higher conductivity at low temperature (T < 250 K). Alteration of the electron transport within the carbon coating also allows detection of a relaxation phenomenon that corresponds to small polaron hopping in bulk LiFePO4. XPS and HRTEM images allow a clear correlation of these findings with the island type oligomeric structure of grafted molecules.

Magnetic susceptibility as a direct measure of oxidation state in LiFePO4 batteries and cyclic water gas shift reactors.

PubMed

Kadyk, Thomas; Eikerling, Michael

2015-08-14

The possibility of correlating the magnetic susceptibility to the oxidation state of the porous active mass in a chemical or electrochemical reactor was analyzed. The magnetic permeability was calculated using a hierarchical model of the reactor. This model was applied to two practical examples: LiFePO4 batteries, in which the oxidation state corresponds with the state-of-charge, and cyclic water gas shift reactors, in which the oxidation state corresponds to the depletion of the catalyst. In LiFePO4 batteries phase separation of the lithiated and delithiated phases in the LiFePO4 particles in the positive electrode gives rise to a hysteresis effect, i.e. the magnetic permeability depends on the history of the electrode. During fast charge or discharge, non-uniform lithium distributionin the electrode decreases the hysteresis effect. However, the overall sensitivity of the magnetic response to the state-of-charge lies in the range of 0.03%, which makes practical measurement challenging. In cyclic water gas shift reactors, the sensitivity is 4 orders of magnitude higher and without phase separation, no hysteresis occurs. This shows that the method is suitable for such reactors, in which large changes of the magnetic permeability of the active material occurs.

Calcio-olivine γ-Ca2SiO4: I. Rietveld refinement of the crystal structure

NASA Astrophysics Data System (ADS)

Gobechiya, E. R.; Yamnova, N. A.; Zadov, A. E.; Gazeev, V. M.

2008-05-01

The structure of the natural mineral calcio-olivine (γ-Ca2SiO4) found in skarn xenoliths in the region of the Lakargi Mountain (North Caucasus, Kabardino-Balkaria, Russia) is refined by the Rietveld method [ a = 5.07389(7) Å, b = 11.21128(14) Å, c = 6.75340(9) Å, V = 384.170(5) Å3, Z = 4, ρcalcd = 2.98 g/cm3, space group Pbnm]. The X-ray diffraction pattern of a powdered sample is recorded on a STOE STADI MP diffractometer [λCu K α1; Ge(111) primary monochromator; 6.00° < 2θ < 100.88°; step width, 2.5° in 2θ; number of reflections, 224]. All calculations are performed with the WYRIET (version 3.3) software package. The structural model is refined in the anisotropic approximation to R p = 6.44, R wp = 8.52, R exp = 5.85, R B = 4.98, R F = 6.90, and s = 1.46. It is shown that the sample under investigation is a mixture of several mineral phases, among which calcio-olivine (the natural analogue of the γ-Ca2SiO4 compound) (83%), hillebrandite (13%), and wadalite (4%) are dominant. Only the scale factors and the unit cell parameters are refined for hillebrandite Ca2SiO3(OH)2 [ a = 3.63472(16) Å, b = 16.4140(10) Å, c = 11.7914(8) Å, space group Cmc21, Z = 6] and wadalite Ca6Al5Si2O16Cl3 ( a = 12.0088 Å, space group, I bar 4 3 d Z = 4). The results of the structure refinement of the main component of the sample confirm that the mineral calcio-olivine is isostructural to the synthetic compound γ-Ca2SiO4. The structure of this compound is formed by the heteropolyhedral framework composed of Ca octahedra joined together into olivine-like ribbons and isolated Si tetrahedra.

Fe K-Edge X-ray absorption near-edge spectroscopy (XANES) and X-ray diffraction (XRD) analyses of LiFePO4 and its base materials

NASA Astrophysics Data System (ADS)

Latif, C.; Negara, V. S. I.; Wongtepa, W.; Thamatkeng, P.; Zainuri, M.; Pratapa, S.

2018-03-01

XANES analysis has been performed with the aim of knowing the Fe oxidation state in a synthesized LiFePO4 and its base materials. XANES measurements were performed at SLRI on energy around Fe K-edge. An XRD analysis has also been performed with the aim of knowing the phase composition, lattice parameters and crystallite size of the LiFePO4 as well as the base materials. From the XRD analysis, it was found that the dominating phase in the iron sand sample was Fe3O4 and the only phase found after calcination was LiFePO4. The latter phase exhibited crystallite size of 100 nm and lattice parameters a = 10.169916 Å, b = 5.919674 Å, c = 4.627893 Å. Qualitative analysis of XANES data revealed that the oxidation number of Fe in the sample before calcination was greater than that after calcination and Fe in the natural iron sand, indicated by the E0 values of 7129.2 eV, 7120.6 eV and 7124.4 eV respectively.

Etched Colloidal LiFePO4 Nanoplatelets toward High-Rate Capable Li-Ion Battery Electrodes

PubMed Central

2014-01-01

LiFePO4 has been intensively investigated as a cathode material in Li-ion batteries, as it can in principle enable the development of high power electrodes. LiFePO4, on the other hand, is inherently “plagued” by poor electronic and ionic conductivity. While the problems with low electron conductivity are partially solved by carbon coating and further by doping or by downsizing the active particles to nanoscale dimensions, poor ionic conductivity is still an issue. To develop colloidally synthesized LiFePO4 nanocrystals (NCs) optimized for high rate applications, we propose here a surface treatment of the NCs. The particles as delivered from the synthesis have a surface passivated with long chain organic surfactants, and therefore can be dispersed only in aprotic solvents such as chloroform or toluene. Glucose that is commonly used as carbon source for carbon-coating procedure is not soluble in these solvents, but it can be dissolved in water. In order to make the NCs hydrophilic, we treated them with lithium hexafluorophosphate (LiPF6), which removes the surfactant ligand shell while preserving the structural and morphological properties of the NCs. Only a roughening of the edges of NCs was observed due to a partial etching of their surface. Electrodes prepared from these platelet NCs (after carbon coating) delivered a capacity of ∼155 mAh/g, ∼135 mAh/g, and ∼125 mAh/g, at 1 C, 5 C, and 10 C, respectively, with significant capacity retention and remarkable rate capability. For example, at 61 C (10.3 A/g), a capacity of ∼70 mAh/g was obtained, and at 122 C (20.7 A/g), the capacity was ∼30 mAh/g. The rate capability and the ease of scalability in the preparation of these surface-treated nanoplatelets make them highly suitable as electrodes in Li-ion batteries. PMID:25372361

Etched colloidal LiFePO4 nanoplatelets toward high-rate capable Li-ion battery electrodes.

PubMed

Paolella, Andrea; Bertoni, Giovanni; Marras, Sergio; Dilena, Enrico; Colombo, Massimo; Prato, Mirko; Riedinger, Andreas; Povia, Mauro; Ansaldo, Alberto; Zaghib, Karim; Manna, Liberato; George, Chandramohan

2014-12-10

LiFePO4 has been intensively investigated as a cathode material in Li-ion batteries, as it can in principle enable the development of high power electrodes. LiFePO4, on the other hand, is inherently "plagued" by poor electronic and ionic conductivity. While the problems with low electron conductivity are partially solved by carbon coating and further by doping or by downsizing the active particles to nanoscale dimensions, poor ionic conductivity is still an issue. To develop colloidally synthesized LiFePO4 nanocrystals (NCs) optimized for high rate applications, we propose here a surface treatment of the NCs. The particles as delivered from the synthesis have a surface passivated with long chain organic surfactants, and therefore can be dispersed only in aprotic solvents such as chloroform or toluene. Glucose that is commonly used as carbon source for carbon-coating procedure is not soluble in these solvents, but it can be dissolved in water. In order to make the NCs hydrophilic, we treated them with lithium hexafluorophosphate (LiPF6), which removes the surfactant ligand shell while preserving the structural and morphological properties of the NCs. Only a roughening of the edges of NCs was observed due to a partial etching of their surface. Electrodes prepared from these platelet NCs (after carbon coating) delivered a capacity of ∼ 155 mAh/g, ∼ 135 mAh/g, and ∼ 125 mAh/g, at 1 C, 5 C, and 10 C, respectively, with significant capacity retention and remarkable rate capability. For example, at 61 C (10.3 A/g), a capacity of ∼ 70 mAh/g was obtained, and at 122 C (20.7 A/g), the capacity was ∼ 30 mAh/g. The rate capability and the ease of scalability in the preparation of these surface-treated nanoplatelets make them highly suitable as electrodes in Li-ion batteries.

Electrochemical and kinetic studies of ultrafast laser structured LiFePO4 electrodes

NASA Astrophysics Data System (ADS)

Mangang, M.; Gotcu-Freis, P.; Seifert, H. J.; Pfleging, W.

2015-03-01

Due to a growing demand of cost-efficient lithium-ion batteries with an increased energy and power density as well as an increased life-time, the focus is set on intercalation cathode materials like LiFePO4. It has a high practical capacity, is environmentally friendly and has low material costs. However, its low electrical conductivity and low ionic diffusivity are major drawbacks for its use in electrochemical storage devices or electric vehicles. By adding conductive agents, the electrical conductivity can be enhanced. By increasing the surface of the cathode material which is in direct contact with the liquid electrolyte the lithium-ion diffusion kinetics can be improved. A new approach to increase the surface of the active material without changing the active particle packing density or the weight proportion of carbon black is the laser-assisted generation of 3D surface structures in electrode materials. In this work, ultrafast laser radiation was used to create a defined surface structure in LiFePO4 electrodes. It was shown that by using ultrashort laser pulses instead of nanosecond laser pulses, the ablation efficiency could be significantly increased. Furthermore, melting and debris formation were reduced. To investigate the diffusion kinetics, electrochemical methods such as cyclic voltammetry and galvanostatic intermittent titration technique were applied. It could be shown that due to a laser generated 3D structure, the lithium-ion diffusion kinetic, the capacity retention and cell life-time can be significantly improved.

Important Variation in Vibrational Properties of LiFePO4 and FePO4 Induced by Magnetism

PubMed Central

Seifitokaldani, Ali; Gheribi, Aïmen E.; Phan, Anh Thu; Chartrand, Patrice; Dollé, Mickaël

2016-01-01

A new thermodynamically self-consistent (TSC) method, based on the quasi-harmonic approximation (QHA), is used to obtain the Debye temperatures of LiFePO4 (LFP) and FePO4 (FP) from available experimental specific heat capacities for a wide temperature range. The calculated Debye temperatures show an interesting critical and peculiar behavior so that a steep increase in the Debye temperatures is observed by increasing the temperature. This critical behavior is fitted by the critical function and the adjusted critical temperatures are very close to the magnetic phase transition temperatures in LFP and FP. Hence, the critical behavior of the Debye temperatures is correlated with the magnetic phase transitions in these compounds. Our first-principle calculations support our conjecture that the change in electronic structures, i.e. electron density of state and electron localization function, and consequently the change in thermophysical properties due to the magnetic transition may be the reason for the observation of this peculiar behavior of the Debye temperatures. PMID:27604551

Important Variation in Vibrational Properties of LiFePO4 and FePO4 Induced by Magnetism

NASA Astrophysics Data System (ADS)

Seifitokaldani, Ali; Gheribi, Aïmen E.; Phan, Anh Thu; Chartrand, Patrice; Dollé, Mickaël

2016-09-01

A new thermodynamically self-consistent (TSC) method, based on the quasi-harmonic approximation (QHA), is used to obtain the Debye temperatures of LiFePO4 (LFP) and FePO4 (FP) from available experimental specific heat capacities for a wide temperature range. The calculated Debye temperatures show an interesting critical and peculiar behavior so that a steep increase in the Debye temperatures is observed by increasing the temperature. This critical behavior is fitted by the critical function and the adjusted critical temperatures are very close to the magnetic phase transition temperatures in LFP and FP. Hence, the critical behavior of the Debye temperatures is correlated with the magnetic phase transitions in these compounds. Our first-principle calculations support our conjecture that the change in electronic structures, i.e. electron density of state and electron localization function, and consequently the change in thermophysical properties due to the magnetic transition may be the reason for the observation of this peculiar behavior of the Debye temperatures.

Important Variation in Vibrational Properties of LiFePO4 and FePO4 Induced by Magnetism.

PubMed

Seifitokaldani, Ali; Gheribi, Aïmen E; Phan, Anh Thu; Chartrand, Patrice; Dollé, Mickaël

2016-09-08

A new thermodynamically self-consistent (TSC) method, based on the quasi-harmonic approximation (QHA), is used to obtain the Debye temperatures of LiFePO4 (LFP) and FePO4 (FP) from available experimental specific heat capacities for a wide temperature range. The calculated Debye temperatures show an interesting critical and peculiar behavior so that a steep increase in the Debye temperatures is observed by increasing the temperature. This critical behavior is fitted by the critical function and the adjusted critical temperatures are very close to the magnetic phase transition temperatures in LFP and FP. Hence, the critical behavior of the Debye temperatures is correlated with the magnetic phase transitions in these compounds. Our first-principle calculations support our conjecture that the change in electronic structures, i.e. electron density of state and electron localization function, and consequently the change in thermophysical properties due to the magnetic transition may be the reason for the observation of this peculiar behavior of the Debye temperatures.

Study on LOC for modern facility agriculture automatic walking equipment LiFePO4 battery

NASA Astrophysics Data System (ADS)

Liu, Xuepeng; Zhao, Dongmei

2017-08-01

LiFePO4 battery LOC (life Of Charge) is the assessment of the ability to work within a cycle of battery charge and discharge period, which likes the miles for vehicle. LOC is related with battery capacity, working condition and stress. LOC consists of the model of the battery's SOC online prediction model, the analysis of RBSOC and the LOC model of multi-condition and multi-stress.

Increasing the Affinity Between Carbon-Coated LiFePO4/C Electrodes and Conventional Organic Electrolyte by Spontaneous Grafting of a Benzene-Trifluoromethylsulfonimide Moiety.

PubMed

Delaporte, Nicolas; Perea, Alexis; Lebègue, Estelle; Ladouceur, Sébastien; Zaghib, Karim; Bélanger, Daniel

2015-08-26

The grafting of benzene-trifluoromethylsulfonimide groups on LiFePO4/C was achieved by spontaneous reduction of in situ generated diazonium ions of the corresponding 4-amino-benzene-trifluoromethylsulfonimide. The diazotization of 4-amino-benzene-trifluoromethylsulfonimide was a slow process that required a high concentration of precursors to promote the spontaneous grafting reaction. Contact angle measurements showed a hydrophilic surface was produced after the reaction that is consistent with grafting of benzene-trifluoromethylsulfonimide groups. Elemental analysis data revealed a 2.1 wt % loading of grafted molecules on the LiFePO4/C powder. Chemical oxidation of the cathode material during the grafting reaction was detected by X-ray diffraction and quantified by inductively coupled plasma atomic emission spectrometry. Surface modification improves the wettability of the cathode material, and better discharge capacities were obtained for modified electrodes at high C-rate. In addition, electrochemical impedance spectroscopy showed the resistance of the modified cathode was lower than that of the bare LiFePO4/C film electrode. Moreover, the modified cathode displayed superior capacity retention after 200 cycles of charge/discharge at 1 C.

High Rate Performing Li-ion Battery

DTIC Science & Technology

2015-02-09

this storage capacity is known so far the highest among all phosphate-based cathode materials. Unlike olivine LiFePO4 with inherent low lithium ion...1 ). 24 However, similar to LiFePO4 , the main drawback of LVP is its intrinsic poor electronic conductivity (10 −8 Scm −1 ) 25 which can hinder...Fisher, C. A. J. & Slater, P. R. Atomic-scale Investigation of Defects, Dopants, and Lithium Transport in the LiFePO4 Olivine-type Battery

Enhanced electrochemical performance of LiMn2O4 by constructing a stable Mn2+-rich interface

NASA Astrophysics Data System (ADS)

Lu, Zhongpei; Lu, Xiaojun; Ding, Jingjing; Zhou, Ting; Ge, Tao; Yang, Gang; Yin, Fan; Wu, Mingfang

2017-12-01

Spinel LiMn2O4 has drawn continuous attentions due to its low cost, good electrochemical performance, environmental friendliness and natural abundant resources. In view of its severe capacity fading, some types of manganese-based compounds with different Mn oxidation states are selected to protect bare LiMn2O4 by constructing a stable coating layer. In this work, LiMn2O4@LiMnPO4 composite, spherical LiMn2O4 (LMO) as core and Mn2+-rich phase of LiMnPO4 (LMP) as shell, is designed and synthesized. Two composites of LiMn2O4 particles coated with 3 wt% and 10 wt% LiMnPO4 have been compared studied. After 100 cycles at 0.5C rate, the two samples deliver capacity retentions of 96.63% and 93.23% of their initial capacities. Moreover, LMO coated by 3 wt% LiMnPO4 delivers 100.3 mAh g-1 after 200 cycles at 10C rate and 76.3 mAh g-1 after 1000 cycles at 20C rate, much higher than bare LiMn2O4 with 90 mAh g-1 and 45.8 mAh g-1, respectively. This core-shell structure with Mn2+-rich phase as a coating layer effectively enhance the material's cycling performance and rate capacity by reducing the contact of LiMn2O4 with electrolyte.

Heat capacity and entropy of Ni2SiO4-olivine from 5 to 1000 K and heat capacity of Co2SiO4 from 360 to 1000 K.

USGS Publications Warehouse

Robie, R.A.; Hemingway, B.S.; Ito, J.; Krupka, K.M.

1984-01-01

The heat capacity of Ni2SiO4-olivine has been measured between 5 and 387 K by cryogenic adiabatic-shield calorimetry and between 360 and 1000 K by differential scanning calorimetry. The heat capacity of Co2SiO4-olivine was measured between 360 and 1000 K by differential scanning calorimetry.-J.A.Z.

Excess lithium storage in LiFePO4-Carbon interface by ball-milling

NASA Astrophysics Data System (ADS)

Guo, Hua; Song, Xiaohe; Zheng, Jiaxin; Pan, Feng

2016-07-01

As one of the most popular cathode materials for high power lithium ion batteries (LIBs) of the electrical-vehicle (EV), lithium iron phosphate (LiFePO4 (LFP)) is limited to its relatively lower theoretical specific capacity of 170mAh g-1. To break the limits and further improve the capacity of LFP is promising but challenging. In this study, the ball-milling method is applied to the mixture of LFP and carbon, and the effective capacity larger than the theoretical one by 30mAh g-1 is achieved. It is demonstrated that ball-milling leads to the LFP-Carbon interface to store the excess Li-ions.

Synthesis of LiFePO4/C composites based on natural iron stone using a sol gel method

NASA Astrophysics Data System (ADS)

Angela, Riyan; Islam, Humaatul; Sari, Vamellia; Latif, Chaironi; Zainuri, Mochamad; Pratapa, Suminar

2017-01-01

Synthesis of LiFePO4/C composites has been carried out using a sol gel method. The Fe precursor was made from a natural iron stone of Tanah Laut, South Kalimantan, while the other raw materials were commercial Li2CO3 powder and NH4H2PO4 powder with HCl and water as solvents. Citric acid was used as the carbon source in the synthesis. This study used a molar ratio of 1:1:2 for Li:Fe:P with variation of added citric acid of 1.5 and 2.5 g. The solutions were dried in air at 100°C. The dried powders were characterized using DSC-TGA and then calcined at 600 and 700°C under argon environment for 10 hours. The calcined powders were characterized by X-ray diffractometry (XRD), scanning electron microscopy-energy dispersive x-ray (SEM-EDX), and LCR meter. It was found that the samples contained LiFePO4 as the dominant phase and LiFeP2O7 and Fe2O3 as secondary phases. The analysis showed that the addition of citric acid influenced the electronic conductivity of the composites. A Rietveld relative weight fraction of up to 94.7% was achieved in the synthesis at temperature 600°C. The LFP/C sample exhibited electronic conductivity of 4.56×10-3 Scm-1 which was six times of that of the pure LFP.

Unleashing the Power and Energy of LiFePO4-Based Redox Flow Lithium Battery with a Bifunctional Redox Mediator.

PubMed

Zhu, Yun Guang; Du, Yonghua; Jia, Chuankun; Zhou, Mingyue; Fan, Li; Wang, Xingzhu; Wang, Qing

2017-05-10

Redox flow batteries, despite great operation flexibility and scalability for large-scale energy storage, suffer from low energy density and relatively high cost as compared to the state-of-the-art Li-ion batteries. Here we report a redox flow lithium battery, which operates via the redox targeting reactions of LiFePO 4 with a bifunctional redox mediator, 2,3,5,6-tetramethyl-p-phenylenediamine, and presents superb energy density as the Li-ion battery and system flexibility as the redox flow battery. The battery has achieved a tank energy density as high as 1023 Wh/L, power density of 61 mW/cm 2 , and voltage efficiency of 91%. Operando X-ray absorption near-edge structure measurements were conducted to monitor the evolution of LiFePO 4 , which provides insightful information on the redox targeting process, critical to the device operation and optimization.

Utilizing recycled LiFePO4 from batteries in combination with B@C3N4 and CuFe2O4 as sustainable nano-junctions for high performance degradation of atenolol.

PubMed

Kumar, Amit; Kumari, Anu; Sharma, Gaurav; Naushad, Mu; Ahamad, Tansir; Stadler, Florian J

2018-06-18

In this report recycled LiFePO 4 (LFP) from exhaust batteries was utilized to form B@C 3 N 4 /LiFePO 4 /CuFe 2 O 4 (BLC) nano-junction as a visible active photocatalyst. The junction synthesized by two routes: Using as extracted LFP and forming LFP by extracted FePO 4 and Li 2 CO 3 via in-situ deposition method. The two ternary junctions BLC and BLC (E) (utilizing as extracted LFP) were utilized for visible and solar powered degradation of beta-blocker drug Atenolol (ATL). Varying the loading of CuFe 2 O 4 (CF) which possesses lowest band gap, BLC (10%), BLC-3 (30%), BLC-5 (50%) and BLC-E (30% CF and as extracted LFP) were produced with BLC-3 exhibiting remarkable activity. The optical band gaps of BLC-3 (2.40 eV) and BLC (E) (2.46 eV) and photocurrent responses reveal high visible absorption and highly diminished recombination. 99.5% and 85.3% of ATL (20 mg L -1 ) could be degraded by BLC-3 and BLC (E) (0.3 g L -1 ) respectively in 60 min of exposure to Xe lamp and retaining of high activity in natural sunlight. Band-junction analysis, effect of scavengers and effect on teraphthalic acid and nitroblue tetrazolium reveal O 2 - and OH radicals as active species and mineralization was confirmed by liquid chromatography-mass spectrometer (LC-MS). Cyto-toxicity studies on human peripheral blood cells and effect on growth of Pseudomonas aeruginosa confirm the complete mineralization. The BLC photocatalyst is a promising multi-functional catalyst utilizing LFP (rarely used as photocatalyst) for treatment of pharmaceutical waste water and other environmental applications. Copyright © 2018 Elsevier Ltd. All rights reserved.

Emergence of Metallic Properties at LiFePO4 Surfaces and LiFePO4/Li2S Interfaces: An Ab Initio Study.

PubMed

Timoshevskii, Vladimir; Feng, Zimin; Bevan, Kirk H; Zaghib, Karim

2015-08-26

The atomic and electronic structures of the LiFePO4 (LFP) surface, both bare and reconstructed upon possible oxygenation, are theoretically studied by ab initio methods. On the basis of total energy calculations, the atomic structure of the oxygenated surface is proposed, and the effect of surface reconstruction on the electronic properties of the surface is clarified. While bare LFP(010) surface is insulating, adsorption of oxygen leads to the emergence of semimetallic behavior by inducing the conducting states in the band gap of the system. The physical origin of these conducting states is investigated. We further demonstrate that deposition of Li2S layers on top of oxygenated LFP(010) surface leads to the formation of additional conducting hole states in the first layer of Li2S surface because of the charge transfer from sulfur p-states to the gap states of LFP surface. This demonstrates that oxygenated LFP surface not only provides conducting layers itself, but also induces conducting channels in the top layer of Li2S. These results help to achieve further understanding of potential role of LFP particles in improving the performance of Li-S batteries through emergent interface conductivity.

Calcio-olivine {gamma}-Ca{sub 2}SiO{sub 4}: I. Rietveld refinement of the crystal structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gobechiya, E. R., E-mail: elgob@mail.ru; Yamnova, N. A.; Zadov, A. E.

2008-05-15

The structure of the natural mineral calcio-olivine ({gamma}-Ca{sub 2}SiO{sub 4}) found in skarn xenoliths in the region of the Lakargi Mountain (North Caucasus, Kabardino-Balkaria, Russia) is refined by the Rietveld method [a = 5.07389(7) A, b = 11.21128(14) A, c = 6.75340(9) A, V = 384.170(5) A{sup 3}, Z = 4, {rho}{sub calcd} = 2.98 g/cm{sup 3}, space group Pbnm]. The X-ray diffraction pattern of a powdered sample is recorded on a STOE STADI MP diffractometer [{lambda}CuK{sub {alpha}1}; Ge(111) primary monochromator; 6.00{sup o} < 2{theta} < 100.88{sup o}; step width, 2.5{sup o} in 2{theta}; number of reflections, 224]. All calculationsmore » are performed with the WYRIET (version 3.3) software package. The structural model is refined in the anisotropic approximation to R{sub p} = 6.44, R{sub wp} = 8.52, R{sub exp} = 5.85, R{sub B} = 4.98, R{sub F} = 6.90, and s = 1.46. It is shown that the sample under investigation is a mixture of several mineral phases, among which calcio-olivine (the natural analogue of the {gamma}-Ca{sub 2}SiO{sub 4} compound) (83%), hillebrandite (13%), and wadalite (4%) are dominant. Only the scale factors and the unit cell parameters are refined for hillebrandite Ca{sub 2}SiO{sub 3}(OH){sub 2} [a = 3.63472(16) A, b = 16.4140(10) A, c = 11.7914(8) A, space group Cmc2{sub 1}, Z = 6] and wadalite Ca{sub 6}Al{sub 5}Si{sub 2}O{sub 16}Cl{sub 3} (a = 12.0088 A, space group, I 4 bar 3d, Z = 4). The results of the structure refinement of the main component of the sample confirm that the mineral calcio-olivine is isostructural to the synthetic compound {gamma}-Ca{sub 2}SiO{sub 4}. The structure of this compound is formed by the heteropolyhedral framework composed of Ca octahedra joined together into olivine-like ribbons and isolated Si tetrahedra.« less

Electrochemical performance of La2O3/Li2O/TiO2 nano-particle coated cathode material LiFePO4.

PubMed

Wang, Hong; Yang, Chi; Liu, Shu-Xin

2014-09-01

Cathode material, LiFePO4 was modified by coating with a thin layer of La2O3/Li2O/TiO2 nano-particles for improving its performance for lithium ion batteries. The morphology and structure of the modified cathode material were characterized by powder X-ray diffraction, scanning electron microcopy and AES. The performance of the battery with the modified cathode material, including cycling stability, C-rate discharge was examined. The results show that the battery composed of the coated cathode materials can discharge at a large current density and show stable cycling performance in the range from 2.5 to 4.0 V. The rate of Li ion diffusion increases in the battery with the La2O3/Li2O/TiO2-coated LiFePO4 as a cathode and the coating layer may acts as a faster ion conductor (La(2/3-x)Li(3x)TiO3).

Sequential Monte Carlo filter for state estimation of LiFePO4 batteries based on an online updated model

NASA Astrophysics Data System (ADS)

Li, Jiahao; Klee Barillas, Joaquin; Guenther, Clemens; Danzer, Michael A.

2014-02-01

Battery state monitoring is one of the key techniques in battery management systems e.g. in electric vehicles. An accurate estimation can help to improve the system performance and to prolong the battery remaining useful life. Main challenges for the state estimation for LiFePO4 batteries are the flat characteristic of open-circuit-voltage over battery state of charge (SOC) and the existence of hysteresis phenomena. Classical estimation approaches like Kalman filtering show limitations to handle nonlinear and non-Gaussian error distribution problems. In addition, uncertainties in the battery model parameters must be taken into account to describe the battery degradation. In this paper, a novel model-based method combining a Sequential Monte Carlo filter with adaptive control to determine the cell SOC and its electric impedance is presented. The applicability of this dual estimator is verified using measurement data acquired from a commercial LiFePO4 cell. Due to a better handling of the hysteresis problem, results show the benefits of the proposed method against the estimation with an Extended Kalman filter.

Lithium potential variations for metastable materials: case study of nanocrystalline and amorphous LiFePO4.

PubMed

Zhu, Changbao; Mu, Xiaoke; Popovic, Jelena; Weichert, Katja; van Aken, Peter A; Yu, Yan; Maier, Joachim

2014-09-10

Much attention has been paid to metastable materials in the lithium battery field, especially to nanocrystalline and amorphous materials. Nonetheless, fundamental issues such as lithium potential variations have not been pertinently addressed. Using LiFePO4 as a model system, we inspect such lithium potential variations for various lithium storage modes and evaluate them thermodynamically. The conclusions of this work are essential for an adequate understanding of the behavior of electrode materials and even helpful in the search for new energy materials.

Solvothermal Synthesis of a Hollow Micro-Sphere LiFePO4/C Composite with a Porous Interior Structure as a Cathode Material for Lithium Ion Batteries

PubMed Central

Liu, Yang; Zhang, Jieyu; Li, Ying; Hu, Yemin; Li, Wenxian; Zhu, Mingyuan; Hu, Pengfei; Chou, Shulei; Wang, Guoxiu

2017-01-01

To overcome the low lithium ion diffusion and slow electron transfer, a hollow micro sphere LiFePO4/C cathode material with a porous interior structure was synthesized via a solvothermal method by using ethylene glycol (EG) as the solvent medium and cetyltrimethylammonium bromide (CTAB) as the surfactant. In this strategy, the EG solvent inhibits the growth of the crystals and the CTAB surfactant boots the self-assembly of the primary nanoparticles to form hollow spheres. The resultant carbon-coat LiFePO4/C hollow micro-spheres have a ~300 nm thick shell/wall consisting of aggregated nanoparticles and a porous interior. When used as materials for lithium-ion batteries, the hollow micro spherical LiFePO4/C composite exhibits superior discharge capacity (163 mAh g−1 at 0.1 C), good high-rate discharge capacity (118 mAh g−1 at 10 C), and fine cycling stability (99.2% after 200 cycles at 0.1 C). The good electrochemical performances are attributed to a high rate of ionic/electronic conduction and the high structural stability arising from the nanosized primary particles and the micro-sized hollow spherical structure. PMID:29099814

Synthesis, characterization and vibrational spectroscopic study of Co, Mg co-doped LiMnPO4

NASA Astrophysics Data System (ADS)

Sronsri, Chuchai; Noisong, Pittayagorn; Danvirutai, Chanaiporn

2016-01-01

The isostructural olivine-like LiM(II)PO4 compounds [M(II) = Mn, Mn0.9Co0.1, Mn0.8Co0.1Mg0.1] were successfully generated through the solid state reaction from the synthesized NH4M(II)PO4• H2O precursors. The TG/DTG/DTA, AAS/AES, FTIR and XRD methods were employed to confirm both NH4M(II)PO4• H2O and LiM(II)PO4 compounds. Their morphologies were studied by SEM method. The shift of two theta angle of XRD to higher values was observed in metal doping compounds, which indicate the formation of the single phase of isodivalent doping of Co2 + and Mg2 + ions according to the change in the lattice parameters and cell volumes. Their infrared spectra are reported and discussed with respect to the normal vibrations of NH4+, PO43 -, P2O74 - and H2O molecules using factor group analysis. The correlation field splitting analysis of PO43 - in NH4M(II)PO4• H2O (orthorhombic system, Pmn21, C2v7 and Z = 2, [(3 × 5) - 6] × 2 = 18 internal modes) symbolized as Td - Cs - C2v7 suggested the number of vibrational modes to be: ΓVib = A1(6) + A2(3) + B1(6) + B2(3) and A1(6) + A2(3) + B1(3) + B2(6) for zx and yz plane respectively. While, LiM(II)PO4 crystallizes in the orthorhombic system the space group Pnma (D2h16), Z = 4 and the site symmetry of PO43 - is Cs. The correlation field splitting of type Td - Cs - D2h16 were reported in relation to [(3 × 5) - 6] × 4 = 36 internal modes for PO43 - unit in the structure.

Reversible chemical delithiation/lithiation of LiFePO4: towards a redox flow lithium-ion battery.

PubMed

Huang, Qizhao; Li, Hong; Grätzel, Michael; Wang, Qing

2013-02-14

Reversible chemical delithiation/lithiation of LiFePO(4) was successfully demonstrated using ferrocene derivatives, based on which a novel energy storage system--the redox flow lithium-ion battery (RFLB), was devised by integrating the operation flexibility of a redox flow battery and high energy density of a lithium-ion battery. Distinct from the recent semi-solid lithium rechargeable flow battery, the energy storage materials of RFLB stored in separate energy tanks remain stationary upon operation, giving us a fresh perspective on building large-scale energy storage systems with higher energy density and improved safety.

Spectroscopic and Electrochemical Properties of Lithium-Rich LiFePO4 Cathode Synthesized by Solid-State Reaction

NASA Astrophysics Data System (ADS)

Rosaiah, P.; Hussain, O. M.; Zhu, Jinghui; Qiu, Yejun

2017-08-01

Lithium iron phosphate (Li x FePO4) is synthesized by a solid-state reaction method. The structural, electrical and electrochemical properties are studied in detail. It is found that the increment of lithium concentration (up to x = 1.05) does not affect the structure of LiFePO4 but improves its electrical conductivity as well as electrochemical performance. Surface morphological studies exhibited the formation of rod-like nanoparticles with small size. Electric and dielectric properties are also investigated over a frequency range of 1 Hz-1 MHz at different temperatures. The conductivity increased with increasing temperature, which follows the Arrhenius relation with the activation energy of about 0.31 eV. And the electrochemical tests found that the Li1.05FePO4 cathode possessed improved discharge capacity with better cycling performance.

Coating effect of LiFePO4 and Al2O3 on Li1.2Mn0.54Ni0.13Co0.13O2 cathode surface for lithium ion batteries

NASA Astrophysics Data System (ADS)

Seteni, Bonani; Rapulenyane, Nomasonto; Ngila, Jane Catherine; Mpelane, Siyasanga; Luo, Hongze

2017-06-01

Lithium-manganese-rich cathode material Li1.2Mn0.54Ni0.13Co0.13O2 is prepared by combustion method, and then coated with nano-sized LiFePO4 and nano-sized Al2O3 particles via a wet chemical process. The as-prepared Li1.2Mn0.54Ni0.13Co0.13O2, LiFePO4-coated Li1.2Mn0.54Ni0.13Co0.13O2 and Al2O3-coated Li1.2Mn0.54Ni0.13Co0.13O2 are characterized by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The scanning electron microscopy shows the agglomeration of the materials and their nanoparticle size ∼100 nm. The transmission electron microscopy confirms that LiFePO4 forms a rough mat-like surface and Al2O3 remain as islandic particles on the surface of the Li1.2Mn0.54Ni0.13Co0.13O2 material. The Li1.2Mn0.54Ni0.13Co0.13O2 coated with LiFePO4 and Li1.2Mn0.54Ni0.13Co0.13O2 coated with Al2O3 exhibits improved electrochemical performance. The initial discharge capacity is enhanced to 267 mAhg-1 after the LiFePO4 coating and 285 mAhg-1 after the Al2O3 coating compared to the as-prepared Li1.2Mn0.54Ni0.13Co0.13O2 material that has an initial discharge capacity of 243 mAhg-1. Galvanostatic charge-discharge tests at C/10 display longer activation of Li2MnO3 phase and higher capacity retention of 88% after 20 cycles for Li1.2Mn0.54Ni0.13Co0.13O2-LiFePO4 compared to Li1.2Mn0.54Ni0.13Co0.13O2-Al2O3 of 80% after 20 cycles and LMNC of 80% after 20 cycles. Meanwhile Li1.2Mn0.54Ni0.13Co0.13O2-LiFePO4 also shows higher rate capability compared to Li1.2Mn0.54Ni0.13Co0.13O2-Al2O3.

Length-Scale-Dependent Phase Transformation of LiFePO4 : An In situ and Operando Study Using Micro-Raman Spectroscopy and XRD.

PubMed

Siddique, N A; Salehi, Amir; Wei, Zi; Liu, Dong; Sajjad, Syed D; Liu, Fuqiang

2015-08-03

The charge and discharge of lithium ion batteries are often accompanied by electrochemically driven phase-transformation processes. In this work, two in situ and operando methods, that is, micro-Raman spectroscopy and X-ray diffraction (XRD), have been combined to study the phase-transformation process in LiFePO4 at two distinct length scales, namely, particle-level scale (∼1 μm) and macroscopic scale (∼several cm). In situ Raman studies revealed a discrete mode of phase transformation at the particle level. Besides, the preferred electrochemical transport network, particularly the carbon content, was found to govern the sequence of phase transformation among particles. In contrast, at the macroscopic level, studies conducted at four different discharge rates showed a continuous but delayed phase transformation. These findings uncovered the intricate phase transformation in LiFePO4 and potentially offer valuable insights into optimizing the length-scale-dependent properties of battery materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanosized LiFePO4-decorated emulsion-templated carbon foam for 3D micro batteries: a study of structure and electrochemical performance

NASA Astrophysics Data System (ADS)

Asfaw, Habtom D.; Roberts, Matthew R.; Tai, Cheuk-Wai; Younesi, Reza; Valvo, Mario; Nyholm, Leif; Edström, Kristina

2014-07-01

In this article, we report a novel 3D composite cathode fabricated from LiFePO4 nanoparticles deposited conformally on emulsion-templated carbon foam by a sol-gel method. The carbon foam is synthesized via a facile and scalable method which involves the carbonization of a high internal phase emulsion (polyHIPE) polymer template. Various techniques (XRD, SEM, TEM and electrochemical methods) are used to fully characterize the porous electrode and confirm the distribution and morphology of the cathode active material. The major benefits of the carbon foam used in our work are closely connected with its high surface area and the plenty of space suitable for sequential coating with battery components. After coating with a cathode material (LiFePO4 nanoparticles), the 3D electrode presents a hierarchically structured electrode in which a porous layer of the cathode material is deposited on the rigid and bicontinuous carbon foam. The composite electrodes exhibit impressive cyclability and rate performance at different current densities affirming their importance as viable power sources in miniature devices. Footprint area capacities of 1.72 mA h cm-2 at 0.1 mA cm-2 (lowest rate) and 1.1 mA h cm-2 at 6 mA cm-2 (highest rate) are obtained when the cells are cycled in the range 2.8 to 4.0 V vs. lithium.In this article, we report a novel 3D composite cathode fabricated from LiFePO4 nanoparticles deposited conformally on emulsion-templated carbon foam by a sol-gel method. The carbon foam is synthesized via a facile and scalable method which involves the carbonization of a high internal phase emulsion (polyHIPE) polymer template. Various techniques (XRD, SEM, TEM and electrochemical methods) are used to fully characterize the porous electrode and confirm the distribution and morphology of the cathode active material. The major benefits of the carbon foam used in our work are closely connected with its high surface area and the plenty of space suitable for sequential coating

Anomalous magnetic structure and spin dynamics in magnetoelectric LiFePO 4

DOE PAGES

Toft-Petersen, Rasmus; Reehuis, Manfred; Jensen, Thomas B. S.; ...

2015-07-06

We report significant details of the magnetic structure and spin dynamics of LiFePO 4 obtained by single-crystal neutron scattering. Our results confirm a previously reported collinear rotation of the spins away from the principal b axis, and they determine that the rotation is toward the a axis. In addition, we find a significant spin-canting component along c. Furthermore, the possible causes of these components are discussed, and their significance for the magnetoelectric effect is analyzed. Inelastic neutron scattering along the three principal directions reveals a highly anisotropic hard plane consistent with earlier susceptibility measurements. While using a spin Hamiltonian, wemore » show that the spin dimensionality is intermediate between XY- and Ising-like, with an easy b axis and a hard c axis. As a result, it is shown that both next-nearest neighbor exchange couplings in the bc plane are in competition with the strongest nearest neighbor coupling.« less

Continuous flame aerosol synthesis of carbon-coated nano-LiFePO4 for Li-ion batteries

PubMed Central

Waser, Oliver; Büchel, Robert; Hintennach, Andreas; Novák, Petr; Pratsinis, Sotiris E.

2013-01-01

Core-shell, nanosized LiFePO4-carbon particles were made in one step by scalable flame aerosol technology at 7 g/h. Core LiFePO4 particles were made in an enclosed flame spray pyrolysis (FSP) unit and were coated in-situ downstream by auto thermal carbonization (pyrolysis) of swirl-fed C2H2 in an O2-controlled atmosphere. The formation of acetylene carbon black (ACB) shell was investigated as a function of the process fuel-oxidant equivalence ratio (EQR). The core-shell morphology was obtained at slightly fuel-rich conditions (1.0 < EQR < 1.07) whereas segregated ACB and LiFePO4 particles were formed at fuel-lean conditions (0.8 < EQR < 1). Post-annealing of core-shell particles in reducing environment (5 vol% H2 in argon) at 700 °C for up to 4 hours established phase pure, monocrystalline LiFePO4 with a crystal size of 65 nm and 30 wt% ACB content. Uncoated LiFePO4 or segregated LiFePO4-ACB grew to 250 nm at these conditions. Annealing at 800 °C induced carbothermal reduction of LiFePO4 to Fe2P by ACB shell consumption that resulted in cavities between carbon shell and core LiFePO4 and even slight LiFePO4 crystal growth but better electrochemical performance. The present carbon-coated LiFePO4 showed superior cycle stability and higher rate capability than the benchmark, commercially available LiFePO4. PMID:23407817

Freeze-drying synthesis of three-dimensional porous LiFePO4 modified with well-dispersed nitrogen-doped carbon nanotubes for high-performance lithium-ion batteries

NASA Astrophysics Data System (ADS)

Tu, Xiaofeng; Zhou, Yingke; Song, Yijie

2017-04-01

The three-dimensional porous LiFePO4 modified with uniformly dispersed nitrogen-doped carbon nanotubes has been successfully prepared by a freeze-drying method. The morphology and structure of the porous composites are characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), and the electrochemical performances are evaluated using the constant current charge/discharge tests, cyclic voltammetry and electrochemical impedance spectroscopy. The nitrogen-doped carbon nanotubes are uniformly dispersed inside the porous LiFePO4 to construct a superior three-dimensional conductive network, which remarkably increases the electronic conductivity and accelerates the diffusion of lithium ion. The porous composite displays high specific capacity, good rate capability and excellent cycling stability, rendering it a promising positive electrode material for high-performance lithium-ion batteries.

The P3 kimberlite and P4 lamproite, Wajrakarur kimberlite field, India: mineralogy, and major and minor element compositions of olivines as records of their phenocrystic vs xenocrystic origin

NASA Astrophysics Data System (ADS)

Shaikh, Azhar M.; Kumar, Satya P.; Patel, Suresh C.; Thakur, Satyajeet S.; Ravi, Subramanian; Behera, Duryadhan

2018-03-01

Distinctly different groundmass mineralogy characterise the hypabyssal facies, Mesoproterozoic diamondiferous P3 and P4 intrusions from the Wajrakarur Kimberlite Field, southern India. P3 is an archetypal kimberlite with macrocrysts of olivine and phlogopite set in a groundmass dominated by phlogopite and monticellite with subordinate amounts of serpentine, spinel, perovskite, apatite, calcite and rare baddeleyite. P4 contains mega- and macrocrysts of olivine set in a groundmass dominated by clinopyroxene and phlogopite with subordinate amounts of serpentine, spinel, perovskite, apatite, and occasional gittinsite, and is mineralogically interpreted as an olivine lamproite. Three distinct populations of olivine, phlogopite and clinopyroxene are recognized based on their microtextural and compositional characteristics. The first population includes glimmerite and phlogopite-clinopyroxene nodules, and Mg-rich olivine macrocrysts (Fo 90-93) which are interpreted to be derived from disaggregated mantle xenoliths. The second population comprises macrocrysts of phlogopite and Fe-rich olivine (Fo 81-89) from P3, megacrysts and macrocrysts of Fe-rich olivine (Fo 85-87) from P4 and a rare olivine-clinopyroxene nodule from P4 which are suggested to have a genetic link with the precursor melt of the respective intrusions. The third population represents clearly magmatic minerals such as euhedral phenocrysts of Fe-rich olivine (Fo 85-90) crystallised at mantle depths, and olivine overgrowth rims formed contemporaneously with groundmass minerals at crustal levels. Close spatial association and contemporaneous emplacement of P3 kimberlite and P4 lamproite is explained by a unifying petrogenetic model which involves the interaction of a silica-poor carbonatite melt with differently metasomatised wall rocks in the lithospheric mantle. It is proposed that the metasomatised wall rock for lamproite contained abundant MARID-type and phlogopite-rich metasomatic veins, while that for

Chemical Imaging of Nanoscale Interfacial Inhomogeneity in LiFePO4 Composite Electrodes from a Cycled Large-Format Battery.

PubMed

Zhou, Jigang; Wang, Jian; Hu, Yongfeng; Lu, Mi

2017-11-15

The nanoscale interfacial inhomogeneity in a cycled large-format LiFePO 4 (LFP) composite electrode has been studied by X-ray photoemission electron microscopy at single particle spatial resolution with a probe depth of ∼5 nm. The loss of active lithium in cycled LFP causes the coexsitence of fully delithiated LFP (FePO 4 ) and partially delithiated LFP (Li 0.6 FePO 4 or Li 0.8 FePO 4 ) as a function of the extent of lithium loss. The distribution of various lithium loss phases along with local agglomeration of LFP and degradation of binder and carbon black are correlatively visualized. This is the first experimental exploration of chemical interplay between components in the composite electrode from a large-format battery, and implications on the LFP degradation in this battery are discussed.

Direct Observation of Active Material Concentration Gradients and Crystallinity Breakdown in LiFePO4 Electrodes During Charge/Discharge Cycling of Lithium Batteries.

PubMed

Roberts, Matthew R; Madsen, Alex; Nicklin, Chris; Rawle, Jonathan; Palmer, Michael G; Owen, John R; Hector, Andrew L

2014-04-03

The phase changes that occur during discharge of an electrode comprised of LiFePO 4 , carbon, and PTFE binder have been studied in lithium half cells by using X-ray diffraction measurements in reflection geometry. Differences in the state of charge between the front and the back of LiFePO 4 electrodes have been visualized. By modifying the X-ray incident angle the depth of penetration of the X-ray beam into the electrode was altered, allowing for the examination of any concentration gradients that were present within the electrode. At high rates of discharge the electrode side facing the current collector underwent limited lithium insertion while the electrode as a whole underwent greater than 50% of discharge. This behavior is consistent with depletion at high rate of the lithium content of the electrolyte contained in the electrode pores. Increases in the diffraction peak widths indicated a breakdown of crystallinity within the active material during cycling even during the relatively short duration of these experiments, which can also be linked to cycling at high rate.

Direct Observation of Active Material Concentration Gradients and Crystallinity Breakdown in LiFePO4 Electrodes During Charge/Discharge Cycling of Lithium Batteries

PubMed Central

2014-01-01

The phase changes that occur during discharge of an electrode comprised of LiFePO4, carbon, and PTFE binder have been studied in lithium half cells by using X-ray diffraction measurements in reflection geometry. Differences in the state of charge between the front and the back of LiFePO4 electrodes have been visualized. By modifying the X-ray incident angle the depth of penetration of the X-ray beam into the electrode was altered, allowing for the examination of any concentration gradients that were present within the electrode. At high rates of discharge the electrode side facing the current collector underwent limited lithium insertion while the electrode as a whole underwent greater than 50% of discharge. This behavior is consistent with depletion at high rate of the lithium content of the electrolyte contained in the electrode pores. Increases in the diffraction peak widths indicated a breakdown of crystallinity within the active material during cycling even during the relatively short duration of these experiments, which can also be linked to cycling at high rate. PMID:24790684

Chemical characterization of solid polymer electrolyte membrane surfaces in LiFePO4 half-cells

NASA Astrophysics Data System (ADS)

Kyu, Thein; He, Ruixuan; Peng, Fang; Dunn, William E.; Kyu's Group Team, Dr.

High temperature (60 °C) capacity retention of succinonitrile plasticized solid polymer electrolyte membrane (PEM) in a LiFePO4 half-cell was investigated with or without lithium bis(oxalato)borate (LiBOB) modification. Various symmetric cells and half-cells were studied under different thermal and electrochemical conditions. At room temperature cycling, the unmodified PEM in the half-cell appeared stable up to 50 cycles tested. Upon cycling at 60 °C, the capacity decays rapidly and concurrently the cell resistance increased. The chemical compositions of the solid PEM surfaces on both cathode and anode sides were analyzed. New IR bands (including those belonged to amide) were discerned on the unmodified PEM surface of the Li electrode side at 60 °C suggestive of side reaction, but no new bands develop during room temperature cycling. To our astonishment, the side reaction was effectively suppressed upon LiBOB addition (0.4 wt%) into the PEM, contributing to increased high temperature capacity retention at 60°C. Plausible mechanisms of capacity fading and improved cycling performance due to LiBOB modification are discussed.

Atomic-Scale Observations of (010) LiFePO4 Surfaces Before and After Chemical Delithiation.

PubMed

Kobayashi, Shunsuke; Fisher, Craig A J; Kato, Takeharu; Ukyo, Yoshio; Hirayama, Tsukasa; Ikuhara, Yuichi

2016-09-14

The ability to view directly the surface structures of battery materials with atomic resolution promises to dramatically improve our understanding of lithium (de)intercalation and related processes. Here we report the use of state-of-the-art scanning transmission electron microscopy techniques to probe the (010) surface of commercially important material LiFePO4 and compare the results with theoretical models. The surface structure is noticeably different depending on whether Li ions are present in the topmost surface layer or not. Li ions are also found to migrate back to surface regions from within the crystal relatively quickly after partial delithiation, demonstrating the facile nature of Li transport in the [010] direction. The results are consistent with phase transformation models involving metastable phase formation and relaxation, providing atomic-level insights into these fundamental processes.

Thermal equation of state of (Mg 0.9Fe 0.1) 2SiO 4 olivine

NASA Astrophysics Data System (ADS)

Liu, Wei; Li, Baosheng

2006-08-01

In situ synchrotron X-ray diffraction measurements have been carried out on San Carlos olivine (Mg 0.9Fe 0.1) 2SiO 4 up to 8 GPa and 1073 K. Data analysis using the high-temperature Birch-Murnaghan (HTBM) equation of state (EoS) yields the temperature derivative of the bulk modulus (∂ KT/∂ T) P = -0.019 ± 0.002 GPa K -1. The thermal pressure (TH) approach gives αKT = 4.08 ± 0.10 × 10 -3 GPa K -1, from which (∂ KT/∂ T) P = -0.019 ± 0.001 GPa K -1 is derived. Fitting the present data to the Mie-Grüneisen-Debye (MGD) formalism, the Grüneisen parameter at ambient conditions γ0 is constrained to be 1.14 ± 0.02 with fixed volume dependence q = 1. Combining the present data with previous results on iron-bearing olivine and fitting to MGD EoS, we obtain γ0 = 1.11 ± 0.01 and q = 0.54 ± 0.36. In this study the thermoelastic parameters obtained from various approaches are in good agreement with one another and previous results.

Nanosized LiFePO4-decorated emulsion-templated carbon foam for 3D micro batteries: a study of structure and electrochemical performance.

PubMed

Asfaw, Habtom D; Roberts, Matthew R; Tai, Cheuk-Wai; Younesi, Reza; Valvo, Mario; Nyholm, Leif; Edström, Kristina

2014-08-07

In this article, we report a novel 3D composite cathode fabricated from LiFePO4 nanoparticles deposited conformally on emulsion-templated carbon foam by a sol-gel method. The carbon foam is synthesized via a facile and scalable method which involves the carbonization of a high internal phase emulsion (polyHIPE) polymer template. Various techniques (XRD, SEM, TEM and electrochemical methods) are used to fully characterize the porous electrode and confirm the distribution and morphology of the cathode active material. The major benefits of the carbon foam used in our work are closely connected with its high surface area and the plenty of space suitable for sequential coating with battery components. After coating with a cathode material (LiFePO4 nanoparticles), the 3D electrode presents a hierarchically structured electrode in which a porous layer of the cathode material is deposited on the rigid and bicontinuous carbon foam. The composite electrodes exhibit impressive cyclability and rate performance at different current densities affirming their importance as viable power sources in miniature devices. Footprint area capacities of 1.72 mA h cm(-2) at 0.1 mA cm(-2) (lowest rate) and 1.1 mA h cm(-2) at 6 mA cm(-2) (highest rate) are obtained when the cells are cycled in the range 2.8 to 4.0 V vs. lithium.

Supervised chaos genetic algorithm based state of charge determination for LiFePO4 batteries in electric vehicles

NASA Astrophysics Data System (ADS)

Shen, Yanqing

2018-04-01

LiFePO4 battery is developed rapidly in electric vehicle, whose safety and functional capabilities are influenced greatly by the evaluation of available cell capacity. Added with adaptive switch mechanism, this paper advances a supervised chaos genetic algorithm based state of charge determination method, where a combined state space model is employed to simulate battery dynamics. The method is validated by the experiment data collected from battery test system. Results indicate that the supervised chaos genetic algorithm based state of charge determination method shows great performance with less computation complexity and is little influenced by the unknown initial cell state.

Raman and FTIR spectroscopy of methane in olivine

NASA Astrophysics Data System (ADS)

Smith, A.; Oze, C.; Rossman, G. R.; Celestian, A. J.

2017-12-01

Olivine has been proposed to be a direct source of methane (CH4) in serpentinization systems and experiments. Here, Raman and Fourier Transform Infrared (FTIR) spectroscopy were used to verify the presence and abundance of CH4 in olivine samples from nine localities, including the San Carlos olivine. Raman analyses did not identify any methane in the olivine samples. As olivine is orthorhombic, three polarized FTIR spectra were obtained for the olivine samples. No methane was detected in any of the olivine samples using FTIR. Overall, olivine investigated in this study does not appear to be a primary source of methane.

Rapid preparation of high electrochemical performance LiFePO4/C composite cathode material with an ultrasonic-intensified micro-impinging jetting reactor.

PubMed

Dong, Bin; Huang, Xiani; Yang, Xiaogang; Li, Guang; Xia, Lan; Chen, George

2017-11-01

A joint chemical reactor system referred to as an ultrasonic-intensified micro-impinging jetting reactor (UIJR), which possesses the feature of fast micro-mixing, was proposed and has been employed for rapid preparation of FePO 4 particles that are amalgamated by nanoscale primary crystals. As one of the important precursors for the fabrication of lithium iron phosphate cathode, the properties of FePO 4 nano particles significantly affect the performance of the lithium iron phosphate cathode. Thus, the effects of joint use of impinging stream and ultrasonic irradiation on the formation of mesoporous structure of FePO 4 nano precursor particles and the electrochemical properties of amalgamated LiFePO 4 /C have been investigated. Additionally, the effects of the reactant concentration (C=0.5, 1.0 and 1.5molL -1 ), and volumetric flow rate (V=17.15, 51.44, and 85.74mLmin -1 ) on synthesis of FePO 4 ·2H 2 O nucleus have been studied when the impinging jetting reactor (IJR) and UIJR are to operate in nonsubmerged mode. It was affirmed from the experiments that the FePO 4 nano precursor particles prepared using UIJR have well-formed mesoporous structures with the primary crystal size of 44.6nm, an average pore size of 15.2nm, and a specific surface area of 134.54m 2 g -1 when the reactant concentration and volumetric flow rate are 1.0molL -1 and 85.74mLmin -1 respectively. The amalgamated LiFePO 4 /C composites can deliver good electrochemical performance with discharge capacities of 156.7mAhg -1 at 0.1C, and exhibit 138.0mAhg -1 after 100 cycles at 0.5C, which is 95.3% of the initial discharge capacity. Copyright © 2017. Published by Elsevier B.V.

Interphase evolution at two promising electrode materials for Li-ion batteries: LiFePO4 and LiNi1/2 Mn1/2O2.

PubMed

Dupré, Nicolas; Cuisinier, Marine; Martin, Jean-Frederic; Guyomard, Dominique

2014-07-21

The present review reports the characterization and control of interfacial processes occurring on olivine LiFePO(4) and layered LiNi(1/2) Mn(1/2)O(2), standing here as model compounds, during storage and electrochemical cycling. The formation and evolution of the interphase created by decomposition of the electrolyte is investigated by using spectroscopic tools such as magic-angle-spinning nuclear magnetic resonance ((7)Li,(19)F and (31)P) and electron energy loss spectroscopy, in parallel to X-ray photoelectron spectroscopy, to quantitatively describe the interphase and unravel its architecture. The influence of the pristine surface chemistry of the active material is carefully examined. The importance of the chemical history of the surface of the electrode material before any electrochemical cycling and the strong correlation between interface phenomena, the formation/evolution of an interphase, and the electrochemical behavior appear clearly from the use of these combined characterization probes. This approach allows identifying interface aging and failure mechanisms. Different types of surface modifications are then investigated, such as intrinsic modifications upon aging in air or methods based on the use of additives in the electrolyte or carbon coatings on the surface of the active materials. In each case, the species detected on the surface of the materials during storage and cycling are correlated with the electrochemical performance of the modified positive electrodes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Water and Carbon Dioxide Adsorption at Olivine Surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kerisit, Sebastien N.; Bylaska, Eric J.; Felmy, Andrew R.

2013-11-14

Plane-wave density functional theory (DFT) calculations were performed to simulate water and carbon dioxide adsorption at the (010) surface of five olivine minerals, namely, forsterite (Mg2SiO4), calcio-olivine (Ca2SiO4), tephroite (Mn2SiO4), fayalite (Fe2SiO4), and Co-olivine (Co2SiO4). Adsorption energies per water molecule obtained from energy minimizations varied from -78 kJ mol-1 for fayalite to -128 kJ mol-1 for calcio-olivine at sub-monolayer coverage and became less exothermic as coverage increased. In contrast, carbon dioxide adsorption energies at sub-monolayer coverage ranged from -20 kJ mol-1 for fayalite to -59 kJ mol-1 for calcio-olivine. Therefore, the DFT calculations show a strong driving force for carbonmore » dioxide displacement by water at the surface of all olivine minerals in a competitive adsorption scenario. Additionally, adsorption energies for both water and carbon dioxide were found to be more exothermic for the alkaline-earth (AE) olivines than for the transition-metal (TM) olivines and to not correlate with the solvation enthalpies of the corresponding divalent cations. However, a correlation was obtained with the charge of the surface divalent cation indicating that the more ionic character of the AE cations in the olivine structure relative to the TM cations leads to greater interactions with adsorbed water and carbon dioxide molecules at the surface and thus more exothermic adsorption energies for the AE olivines. For calcio-olivine, which exhibits the highest divalent cation charge of the five olivines, ab initio molecular dynamics simulations showed that this effect leads both water and carbon dioxide to react with the surface and form hydroxyl groups and a carbonate-like species, respectively.« less

Preparing high performance of LiFe(1-x)MxPO4 by using Fe(1-x)MxC2O4 as raw material precipitated from ferrochrome alloy leaching solution

NASA Astrophysics Data System (ADS)

Hu, Guo-rong; Liu, Ji-jun; Du, Ke; Peng, Zhong-dong; Cao, Yan-bing; Wang, Wei-gang; Duan, Jian-guo

2014-08-01

To separate ferrum from chromium in the leaching sulfate solution of ferrochrome alloy, the oxalic acid was employed to precipitate the ferrum as the form of FeC2O4 and Cr was left in the solution. In this route, small amount of nickel, cobalt and manganese exited in ferrochrome alloy were also precipitated simultaneously together with ferrous oxalate. Analysis from ICP shows that the molar percent of Fe in oxalic precipitate is 97.9% and the main doped elements are Ni (1.1%) and Mn (0.4%).The mixed metal oxalate Fe(1-x)MxC2O4 was used as a raw material to prepare doped LiFePO4 cathode material of lithium ion batteries. The obtained LiFe(1-x)MxPO4/C was a single olivine-type phase with higher crystallinity and presents the well-distributed fine particles. It shows an outstanding electrochemical performance with a discharge capacity of 162 mAh/g at the rate of 0.1 C, 136 mAh/g at 1 C and 103 mAh/g at 5 C. When cycled at 1 C for 50 times, the capacity retention is 98.2%.

An in situ X ray diffraction study of the kinetics of the Ni2SiO4 olivine-spinel transformation

NASA Technical Reports Server (NTRS)

Rubie, D. C.; Tsuchida, Y.; Yagi, T.; Utsumi, W.; Kikegawa, T.

1990-01-01

The kinetics of the olivine-spinel transformation in Ni2SiO4 were investigated in an in situ X-ray diffraction experiments in which synchrotron radiation was used as an X-ray source. The starting material was Ni2SO4 olivine which was hot-pressed in situ at 980 C and 2.5 GPa; during the transformation, X-ray diffraction patterns were collected at intervals of 30 or 120 sec. The kinetic data were analyzed using Cahn's (1956) model. The activation energy for growth at 3.6-3.7 GPa was estimated as 438 + or - 199 kJ/mol. It is shown that, in order to make significant extrapolations of the kinetic data to a geological scale, the dependence of the rates of both nucleation and growth on temperature and pressure must be evaluated separately.

Electroactive ionic liquids based on 2,5-ditert-butyl-1,4-dimethoxybenzene and triflimide anion as redox shuttle for Li4Ti5O12/LiFePO4 lithium-ion batteries

NASA Astrophysics Data System (ADS)

Gélinas, Bruno; Bibienne, Thomas; Dollé, Mickael; Rochefort, Dominic

2017-12-01

In order to increase the solubility and oxidation potential of redox shuttles, electroactive ionic liquids (RILs) based on the modification of 1,4-dimethoxybenzene with triflimide anions were synthesized. We developed two synthetic routes to obtain these RILs in which the triflimide was either linked on the benzene ring or as a ether on 2,5-ditert-butyl-1,4-dimethoxybenzene (DDB). These RILs all have melting points below 100 °C, but above room temperature. The structural impact of electroactive anion was evaluated in this study by determining the redox potential and electrochemical stability. The electrochemical properties of these RILs were investigated by cyclic voltammetry and the diffusion coefficients were measured by double potential step chronoamperometry. The viscosity and ionic conductivity measurements of redox-active electrolyte were obtained at different temperatures and the RIL additives are shown to have a low impact on these electrolyte properties at concentrations up to 0.3 M. The charge-overcharge-discharge cycles of Li/LiFePO4 half-cells and Li4Ti5O12/LiFePO4 full cells with a 100% overcharge are presented using redox-active electrolyte (0.3 M concentration level) at 0.1 C rate. This study highlights the potential of electroactive ionic liquids as highly soluble and stable functional additives in Li-ion battery electrolytes.

Modeling the degradation mechanisms of C6/LiFePO4 batteries

NASA Astrophysics Data System (ADS)

Li, Dongjiang; Danilov, Dmitri L.; Zwikirsch, Barbara; Fichtner, Maximilian; Yang, Yong; Eichel, Rüdiger-A.; Notten, Peter H. L.

2018-01-01

A fundamental electrochemical model is developed, describing the capacity fade of C6/LiFePO4 batteries as a function of calendar time and cycling conditions. At moderate temperatures the capacity losses are mainly attributed to Li immobilization in Solid-Electrolyte-Interface (SEI) layers at the anode surface. The SEI formation model presumes the availability of an outer and inner SEI layers. Electron tunneling through the inner SEI layer is regarded as the rate-determining step. The model also includes high temperature degradation. At elevated temperatures, iron dissolution from the positive electrode and the subsequent metal sedimentation on the negative electrode influence the capacity loss. The SEI formation on the metal-covered graphite surface is faster than the conventional SEI formation. The model predicts that capacity fade during storage is lower than during cycling due to the generation of SEI cracks induced by the volumetric changes during (dis)charging. The model has been validated by cycling and calendar aging experiments and shows that the capacity loss during storage depends on the storage time, the State-of-Charge (SoC), and temperature. The capacity losses during cycling depend on the cycling current, cycling time, temperature and cycle number. All these dependencies can be explained by the single model presented in this paper.

Mapping Structure-Composition-Property Relationships in V- and Fe-Doped LiMnPO4 Cathodes for Lithium-Ion Batteries.

PubMed

Johnson, Ian D; Loveridge, Melanie; Bhagat, Rohit; Darr, Jawwad A

2016-11-14

A series of LiMn 1-x-y Fe x V y PO 4 (LMFVP) nanomaterials have been synthesized using a pilot-scale continuous hydrothermal synthesis process (CHFS) and evaluated as high voltage cathodes in Li-ion batteries at a production rate of 0.25 kg h -1 . The rapid synthesis and screening approach has allowed the specific capacity of the high Mn content olivines to be optimized, particularly at high discharge rates. Consistent and gradual changes in the structure and performance are observed across the compositional region under investigation; the doping of Fe at 20 at% (with respect to Mn) into lithium manganese phosphate, rather than V or indeed codoping of Fe and V, gives the best balance of high capacity and high rate performance.

Particle size dependent confinement and lattice strain effects in LiFePO4.

PubMed

Shahid, Raza; Murugavel, Sevi

2013-11-21

We report the intrinsic electronic properties of LiFePO4 (LFP) with different particle sizes measured by broad-band impedance spectroscopy and diffuse reflectance spectroscopy. The electronic properties show typical size-dependent effects with decreasing particle size (up to 150 nm). However, at the nanoscale level, we observed an enhancement in the polaronic conductivity about an order of magnitude. We found that the origin of the enhanced electronic conductivity in LFP is due to the significant lattice strain associated with the reduction of particle size. The observed lattice strain component corresponds to the compressive part which leads to a decrease in the hopping length of the polarons. We reproduce nonlinearities in the transport properties of LFP with particle size, to capture the interplay between confinement and lattice strain, and track the effects of strain on the electron-phonon interactions. These results could explain why nano-sized LFP has a better discharge capacity and higher rate capability than the bulk counterpart. We suggest that these new correlations will bring greater insight and better understanding for the optimization of LFP as a cathode material for advanced lithium ion batteries.

Assessing the Health of LiFePO4 Traction Batteries through Monotonic Echo State Networks

PubMed Central

Anseán, David; Otero, José; Couso, Inés

2017-01-01

A soft sensor is presented that approximates certain health parameters of automotive rechargeable batteries from on-vehicle measurements of current and voltage. The sensor is based on a model of the open circuit voltage curve. This last model is implemented through monotonic neural networks and estimate over-potentials arising from the evolution in time of the Lithium concentration in the electrodes of the battery. The proposed soft sensor is able to exploit the information contained in operational records of the vehicle better than the alternatives, this being particularly true when the charge or discharge currents are between moderate and high. The accuracy of the neural model has been compared to different alternatives, including data-driven statistical models, first principle-based models, fuzzy observers and other recurrent neural networks with different topologies. It is concluded that monotonic echo state networks can outperform well established first-principle models. The algorithms have been validated with automotive Li-FePO4 cells. PMID:29267219

Carbon coatings with olive oil, soybean oil and butter on nano-LiFePO 4

NASA Astrophysics Data System (ADS)

Kim, Ketack; Jeong, Ji Hwa; Kim, Ick-Jun; Kim, Hyun-Soo

Kitchen oils (olive, soybean and butter) are selected for carbon coatings on LiFePO 4. The surface properties of LiFePO 4 are unknown or vary depending on synthetic methods. The multi-functional groups of fatty acids in the oils can orient properly to cope with the variable surface properties of LiFePO 4, which can lead to dense carbon coatings. The low price and low toxicity of kitchen oils are other advantages of the coating process. LiFePO 4 (D 50 = 121 nm)combined with the carbon coating enhances the rate capability. Capacities at the 2 C rate reach 150 mAh g -1 or higher. The charge retention values of 2.0 C/0.2 C are between 94.4 and 98.9%.

Synthesis of superior fast charging-discharging nano-LiFePO4/C from nano-FePO4 generated using a confined area impinging jet reactor approach.

PubMed

Liu, Xiao-min; Yan, Pen; Xie, Yin-Yin; Yang, Hui; Shen, Xiao-dong; Ma, Zi-Feng

2013-06-14

LiFePO4/C nanocomposites with excellent electrochemical performance is synthesized from nano-FePO4, generated by a novel method using a confined area impinging jet reactor (CIJR). When discharged at 80 C (13.6 Ag(-1)), the LiFePO4/C delivers a discharge capacity of 95 mA h g(-1), an energy density of 227 W h kg(-1) and a power density of 34 kW kg(-1).

Small polaron hopping conduction mechanism in LiFePO4 glass and crystal

NASA Astrophysics Data System (ADS)

Banday, Azeem; Murugavel, Sevi

2017-01-01

The optimization of a cathode material is the most important criterion of lithium ion battery technology, which decides the power density. In order to improve the rate capability, a cathode material must possess high electronic and ionic conductivities. Therefore, it is important to understand the charge transport mechanism in such an advanced cathode material in its intrinsic state before modifying it by various means. In this work, we report the thermal, structural, and electrical conductivity studies on lithium iron phosphate, LiFePO4, both in its polycrystalline (LFPC) and glassy (LFPG) counterpart states. The vibrational spectroscopic measurements reveal the characteristic vibrational modes, which are the intrinsic part of LFPC, whereas in LFPG, the phonon modes become broader and overlap with each other due to the lattice disorder. The electrical conductivity measurements reveal that LFPG exhibits a higher polaronic conductivity of 1.6 orders than the LFPC sample. The temperature dependent dc conductivity has been analyzed with the Mott model of polarons and reveals the origin of enhanced polaronic conductivity in LFPG. Based on the analysis, the enhanced polaronic conductivity in LFPG has been attributed to the combined effect of reduced hopping length, decreased activation energy, and enhanced polaron concentration.

Facile Synthesis of Carbon-Coated Spinel Li4Ti5O12/Rutile-TiO2 Composites as an Improved Anode Material in Full Lithium-Ion Batteries with LiFePO4@N-Doped Carbon Cathode.

PubMed

Wang, Ping; Zhang, Geng; Cheng, Jian; You, Ya; Li, Yong-Ke; Ding, Cong; Gu, Jiang-Jiang; Zheng, Xin-Sheng; Zhang, Chao-Feng; Cao, Fei-Fei

2017-02-22

The spinel Li 4 Ti 5 O 12 /rutile-TiO 2 @carbon (LTO-RTO@C) composites were fabricated via a hydrothermal method combined with calcination treatment employing glucose as carbon source. The carbon coating layer and the in situ formed rutile-TiO 2 can effectively enhance the electric conductivity and provide quick Li + diffusion pathways for Li 4 Ti 5 O 12 . When used as an anode material for lithium-ion batteries, the rate capability and cycling stability of LTO-RTO@C composites were improved in comparison with those of pure Li 4 Ti 5 O 12 or Li 4 Ti 5 O 12 /rutile-TiO 2 . Moreover, the potential of approximately 1.8 V rechargeable full lithium-ion batteries has been achieved by utilizing an LTO-RTO@C anode and a LiFePO 4 @N-doped carbon cathode.

Conductivity and electrochemical performance of LiFePO4 slurry in the lithium slurry battery

NASA Astrophysics Data System (ADS)

Feng, Caimei; Chen, Yongchong; Liu, Dandan; Zhang, Ping

2017-06-01

Lithium slurry battery is a new type of energy storage technique which uses the slurry of solid active materials, conductive additions and liquid electrolyte as the electrode. The proportion of conductive addition and the active material has significant influence on the conductivity and electrochemical performance of the slurry electrode. In the present work, slurries with different volume ratios of LiFePO4 (LFP) and Ketjenblack (KB) were investigated by the electrochemical workstation and charge-discharge testing system (vs. Li/Li+). Results show that the conductivity of the slurry increases linearly with the addition of KB, and the measured specific capacity of the slurry reaches its theoretical value when the volume ratio of KB to LFP is around 0.2. Based on this ratio, a slurry battery with higher loading of LFP (19.1 wt.% in the slurry) was tested, and a specific capacity of 165 mAh/g at 0.2 mA/cm2 and 102 mAh/g at 5 mA/cm2 was obtained for LFP.

Theoretical evaluation of high-energy lithium metal phosphate cathode materials in Li-ion batteries

NASA Astrophysics Data System (ADS)

Howard, Wilmont F.; Spotnitz, Robert M.

Lithium metal phosphates (olivines) are emerging as long-lived, safe cathode materials in Li-ion batteries. Nano-LiFePO 4 already appears in high-power applications, and LiMnPO 4 development is underway. Current and emerging Fe- and Mn-based intercalants, however, are low-energy producers compared to Ni and Co compounds. LiNiPO 4, a high voltage olivine, has the potential for superior energy output (>10.7 Wh in 18650 batteries), compared with commercial Li(Co,Ni)O 2 derivatives (up to 9.9 Wh). Speculative Co and Ni olivine cathode materials charged to above 4.5 V will require significant advances in electrolyte compositions and nanotechnology before commercialization. The major drivers toward 5 V battery chemistries are the inherent abuse tolerance of phosphates and the economic benefit of LiNiPO 4: it can produce 34% greater energy per dollar of cell material cost than LiAl 0.05Co 0.15Ni 0.8O 2, today's "standard" cathode intercalant in Li-ion batteries.

Hybrid excitations due to crystal field, spin-orbit coupling, and spin waves in LiFePO4

NASA Astrophysics Data System (ADS)

Yiu, Yuen; Le, Manh Duc; Toft-Peterson, Rasmus; Ehlers, Georg; McQueeney, Robert J.; Vaknin, David

2017-03-01

We report on the spin waves and crystal field excitations in single crystal LiFePO4 by inelastic neutron scattering over a wide range of temperatures, below and above the antiferromagnetic transition of this system. In particular, we find extra excitations below TN=50 K that are nearly dispersionless and are most intense around magnetic zone centers. We show that these excitations correspond to transitions between thermally occupied excited states of Fe2 + due to splitting of the S =2 levels that arise from the crystal field and spin-orbit interactions. These excitations are further amplified by the highly distorted nature of the oxygen octahedron surrounding the iron atoms. Above TN, magnetic fluctuations are observed up to at least 720 K, with an additional inelastic excitation around 4 meV, which we attribute to single-ion effects, as its intensity weakens slightly at 720 K compared to 100 K, which is consistent with the calculated cross sections using a single-ion model. Our theoretical analysis, using the MF-RPA model, provides both detailed spectra of the Fe d shell and estimates of the average ordered magnetic moment and TN. By applying the MF-RPA model to a number of existing spin-wave results from other Li M PO4 (M =Mn , Co, and Ni), we are able to obtain reasonable predictions for the moment sizes and transition temperatures.

Olivine-modified spinel-spinel transitions in the system Mg2SiO4-Fe2SiO4: Calorimetric measurements, thermochemical calculation, and geophysical application

NASA Astrophysics Data System (ADS)

Akaogi, Masaki; Ito, Eiji; Navrotsky, Alexandra

1989-11-01

The olivine(α)-modified spinel(β)-spinel (γ) transitions in the system Mg2SiO4-Fe2SiO4 were studied by high-temperature solution calorimetry. Enthalpies of the β-γ and a α-γ transitions in Mg2SiO4 at 975 K and of the α-γ transition in Fe2SiO4 at 298 K were measured. The γ solid solution showed a positive enthalpy of mixing. Phase relations at high pressures and high temperatures were calculated from these thermochemical data including correction for the effect of nonideality of α, β, and γ solid solutions. The calculated phase diagrams agree well with those determined experimentally by Katsura and Ito very recently. The α - (Mg0.89, Fe0.11)2SiO4 transforms to β through a region of α+β without passing through the α+γ phase field at around 400 km depth in the mantle with an interval of about 18(±5) km. Temperatures at 390 and 650 km depths are estimated to be about 1673 and 1873 K, respectively, assuming an adiabatic geotherm.

Polyanion Driven Antiferromagnetic and Insulating Ground State of Olivine Phosphates: LiMPO4

NASA Astrophysics Data System (ADS)

Jena, Ajit Kumar; Nanda, B. R. K.; Condensed Matter Theory; Computation Team

Through density functional calculations we have investigated the electronic and magnetic properties of LiMPO4, where M is a 3d transition metal element. We find that contrary to many transition metal oxides, in these Olivine phosphates the band gap is originated due to crystal field anisotropy as well as weak O-p - M-d covalent interaction. Both of them are attributed to the presence of PO43- polyanion. The anisotropic crystal field, in the absence of covalent interactions, creates atomically localized non-degenerate M-d states and therefore the gap is a natural outcome. Onsite repulsion, due to strong correlation effect, further enhances the gap. These localized d states favor high-spin configuration which leads to antiferromagnetic ordering due to Hund's coupling. Experimentally observed low Neel temperature of this family of compounds is explained from the DFT obtained spin exchange interaction parameters. Work supported by Nissan Research Program.

Effect of in situ pyrolysis of acetylene (C2H2) gas as a carbon source on the electrochemical performance of LiFePO4 for rechargeable lithium-ion batteries

NASA Astrophysics Data System (ADS)

Saroha, Rakesh; Panwar, Amrish K.

2017-06-01

The intention of this work is to study the effect of in situ pyrolysis of acetylene (C2H2) gas used as a carbon source on the physicochemical and electrochemical performance of pristine LiFePO4 (LFP). Acetylene gas, which decomposed to carbon and methane along with some side products when exposed to high temperature (>625 °C), is used as a carbon source for coating over the surface of LFP particles. Thermogravimetric (TGA) measurements were performed in an air atmosphere, primarily to estimate the exact amount of carbon deposited on the surface of the olivine cathode material due to the decomposition of C2H2 gas. Raman and TGA results confirm the presence of carbon as coated on the surface of the prepared compositions. Among all the synthesized samples, LFP with 10 min C2H2 treatment (LFPC10) shows the highest discharge capacity at all C-rates and exhibits excellent rate performance. LFPC10 delivers a specific discharge capacity of 144 (±5) mAh g-1 (~85% of the theoretical capacity of 170 mAh g-1) at 0.1C rate. LFPC10 demonstrates the best cycling performance as it offers an initial discharge capacity of about 117 (±5) mAh g-1 (~69% of the theoretical capacity) at 1C-rate and has 97% capacity retention even after 100 charge/discharge cycles.

Hybrid excitations due to crystal field, spin-orbit coupling, and spin waves in LiFePO 4

DOE PAGES

Yiu, Yuen; Le, Manh Duc; Toft-Peterson, Rasmus; ...

2017-03-09

Here, we report on the spin waves and crystal field excitations in single crystal LiFePO 4 by inelastic neutron scattering over a wide range of temperatures, below and above the antiferromagnetic transition of this system. In particular, we find extra excitations below T N = 50 K that are nearly dispersionless and are most intense around magnetic zone centers. Furthermore, we show that these excitations correspond to transitions between thermally occupied excited states of Fe 2 + due to splitting of the S = 2 levels that arise from the crystal field and spin-orbit interactions. These excitations are further amplifiedmore » by the highly distorted nature of the oxygen octahedron surrounding the iron atoms. Above T N , magnetic fluctuations are observed up to at least 720 K, with an additional inelastic excitation around 4 meV, which we attribute to single-ion effects, as its intensity weakens slightly at 720 K compared to 100 K, which is consistent with the calculated cross sections using a single-ion model. This theoretical analysis, using the MF-RPA model, provides both detailed spectra of the Fe d shell and estimates of the average ordered magnetic moment and T N . By applying the MF-RPA model to a number of existing spin-wave results from other Li M PO 4 ( M = Mn , Co, and Ni), we are able to obtain reasonable predictions for the moment sizes and transition temperatures.« less

Solvothermal synthesis of monodisperse LiFePO4 micro hollow spheres as high performance cathode material for lithium ion batteries.

PubMed

Yang, Shiliu; Hu, Mingjun; Xi, Liujiang; Ma, Ruguang; Dong, Yucheng; Chung, C Y

2013-09-25

A microspherical, hollow LiFePO4 (LFP) cathode material with polycrystal structure was simply synthesized by a solvothermal method using spherical Li3PO4 as the self-sacrificed template and FeCl2·4H2O as the Fe(2+) source. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show that the LFP micro hollow spheres have a quite uniform size of ~1 μm consisting of aggregated nanoparticles. The influences of solvent and Fe(2+) source on the phase and morphology of the final product were chiefly investigated, and a direct ion exchange reaction between spherical Li3PO4 templates and Fe(2+) ions was firstly proposed on the basis of the X-ray powder diffraction (XRD) transformation of the products. The LFP nanoparticles in the micro hollow spheres could finely coat a uniform carbon layer ~3.5 nm by a glucose solution impregnating-drying-sintering process. The electrochemical measurements show that the carbon coated LFP materials could exhibit high charge-discharge capacities of 158, 144, 125, 101, and even 72 mAh g(-1) at 0.1, 1, 5, 20, and 50 C, respectively. It could also maintain 80% of the initial discharge capacity after cycling for 2000 times at 20 C.

Aligned Li+ Tunnels in Core-Shell Li(NixMnyCoz)O2@LiFePO4 Enhances Its High Voltage Cycling Stability as Li-ion Battery Cathode.

PubMed

Wu, Zhongzhen; Ji, Shunping; Liu, Tongchao; Duan, Yandong; Xiao, Shu; Lin, Yuan; Xu, Kang; Pan, Feng

2016-10-12

Layered transition-metal oxides (Li[Ni x Mn y Co z ]O 2 , NMC, or NMCxyz) due to their poor stability when cycled at a high operating voltage (>4.5 V) have limited their practical applications in industry. Earlier researches have identified Mn(II)-dissolution and some parasitic reactions between NMC surface and electrolyte, especially when NMC is charged to a high potential, as primarily factors responsible for the fading. In our previous work, we have achieved a capacity of NMC active material close to theoretical value and optimized its cycling performance by a depolarized carbon nanotubes (CNTs) network and an unique "pre-lithiation process" that generates an in situ organic coating (∼40 nm) to prevent Mn(II) dissolution and minimize the parasitic reactions. Unfortunately, this organic coating is not durable enough during a long-term cycling when the cathode operates at a high potential (>4.5 V). This work attempts to improve the surface protection of the NMC532 particles by applying an active inorganic coating consisting of nanosized- and crystal-orientated LiFePO 4 (LFP) (about 50 nm, exposed (010) face) to generate a core-shell nanostructure of Li(Ni x Mn y Co z )O 2 @LiFePO 4 . Transmission electron microscopy (TEM) and etching X-ray photoelectron spectroscopy have confirmed an intimate contact coating (about 50 nm) between the original structure of NMC and LFP single-particle with atomic interdiffusion at the core-shell interface, and an array of interconnected aligned Li + tunnels are observed at the interface by cross-sectional high-resolution TEM, which were formed by ball-milling and then strictly controlling the temperature below 100 °C. Batteries based on this modified NMC cathode material show a high reversible capacity when cycled between 3.0 and 4.6 V during a long-term cycling.

High power Nb-doped LiFePO4 Li-ion battery cathodes; pilot-scale synthesis and electrochemical properties

NASA Astrophysics Data System (ADS)

Johnson, Ian D.; Blagovidova, Ekaterina; Dingwall, Paul A.; Brett, Dan J. L.; Shearing, Paul R.; Darr, Jawwad A.

2016-09-01

High power, phase-pure Nb-doped LiFePO4 (LFP) nanoparticles are synthesised using a pilot-scale continuous hydrothermal flow synthesis process (production rate of 6 kg per day) in the range 0.01-2.00 at% Nb with respect to total transition metal content. EDS analysis suggests that Nb is homogeneously distributed throughout the structure. The addition of fructose as a reagent in the hydrothermal flow process, followed by a post synthesis heat-treatment, affords a continuous graphitic carbon coating on the particle surfaces. Electrochemical testing reveals that cycling performance improves with increasing dopant concentration, up to a maximum of 1.0 at% Nb, for which point a specific capacity of 110 mAh g-1 is obtained at 10 C (6 min for the charge or discharge). This is an excellent result for a high power cathode LFP based material, particularly when considering the synthesis was performed on a large pilot-scale apparatus.

Direct view on the phase evolution in individual LiFePO4 nanoparticles during Li-ion battery cycling.

PubMed

Zhang, Xiaoyu; van Hulzen, Martijn; Singh, Deepak P; Brownrigg, Alex; Wright, Jonathan P; van Dijk, Niels H; Wagemaker, Marnix

2015-09-23

Phase transitions in Li-ion electrode materials during (dis)charge are decisive for battery performance, limiting high-rate capabilities and playing a crucial role in the cycle life of Li-ion batteries. However, the difficulty to probe the phase nucleation and growth in individual grains is hindering fundamental understanding and progress. Here we use synchrotron microbeam diffraction to disclose the cycling rate-dependent phase transition mechanism within individual particles of LiFePO4, a key Li-ion electrode material. At low (dis)charge rates well-defined nanometer thin plate-shaped domains co-exist and transform much slower and concurrent as compared with the commonly assumed mosaic transformation mechanism. As the (dis)charge rate increases phase boundaries become diffuse speeding up the transformation rates of individual grains. Direct observation of the transformation of individual grains reveals that local current densities significantly differ from what has previously been assumed, giving new insights in the working of Li-ion battery electrodes and their potential improvements.

Direct view on the phase evolution in individual LiFePO4 nanoparticles during Li-ion battery cycling

PubMed Central

Zhang, Xiaoyu; van Hulzen, Martijn; Singh, Deepak P.; Brownrigg, Alex; Wright, Jonathan P.; van Dijk, Niels H.; Wagemaker, Marnix

2015-01-01

Phase transitions in Li-ion electrode materials during (dis)charge are decisive for battery performance, limiting high-rate capabilities and playing a crucial role in the cycle life of Li-ion batteries. However, the difficulty to probe the phase nucleation and growth in individual grains is hindering fundamental understanding and progress. Here we use synchrotron microbeam diffraction to disclose the cycling rate-dependent phase transition mechanism within individual particles of LiFePO4, a key Li-ion electrode material. At low (dis)charge rates well-defined nanometer thin plate-shaped domains co-exist and transform much slower and concurrent as compared with the commonly assumed mosaic transformation mechanism. As the (dis)charge rate increases phase boundaries become diffuse speeding up the transformation rates of individual grains. Direct observation of the transformation of individual grains reveals that local current densities significantly differ from what has previously been assumed, giving new insights in the working of Li-ion battery electrodes and their potential improvements. PMID:26395323

LiFePO4 microcrystals as an efficient heterogeneous Fenton-like catalyst in degradation of rhodamine 6G.

PubMed

Li, Zhan Jun; Ali, Ghafar; Kim, Hyun Jin; Yoo, Seong Ho; Cho, Sung Oh

2014-01-01

We present a novel heterogeneous Fenton-like catalyst of LiFePO4 (LFP). LFP has been widely used as an electrode material of a lithium ion battery, but we observed that commercial LFP (LFP-C) could act as a good Fenton-like catalyst to decompose rhodamine 6G. The catalytic activity of LFP-C microparticles was much higher than a popular catalyst, magnetite nanoparticles. Furthermore, we found that the catalytic activity of LFP-C could be further increased by increasing the specific surface area. The reaction rate constant of the hydrothermally synthesized LFP microcrystals (LFP-H) is at least 18 times higher than that of magnetite nanoparticles even though the particle size of LFP is far larger than magnetite nanoparticles. The LFP catalysts also exhibited a good recycling behavior and high stability under an oxidizing environment. The effects of the experimental parameters such as the concentration of the catalysts, pH, and the concentration of hydrogen peroxide on the catalytic activity of LFP were also analyzed.

Fast charging technique for high power LiFePO4 batteries: A mechanistic analysis of aging

NASA Astrophysics Data System (ADS)

Anseán, D.; Dubarry, M.; Devie, A.; Liaw, B. Y.; García, V. M.; Viera, J. C.; González, M.

2016-07-01

One of the major issues hampering the acceptance of electric vehicles (EVs) is the anxiety associated with long charging time. Hence, the ability to fast charging lithium-ion battery (LIB) systems is gaining notable interest. However, fast charging is not tolerated by all LIB chemistries because it affects battery functionality and accelerates its aging processes. Here, we investigate the long-term effects of multistage fast charging on a commercial high power LiFePO4-based cell and compare it to another cell tested under standard charging. Coupling incremental capacity (IC) and IC peak area analysis together with mechanistic model simulations ('Alawa' toolbox with harvested half-cell data), we quantify the degradation modes that cause aging of the tested cells. The results show that the proposed fast charging technique caused similar aging effects as standard charging. The degradation is caused by a linear loss of lithium inventory, coupled with a less degree of linear loss of active material on the negative electrode. This study validates fast charging as a feasible mean of operation for this particular LIB chemistry and cell architecture. It also illustrates the benefits of a mechanistic approach to understand cell degradation on commercial cells.

Carboxymethyl chitosan/conducting polymer as water-soluble composite binder for LiFePO4 cathode in lithium ion batteries

NASA Astrophysics Data System (ADS)

Zhong, Haoxiang; He, Aiqin; Lu, Jidian; Sun, Minghao; He, Jiarong; Zhang, Lingzhi

2016-12-01

A water-soluble conductive composite binder consisting of carboxymethyl chitosan (CCTS) as a binder and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) as a conduction-promoting agent is reported for the LiFePO4 (LFP) cathode in Li-ion batteries. The introduction of conductive PEDOT:PSS as a conductive composite binder facilitates the formation of homogeneous and continuous conducting bridges throughout the electrode and raises the compaction density of the electrode sheet by decreasing the amounts of the commonly used conducting agent of acetylene black. The optimized replacement ratios of acetylene black with PEDOT:PSS (acetylene black/PEDOT:PSS = 1:1, by weight) are obtained by measuring electrical conductivity, peel strength and compaction density of the electrode sheets. The LFP half-cell with the optimized conductive binder exhibits better cycling and rate performance and more favorable electrochemical kinetics than that using only acetylene black conducting agent. The pilot application of PEDOT:PSS/CCTS binder in 10 Ah CCTS-LFP prismatic cell exhibits a comparable cycling performance, retaining 89.7% of capacity at 1 C/2 C (charge/discharge) rate as compared with 90% for commercial PVDF-LFP over 1000 cycles, and better rate capability than that of commercial PVDF-LFP, retaining 98% capacity of 1 C at 7 C rate as compared with 95.4% for PVDF-LFP.

Synthesis of triaxial LiFePO4 nanowire with a VGCF core column and a carbon shell through the electrospinning method.

PubMed

Hosono, Eiji; Wang, Yonggang; Kida, Noriyuki; Enomoto, Masaya; Kojima, Norimichi; Okubo, Masashi; Matsuda, Hirofumi; Saito, Yoshiyasu; Kudo, Tetsuichi; Honma, Itaru; Zhou, Haoshen

2010-01-01

A triaxial LiFePO4 nanowire with a multi wall carbon nanotube (VGCF:Vapor-grown carbon fiber) core column and an outer shell of amorphous carbon was successfully synthesized through the electrospinning method. The carbon nanotube core oriented in the direction of the wire played an important role in the conduction of electrons during the charge-discharge process, whereas the outer amorphous carbon shell suppressed the oxidation of Fe2+. An electrode with uniformly dispersed carbon and active materials was easily fabricated via a single process by heating after the electrospinning method is applied. Mossbauer spectroscopy for the nanowire showed a broadening of the line width, indicating a disordered coordination environment of the Fe ion near the surface. The electrospinning method was proven to be suitable for the fabrication of a triaxial nanostructure.

Synthesis of nanometer-sized fayalite and magnesium-iron(II) mixture olivines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qafoku, Odeta; Ilton, Eugene S.; Bowden, Mark E.

Olivines are divalent orthosilicates with important geologic, biological, and industrial significance and are typically comprised of mixtures of Mg2+ and Fe2+ ranging from forsterite (Mg2SiO4) to fayalite (Fe2SiO4). Investigating the role of Fe(II) in olivine reactivity requires the ability to synthesize olivines that are nanometer-sized, have different percentages of Mg2+ and Fe2+, and have good bulk and surface purity. This article demonstrates a new method for synthesizing nanosized fayalite and Mg-Fe mixture olivines. First, carbonaceous precursors are generated from sucrose, PVA, colloidal silica, Mg2+, and Fe3+. Second, these precursors are calcined in air to burn carbon and create mixtures ofmore » Fe(III)-oxides, forsterite, and SiO2. Finally, calcination in reducing CO-CO2 gas buffer leads to Fe(II)-rich olivines. XRD, Mössbauer, and IR analyses verify good bulk purity and composition. XPS indicates that surface iron is in its reduced Fe(II) form, and surface Si is consistent with olivine. SEM shows particle sizes predominately between 50 and 450 nm, and BET surface areas are 2.8-4.2 m2/g. STEM HAADF analysis demonstrates even distributions of Mg and Fe among the available M1 and M2 sites of the olivine crystals. These nanosized Fe(II)-rich olivines are suitable for laboratory studies with in situ probes that require mineral samples with high reactivity at short timescales.« less

Seismicity triggered by the olivine-spinel transition: New insights from combined XRD and acoustic emission monitoring during deformation experiments in Mg2GeO4

NASA Astrophysics Data System (ADS)

Schubnel, A. J.; Hilairet, N.; Gasc, J.; Héripré, E.; Brunet, F.; Wang, Y.

2010-12-01

Polycrystalline Mg2GeO4-olivine has been deformed (strain rates from 2.10-4/s to 10-5/s) in the deformation-DIA in 13-BM-D at GSECARS (Advanced Photon Source) at ca. 2 GPa confining pressure for temperatures between 973 and 1573 K (i.e., in the Mg2GeO4-ringwoodite field). Stress, advancement of transformation, and strain were measured in-situ using X-ray diffraction (XRD) and imaging, and acoustic emissions (AE) full waveforms were recorded simultaneously. When differential stress is applied (ca. 1- to 2 GPa) and temperature is increased, the very beginning of the transformation to the ringwoodite structure (as evidenced by in situ XRD) is accompanied by AE bursts which locate within the sample. At high strain rates (>10-4/s) and low temperatures (800-900 degrees C), the number of AEs is comparable, if not larger, to that observed during the cold compression of quartz grains. The largest events always occur at a temperature slightly below that of appearance of the ringwoodite-structure phase on the XRD images patterns. This suggests that AEs are generated while the transition is still nucleation controlled (pseudo-martensitic stage). During stress-relaxation periods, the rate of AE triggering decreases, but does not completely vanish. The AE production rate increases again as soon as deformation is started again. Importantly, we still observed very large AEs at strain rates as low as approx. 10-5/ s. At these early stages of the transformation, the samples did not show any macroscopic rheological weakening. Focal mechanism analysis of the largest AEs showed that they are all of shear type, some being even pure double couple. They radiate about the same amount of energy as typically recorded during fast crack propagation in amorphous glass material. This suggests that they cannot only originate from the martensitic nucleation of oriented spinel-lamellae within a single germanium olivine crystal. Preliminary microstructural analysis (SEM and EBSD) highlights the

A Calcium-in-Olivine Geohygrometer and its Application to Subduction Zone Magmatism

NASA Astrophysics Data System (ADS)

Gavrilenko, M.; Herzberg, C. T.; Vidito, C. A.; Carr, M. J.; Tenner, T.; Ozerov, A.

2016-12-01

Calcium contents of subduction zone olivines are lower than those for olivines from modern MORB, Archean komatiites, and Hawaii (Fig. 1). A role for magmatic H2O is likely for subduction zone olivines, and we have explored the suggestion by [1] that H2O has affected the partitioning of CaO between olivine and silicate melt. We provide a provisional calibration of DCaOOl/L as a function of magmatic MgO and H2O, based on nominally anhydrous experiments (Fig. 2) and minimally degassed H2O contents of olivine-hosted melt inclusions (Fig. 3). The low diffusivity of Ca in olivine [2], when compared to that of H+ [3, 4, 5, 6], might help to retain the memory of magmatic water that is otherwise lost by diffusion and degassing. Application of our geohygrometer (Fig. 4) typically yields 3 to 4 wt. % magmatic H2O at the Kamchatka and Central American arcs for olivines having 1000 ppm Ca, which agrees with H2O maxima from melt inclusion studies [7]; Cerro Negro and Shiveluch volcanoes are exceptions, with about 6% H2O. Our geohygrometer is by no means a replacement for more accurate methods of H2O analysis, but it has the advantage of applicability in cases where olivine-hosted melt inclusions do not exist (or in case when melt inclusions are partly or completely degassed). Additionally, application of the geohygrometer to core-rim olivine Ca analyses has the potential to reveal changes in magmatic H2O, as revealed by Klyuchevskoy and Shiveluch volcanoes. High precision EMPA analyses with 10-20 µm spatial resolution on some olivine grains from Klyuchevskoy and Shiveluch show a decrease in Ca content from core centers to the rim contacts. Our geohygrometer indicates the olivine grains may record changing magmatic H2O. Furthermore, high Mg numbers and Ni contents indicate these are mantle olivines, and the inferred H2O may be recording entry from the slab to the mantle wedge, a prediction that will be tested by SIMS analyses. References: [1] Feig et al. (2006) CMP, 152

Novel Organic-Inorganic Hybrid Electrolyte to Enable LiFePO4 Quasi-Solid-State Li-Ion Batteries Performed Highly around Room Temperature.

PubMed

Tan, Rui; Gao, Rongtan; Zhao, Yan; Zhang, Mingjian; Xu, Junyi; Yang, Jinlong; Pan, Feng

2016-11-16

A novel type of organic-inorganic hybrid polymer electrolytes with high electrochemical performances around room temperature is formed by hybrid of nanofillers, Y-type oligomer, polyoxyethylene and Li-salt (PBA-Li), of which the T g and T m are significantly lowered by blended heterogeneous polyethers and embedded nanofillers with benefit of the dipole modification to achieve the high Li-ion migration due to more free-volume space. The quasi-solid-state Li-ion batteries based on the LiFePO 4 /15PBA-Li/Li-metal cells present remarkable reversible capacities (133 and 165 mAh g -1 @0.2 C at 30 and 45 °C, respectively), good rate ability and stable cycle performance (141.9 mAh g -1 @0.2 C at 30 °C after 150 cycles).

Tuning Li-Ion Diffusion in α-LiMn 1–x Fe x PO 4 Nanocrystals by Antisite Defects and Embedded β-Phase for Advanced Li-Ion Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Jiangtao; Xiao, Yinguo; Tang, Hanting

Olivine-structured LiMn1-xFexPO4 has become a promising candidate for cathode materials owing to its higher working voltage of 4.1 V and thus larger energy density than that of LiFePO4, which has been used for electric vehicles batteries with the advantage of high safety but disadvantage of low energy density due to its lower working voltage of 3.4 V. One drawback of LiMn1-xFexPO4 electrode is its relatively low electronic and Li-ionic conductivity with Li-ion one-dimensional diffusion. Herein, olivine-structured α-LiMn0.5Fe0.5PO4 nanocrystals were synthesized with optimized Li-ion diffusion channels in LiMn1-xFexPO4 nanocrystals by inducing high concentrations of Fe2+-Li+ antisite defects, which showed impressive capacitymore » improvements of approaching 162, 127, 73, and 55 mAh g-1 at 0.1, 10, 50, and 100 C, respectively, and a long-term cycling stability of maintaining about 74% capacity after 1000 cycles at 10 C. By using high-resolution transmission electron microscopy imaging and joint refinement of hard X-ray and neutron powder diffraction patterns, we revealed that the extraordinary high-rate performance could be achieved by suppressing the formation of electrochemically inactive phase (β-LiMn1-xFexPO4, which is first reported in this work) embedded in α-LiMn0.5Fe0.5PO4. Because of the coherent orientation relationship between β- and α- phases, the β-phase embedded would impede the Li+ diffusion along the [100] and/or [001] directions that was activated by the high density of Fe2+-Li+ antisite (4.24%) in α-phase. Thus, by optimizing concentrations of Fe2+-Li+ antisite defects and suppressing β-phase-embedded olivine structure, Li-ion diffusion properties in LiMn1-xFexPO4 nanocrystals can be tuned by generating new Li+ tunneling. These findings may provide insights into the design and generation of other advanced electrode materials with improved rate performance.« less

Tuning Li-Ion Diffusion in α-LiMn 1–xFe xPO 4 Nanocrystals by Antisite Defects and Embedded β-Phase for Advanced Li-Ion Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Jiangtao; Xiao, Yinguo; Tang, Hanting

Olivine-structured LiMn 1–xFe xPO 4 has become a promising candidate for cathode materials owing to its higher working voltage of 4.1 V and thus larger energy density than that of LiFePO 4, which has been used for electric vehicles batteries with the advantage of high safety but disadvantage of low energy density due to its lower working voltage of 3.4 V. One drawback of LiMn 1–xFe xPO 4 electrode is its relatively low electronic and Li-ionic conductivity with Li-ion one-dimensional diffusion. In this paper, olivine-structured α-LiMn 0.5Fe 0.5PO 4 nanocrystals were synthesized with optimized Li-ion diffusion channels in LiMn 1–xFemore » xPO 4 nanocrystals by inducing high concentrations of Fe 2+–Li + antisite defects, which showed impressive capacity improvements of approaching 162, 127, 73, and 55 mAh g –1 at 0.1, 10, 50, and 100 C, respectively, and a long-term cycling stability of maintaining about 74% capacity after 1000 cycles at 10 C. By using high-resolution transmission electron microscopy imaging and joint refinement of hard X-ray and neutron powder diffraction patterns, we revealed that the extraordinary high-rate performance could be achieved by suppressing the formation of electrochemically inactive phase (β-LiMn 1–xFe xPO 4, which is first reported in this work) embedded in α-LiMn 0.5Fe 0.5PO 4. Because of the coherent orientation relationship between β- and α-phases, the β-phase embedded would impede the Li + diffusion along the [100] and/or [001] directions that was activated by the high density of Fe 2+–Li + antisite (4.24%) in α-phase. Thus, by optimizing concentrations of Fe 2+–Li + antisite defects and suppressing β-phase-embedded olivine structure, Li-ion diffusion properties in LiMn 1–xFe xPO 4 nanocrystals can be tuned by generating new Li + tunneling. Finally, these findings may provide insights into the design and generation of other advanced electrode materials with improved rate performance.« less

Tuning Li-Ion Diffusion in α-LiMn 1–xFe xPO 4 Nanocrystals by Antisite Defects and Embedded β-Phase for Advanced Li-Ion Batteries

DOE PAGES

Hu, Jiangtao; Xiao, Yinguo; Tang, Hanting; ...

2017-07-13

Olivine-structured LiMn 1–xFe xPO 4 has become a promising candidate for cathode materials owing to its higher working voltage of 4.1 V and thus larger energy density than that of LiFePO 4, which has been used for electric vehicles batteries with the advantage of high safety but disadvantage of low energy density due to its lower working voltage of 3.4 V. One drawback of LiMn 1–xFe xPO 4 electrode is its relatively low electronic and Li-ionic conductivity with Li-ion one-dimensional diffusion. In this paper, olivine-structured α-LiMn 0.5Fe 0.5PO 4 nanocrystals were synthesized with optimized Li-ion diffusion channels in LiMn 1–xFemore » xPO 4 nanocrystals by inducing high concentrations of Fe 2+–Li + antisite defects, which showed impressive capacity improvements of approaching 162, 127, 73, and 55 mAh g –1 at 0.1, 10, 50, and 100 C, respectively, and a long-term cycling stability of maintaining about 74% capacity after 1000 cycles at 10 C. By using high-resolution transmission electron microscopy imaging and joint refinement of hard X-ray and neutron powder diffraction patterns, we revealed that the extraordinary high-rate performance could be achieved by suppressing the formation of electrochemically inactive phase (β-LiMn 1–xFe xPO 4, which is first reported in this work) embedded in α-LiMn 0.5Fe 0.5PO 4. Because of the coherent orientation relationship between β- and α-phases, the β-phase embedded would impede the Li + diffusion along the [100] and/or [001] directions that was activated by the high density of Fe 2+–Li + antisite (4.24%) in α-phase. Thus, by optimizing concentrations of Fe 2+–Li + antisite defects and suppressing β-phase-embedded olivine structure, Li-ion diffusion properties in LiMn 1–xFe xPO 4 nanocrystals can be tuned by generating new Li + tunneling. Finally, these findings may provide insights into the design and generation of other advanced electrode materials with improved rate performance.« less

ZnFe2O4-C/LiFePO4-CNT: A Novel High-Power Lithium-Ion Battery with Excellent Cycling Performance.

PubMed

Varzi, Alberto; Bresser, Dominic; von Zamory, Jan; Müller, Franziska; Passerini, Stefano

2014-07-15

An innovative and environmentally friendly battery chemistry is proposed for high power applications. A carbon-coated ZnFe 2 O 4 nanoparticle-based anode and a LiFePO 4 -multiwalled carbon nanotube-based cathode, both aqueous processed with Na-carboxymethyl cellulose, are combined, for the first time, in a Li-ion full cell with exceptional electrochemical performance. Such novel battery shows remarkable rate capabilities, delivering 50% of its nominal capacity at currents corresponding to ≈20C (with respect to the limiting cathode). Furthermore, the pre-lithiation of the negative electrode offers the possibility of tuning the cell potential and, therefore, achieving remarkable gravimetric energy and power density values of 202 Wh kg -1 and 3.72 W kg -1 , respectively, in addition to grant a lithium reservoir. The high reversibility of the system enables sustaining more than 10 000 cycles at elevated C-rates (≈10C with respect to the LiFePO 4 cathode), while retaining up to 85% of its initial capacity.

Analysis of laser induced plasma of lithium iron phosphate/LiFePO4 using Nd:YAG laser at low pressure

NASA Astrophysics Data System (ADS)

Suliyanti, M. M.; Hidayah, A. N.; Isnaeni

2017-04-01

Preliminary analysis of lithium in Lithium Iron Phosphate (LiFePO4) powder using laser induced plasma spectroscopy at low pressure had been done. Recently, LiFePO4-based batteries are widely used in most electric cars and bikes due to less toxic. However, lithium (Li) element is very difficult to detect since it is a very light element. In this work, we used a Nd:YAG laser (1064 nm wavelength, 5 ns pulse width at 10 Hz repetition rate) that was focused on LiFePO4 sample at low pressure. The main Li peak emission in LiFePO4 powder and sheet can be easily detected using this technique. We report the results of experimental study on Li element emission lines at wavelength 460.18 nm, 610.37 nm and 670.83 nm using 2 mJ and 12 mJ laser irradiation at 5 Torr and 35 Torr air atmosphere. The results of this study showed promising application of laser-induced plasma spectroscopy to detect and analyse Li in various samples.

Olivines and olivine coronas in mesosiderites

NASA Technical Reports Server (NTRS)

Nehru, C. E.; Zucker, S. M.; Harlow, G. E.; Prinz, M.

1980-01-01

The paper presents a study of olivines and their surrounding coronas in mesosiderites texturally and compositionally using optical and microprobe methods. Olivine composition ranges from Fo(58-92) and shows no consistent pattern of distribution within and between mesosiderites; olivine occurs as large single crystals or as partially recrystallized mineral clasts, except for two lithic clasts. These are Emery and Vaca Muerta, and both are shock-modified olivine orthopyroxenites. Fine-grained coronas surround olivine, except for those in impact-melt group mesosiderites and those without tridymite in their matrices. Coronas consist largely of orthopyroxene, plagioclase, clinopyroxene, chromite, merillite, and ilmenite, and are similar to the matrix, but lack metal and tridymite. Texturally the innermost parts of the corona can be divided into three stages of development: (1) radiating acicular, (2) intermediate, and (3) granular.

Systematic aging of commercial LiFePO4|Graphite cylindrical cells including a theory explaining rise of capacity during aging

NASA Astrophysics Data System (ADS)

Lewerenz, Meinert; Münnix, Jens; Schmalstieg, Johannes; Käbitz, Stefan; Knips, Marcus; Sauer, Dirk Uwe

2017-03-01

The contribution introduces a new theory explaining the capacity increase that is often observed in early stages of life of lithium-ion batteries. This reversible and SOC-depending capacity rise is explained by the passive electrode effect in this work. The theory assumes a slow, compensating flow of active lithium between the passive and the active part of the anode, where the passive part represents the geometric excess anode with respect to the cathode. The theory is validated using a systematic test of 50 cylindrical 8 Ah LiFePO4|Graphite battery cells analyzed during cyclic and calendaric aging. The cyclic aging has been performed symmetrically at 40 °C cell temperature, varying current rates and DODs. The calendar aging is executed at three temperatures and up to four SOCs. The aging is dominated by capacity fade while the increase of internal resistance is hardly influenced. Surprisingly shallow cycling between 45 and 55% SOC shows stronger aging than aging at higher DOD and tests at 4 C exhibit less aging than aging at lower C-rates. Aging mechanisms at 60 °C seem to deviate from those at 40 °C or lower. The data of this aging matrix is used for further destructive and non-destructive characterization in future contributions.

Large Charge-Transfer Energy in LiFePO4 Revealed by Full-Multiplet Calculation for the Fe L3 -edge Soft X-ray Emission Spectra.

PubMed

Asakura, Daisuke; Nanba, Yusuke; Makinose, Yuki; Matsuda, Hirofumi; Glans, Per-Anders; Guo, Jinghua; Hosono, Eiji

2018-04-17

We analyzed the Fe 3d electronic structure in LiFePO 4 /FePO 4 (LFP/FP) nanowire with a high cyclability by using soft X-ray emission spectroscopy (XES) combined with configuration-interaction full-multiplet (CIFM) calculation. The ex situ Fe L 2,3 -edge resonant XES (RXES) spectra for LFP and FP are ascribed to oxidation states of Fe 2+ and Fe 3+ , respectively. CIFM calculations for Fe 2+ and Fe 3+ states reproduced the Fe L 3 RXES spectra for LFP and FP, respectively. In the calculations for both states, the charge-transfer energy was considerably larger than those for typical iron oxides, indicating very little electron transfer from the O 2p to Fe 3d orbitals and a weak hybridization on the Fe-O bond during the charge-discharge reactions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The ascent of kimberlite: Insights from olivine

NASA Astrophysics Data System (ADS)

Brett, R. C.; Russell, J. K.; Andrews, G. D. M.; Jones, T. J.

2015-08-01

Olivine xenocrysts are ubiquitous in kimberlite deposits worldwide and derive from the disaggregation of mantle-derived peridotitic xenoliths. Here, we provide descriptions of textural features in xenocrystic olivine from kimberlite deposits at the Diavik Diamond Mine, Canada and at Igwisi Hills volcano, Tanzania. We establish a relative sequence of textural events recorded by olivine during magma ascent through the cratonic mantle lithosphere, including: xenolith disaggregation, decompression fracturing expressed as mineral- and fluid-inclusion-rich sealed and healed cracks, grain size and shape modification by chemical dissolution and abrasion, late-stage crystallization of overgrowths on olivine xenocrysts, and lastly, mechanical milling and rounding of the olivine cargo prior to emplacement. Ascent through the lithosphere operates as a "kimberlite factory" wherein progressive upward dyke propagation of the initial carbonatitic melt fractures the overlying mantle to entrain and disaggregate mantle xenoliths. Preferential assimilation of orthopyroxene (Opx) xenocrysts by the silica-undersaturated carbonatitic melt leads to deep-seated exsolution of CO2-rich fluid generating buoyancy and supporting rapid ascent. Concomitant dissolution of olivine produces irregular-shaped relict grains preserved as cores to most kimberlitic olivine. Multiple generations of decompression cracks in olivine provide evidence for a progression in ambient fluid compositions (e.g., from carbonatitic to silicic) during ascent. Numerical modelling predicts tensile failure of xenoliths (disaggregation) and olivine (cracks) over ascent distances of 2-7 km and 15-25 km, respectively, at velocities of 0.1 to >4 m s-1. Efficient assimilation of Opx during ascent results in a silica-enriched, olivine-saturated kimberlitic melt (i.e. SiO2 >20 wt.%) that crystallizes overgrowths on partially digested and abraded olivine xenocrysts. Olivine saturation is constrained to occur at pressures <1 GPa; an

Morphology-controlled synthesis of self-assembled LiFePO4/C/RGO for high-performance Li-ion batteries.

PubMed

Lin, Mei; Chen, Yuming; Chen, Bolei; Wu, Xiao; Kam, Kifung; Lu, Wei; Chan, Helen Lai Wa; Yuan, Jikang

2014-10-22

Novel architectured LiFePO4 (LFP) that consisted of ordered LFP nanocubes was prepared through a facile hydrothermal method using polyethylene glycol (PEG) as a surfactant. The micro/nanostructured LFP with various morphologies ranging from cube cluster to rugby-like structure was synthesized via controlling the pH values of the precursor. A reasonable assembly process elucidating the formation of the hierarchical structure is also provided based on the experimental results. After a combination of carbon (C) coating and reduced graphene oxide (RGO) wrapping, the obtained LFP/C/RGO composites exhibit enhanced electrochemical performance compared to that of blank LFP synthesized under the same condition. Among as-synthesized cube-cluster-like, dumbbell-like, rod-like, and rugby-like composites, the rugby-like LFP/C/RGO reveal the best electrochemical properties with the discharge specific capacity of ∼150 mA h g(-1) after 100 cycles and a high reversible specific capacity of 152 mA h g(-1) at 0.1 C. The prepared LFP/C/RGO composite can be a promising cathode material for high energy, low cost, and environmentally friendly lithium-ion batteries.

The optimization of CMC concentration as graphite binder on the anode of LiFePO4 battery

NASA Astrophysics Data System (ADS)

Hidayat, S.; Cahyono, T.; Mindara, J. Y.; Riveli, N.; Alamsyah, W.; Rahayu, I.

2017-05-01

Recently, the most dominating power supply on the mobile electronics market are rechargeable Lithium-ion batteries. This is because of a higher energy density and a longer lifetime compared to similar rechargeable battery systems. Graphite is commonly used as anode material in the Lithium-ion batteries, because of its excellent electrochemical characteristics and low cost fabrication. In this paper, we reported the optimization of the concentration of the CMC (carboxymethyl cellulose), that acts as the binder for graphite anode. Based on our experimental results, the best composition of graphite : C : CMC is 90 : 8 : 2 in weight %. Anode with such composition has, based on SEM measurement, a relatively good surface morphology, while it also has relatively high conductivity, about 2.68 S/cm. The result of cyclic voltammogram with a scan rate of 10 mV/s in the voltage range of 0 to 1 Volt, shows the peak of reduction voltage at 0.85 Volts and the peak voltage of oxidation is at -1.5 Volt. The performance of the battery system with LiFePO4 set as the cathode, shows that the working voltage is about 2.67 Volts at 1 mA current-loading, with the efficiency around 47%.

Heat loss distribution: Impedance and thermal loss analyses in LiFePO4/graphite 18650 electrochemical cell

NASA Astrophysics Data System (ADS)

Balasundaram, Manikandan; Ramar, Vishwanathan; Yap, Christopher; Lu, Li; Tay, Andrew A. O.; Palani, Balaya

2016-10-01

We report here thermal behaviour and various components of heat loss of 18650-type LiFePO4/graphite cell at different testing conditions. In this regard, the total heat generated during charging and discharging processes at various current rates (C) has been quantified in an Accelerating Rate Calorimeter experiment. Irreversible heat generation, which depends on applied current and internal cell resistance, is measured under corresponding charge/discharge conditions using intermittent pulse techniques. On the other hand, reversible heat generation which depends on entropy changes of the electrode materials during the cell reaction is measured from the determination of entropic coefficient at various states of charge/discharge. The contributions of irreversible and reversible heat generation to the total heat generation at both high and low current rates are evaluated. At every state of charge/discharge, the nature of the cell reaction is found to be either exothermic or endothermic which is especially evident at low C rates. In addition, electrochemical impedance spectroscopy measurements are performed on above 18650 cells at various states of charge to determine the components of internal resistance. The findings from the impedance and thermal loss analysis are helpful for understanding the favourable states of charge/discharge for battery operation, and designing better thermal management systems.

Critical evaluation of the stability of highly concentrated LiTFSI - Acetonitrile electrolytes vs. graphite, lithium metal and LiFePO4 electrodes

NASA Astrophysics Data System (ADS)

Nilsson, Viktor; Younesi, Reza; Brandell, Daniel; Edström, Kristina; Johansson, Patrik

2018-04-01

Highly concentrated LiTFSI - acetonitrile electrolytes have recently been shown to stabilize graphite electrodes in lithium-ion batteries (LIBs) much better than comparable more dilute systems. Here we revisit this system in order to optimise the salt concentration vs. both graphite and lithium metal electrodes with respect to electrochemical stability. However, we observe an instability regardless of concentration, making lithium metal unsuitable as a counter electrode, and this also affects evaluation of e.g. graphite electrodes. While the highly concentrated electrolytes have much improved electrochemical stabilities, their reductive decomposition below ca. 1.2 V vs. Li+/Li° still makes them less practical vs. graphite electrodes, and the oxidative reaction with Al at ca. 4.1 V vs. Li+/Li° makes them problematic for high voltage LIB cells. The former originates in an insufficiently stable solid electrolyte interphase (SEI) dissolving and continuously reforming - causing self-discharge, as observed by paused galvanostatic cycling, while the latter is likely caused by aluminium current collector corrosion. Yet, we show that medium voltage LiFePO4 positive electrodes can successfully be used as counter and reference electrodes.

Helium Diffusion in Olivine

NASA Astrophysics Data System (ADS)

Cherniak, D. J.; Watson, E. B.

2011-12-01

Diffusion of helium has been characterized in natural Fe-bearing olivine (~Fo90) and synthetic forsterite. Polished, oriented slabs of olivine were implanted with 3He, at 100 keV at a dose of 5x1015/cm2 or at 3.0 MeV at a dose of 1x1016/cm2. A set of experiments on the implanted olivine were run in 1-atm furnaces. In addition to the one-atm experiments, experiments on implanted samples were also run at higher pressures (2.6 and 2.7 GPa) to assess the potential effects of pressure on He diffusion and the applicability of the measured diffusivities in describing He transport in the mantle. The high-pressure experiments were conducted in a piston-cylinder apparatus using an "ultra-soft" pressure cell, with the diffusion sample directly surrounded by AgCl. 3He distributions following experiments were measured with Nuclear Reaction Analysis using the reaction 3He(d,p)4He. This direct profiling method permits us to evaluate anisotropy of diffusion, which cannot be easily assessed using bulk-release methods. For diffusion in forsterite parallel to c we obtain the following Arrhenius relation over the temperatures 250-950°C: D = 3.91x10-6exp(-159 ± 4 kJ mol-1/RT) m2/sec. The data define a single Arrhenius line spanning more than 7 orders of magnitude in D and 700°C in temperature. Diffusion parallel to a appears slightly slower, yielding an activation energy for diffusion of 135 kJ/mol and a pre-exponential factor of 3.73x10-8 m2/sec. Diffusion parallel to b is slower than diffusion parallel to a (by about two-thirds of a log unit); for this orientation an activation energy of 138 kJ/mol and a pre-exponential factor of 1.34x10-8 m2/sec are obtained. This anisotropy is broadly consistent with observations for diffusion of Ni and Fe-Mg in olivine. Diffusion in Fe-bearing olivine (transport parallel to b) agrees within uncertainty with findings for He diffusion in forsterite. The higher-pressure experiments yield diffusivities in agreement with those from the 1-atm

ZnFe2O4-C/LiFePO4-CNT: A Novel High-Power Lithium-Ion Battery with Excellent Cycling Performance

PubMed Central

Varzi, Alberto; Bresser, Dominic; von Zamory, Jan; Müller, Franziska; Passerini, Stefano

2014-01-01

An innovative and environmentally friendly battery chemistry is proposed for high power applications. A carbon-coated ZnFe2O4 nanoparticle-based anode and a LiFePO4-multiwalled carbon nanotube-based cathode, both aqueous processed with Na-carboxymethyl cellulose, are combined, for the first time, in a Li-ion full cell with exceptional electrochemical performance. Such novel battery shows remarkable rate capabilities, delivering 50% of its nominal capacity at currents corresponding to ≈20C (with respect to the limiting cathode). Furthermore, the pre-lithiation of the negative electrode offers the possibility of tuning the cell potential and, therefore, achieving remarkable gravimetric energy and power density values of 202 Wh kg−1 and 3.72 W kg−1, respectively, in addition to grant a lithium reservoir. The high reversibility of the system enables sustaining more than 10 000 cycles at elevated C-rates (≈10C with respect to the LiFePO4 cathode), while retaining up to 85% of its initial capacity. PMID:26190956

[Laser Raman spectral investigations of the carbon structure of LiFePO4/C cathode material].

PubMed

Yang, Chao; Li, Yong-Mei; Zhao, Quan-Feng; Gan, Xiang-Kun; Yao, Yao-Chun

2013-10-01

In the present paper, Laser Raman spectral was used to study the carbon structure of LiFePO4/C positive material. The samples were also been characterized by X-ray diffraction (XRD), scanning electron microscope(SEM), selected area electron diffraction (SEAD) and resistivity test. The result indicated that compared with the sp2/sp3 peak area ratios the I(D)/I(G) ratios are not only more evenly but also exhibited some similar rules. However, the studies indicated that there exist differences of I(D)/ I(G) ratios and sp2/sp3 peak area ratios among different points in the same sample. And compared with the samples using citric acid or sucrose as carbon source, the sample which was synthetized with mixed carbon source (mixed by citric acid and sucrose) exhibited higher I(D)/I(G) ratios and sp2/sp3 peak area ratios. Also, by contrast, the differences of I(D)/I(G) ratios and sp2/sp3 peak area ratios among different points in the same sample are less than the single carbon source samples' datas. In the scanning electron microscopy (sem) and transmission electron microscopy (sem) images, we can observed the uneven distributions of carbon coating of the primary particles and the secondary particles, this may be the main reason for not being uniform of difference data in the same sample. The obvious discreteness will affect the normal use of Raman spectroscopy in these tests.

Three-Dimensional, Fibrous Lithium Iron Phosphate Structures Deposited by Magnetron Sputtering.

PubMed

Bünting, Aiko; Uhlenbruck, Sven; Sebold, Doris; Buchkremer, H P; Vaßen, R

2015-10-14

Crystalline, three-dimensional (3D) structured lithium iron phosphate (LiFePO4) thin films with additional carbon are fabricated by a radio frequency (RF) magnetron-sputtering process in a single step. The 3D structured thin films are obtained at deposition temperatures of 600 °C and deposition times longer than 60 min by using a conventional sputtering setup. In contrast to glancing angle deposition (GLAD) techniques, no tilting of the substrate is required. Thin films are characterized by X-ray diffraction (XRD), Raman spectrospcopy, scanning electron microscopy (SEM), cyclic voltammetry (CV), and galvanostatic charging and discharging. The structured LiFePO4+C thin films consist of fibers that grow perpendicular to the substrate surface. The fibers have diameters up to 500 nm and crystallize in the desired olivine structure. The 3D structured thin films have superior electrochemical properties compared with dense two-dimensional (2D) LiFePO4 thin films and are, hence, very promising for application in 3D microbatteries.

Mesoscopic modeling and parameter estimation of a lithium-ion battery based on LiFePO4/graphite

NASA Astrophysics Data System (ADS)

Jokar, Ali; Désilets, Martin; Lacroix, Marcel; Zaghib, Karim

2018-03-01

A novel numerical model for simulating the behavior of lithium-ion batteries based on LiFePO4(LFP)/graphite is presented. The model is based on the modified Single Particle Model (SPM) coupled to a mesoscopic approach for the LFP electrode. The model comprises one representative spherical particle as the graphite electrode, and N LFP units as the positive electrode. All the SPM equations are retained to model the negative electrode performance. The mesoscopic model rests on non-equilibrium thermodynamic conditions and uses a non-monotonic open circuit potential for each unit. A parameter estimation study is also carried out to identify all the parameters needed for the model. The unknown parameters are the solid diffusion coefficient of the negative electrode (Ds,n), reaction-rate constant of the negative electrode (Kn), negative and positive electrode porosity (εn&εn), initial State-Of-Charge of the negative electrode (SOCn,0), initial partial composition of the LFP units (yk,0), minimum and maximum resistance of the LFP units (Rmin&Rmax), and solution resistance (Rcell). The results show that the mesoscopic model can simulate successfully the electrochemical behavior of lithium-ion batteries at low and high charge/discharge rates. The model also describes adequately the lithiation/delithiation of the LFP particles, however, it is computationally expensive compared to macro-based models.

Extraction of in situ cosmogenic 14C from olivine

USGS Publications Warehouse

Pigati, J.S.; Lifton, N.A.; Timothy, Jull A.J.; Quade, Jay

2010-01-01

Chemical pretreatment and extraction techniques have been developed previously to extract in situ cosmogenic radiocarbon (in situ 14C) from quartz and carbonate. These minerals can be found in most environments on Earth, but are usually absent from mafic terrains. To fill this gap, we conducted numerous experiments aimed at extracting in situ 14C from olivine ((Fe,Mg)2SiO4). We were able to extract a stable and reproducible in situ 14C component from olivine using stepped heating and a lithium metaborate (LiBO2) flux, following treatment with dilute HNO3 over a variety of experimental conditions. However, measured concentrations for samples from the Tabernacle Hill basalt flow (17.3 ?? 0.3 ka4) in central Utah and the McCarty's basalt flow (3.0 ?? 0.2 ka) in western New Mexico were significantly lower than expected based on exposure of olivine in our samples to cosmic rays at each site. The source of the discrepancy is not clear. We speculate that in situ 14C atoms may not have been released from Mg-rich crystal lattices (the olivine composition at both sites was ~Fo65Fa35). Alternatively, a portion of the 14C atoms released from the olivine grains may have become trapped in synthetic spinel-like minerals that were created in the olivine-flux mixture during the extraction process, or were simply retained in the mixture itself. Regardless, the magnitude of the discrepancy appears to be inversely proportional to the Fe/(Fe+Mg) ratio of the olivine separates. If we apply a simple correction factor based on the chemical composition of the separates, then corrected in situ 14C concentrations are similar to theoretical values at both sites. At this time, we do not know if this agreement is fortuitous or real. Future research should include measurement of in situ 14C concentrations in olivine from known-age basalt flows with different chemical compositions (i.e. more Fe-rich) to determine if this correction is robust for all olivine-bearing rocks. ?? 2010 by the Arizona

An Amoeboid Olivine Aggregate in LEW 85300

NASA Technical Reports Server (NTRS)

Komatsu, M. D.; Yamaguchi, A.; Fagan, T. J.; Zolensky, M. E.; Shiran, N.; Mikouchi, T.

2016-01-01

Amoeboid Olivine aggregates (AOAs) are irregularly shaped objects commonly observed in carbonaceous chondrites. Because they are composed of fine-grained olivine and Ca-Al-rich minerals, they are sensitive indicators for nebular process and parent body alteration of their parent bodies. Recently an AOA was found in a carbonaceous clast in polymict eucrite LEW 85300. The bulk major element composition of the clast matrix in LEW 85300 suggests a relation to CM, CO and CV chondrites, whereas bulk clast trace and major element compositions do not match any carbonaceous chondrite, suggesting they have a unique origin. Here we characterize the mineralogy of AOA in LEW 85300 and discuss the origin of the carbonaceous clasts. Results and Discussion: The AOA is located in an impact melt vein. Half of the aggregate shows recrystallization textures (euhedral pyroxene and molten metal/FeS) due to impact melting, but the remaining part preserves the original texture. The AOA is composed of olivine, FeS and Mg,Al-phyllosilicate. Individual olivine grains measure 1-8 microns, with Fe-rich rims, probably due to impact heating. Olivines in the AOA are highly forsteritic (Fo95-99), indicating that the AOA escaped thermal metamorphism [4]. Although no LIME (Low-Fe, Mn-Enriched) olivine is observed, forsterite composition and the coexistence of Mg,Al-phyllosilicate suggest that the AOA is similar to those in the Bali-type oxidized CV (CVoxB) and CR chondrites. However, it should be noted that fayalitic olivine, which commonly occurs in CVoxB AOA, is not observed in this AOA. Also, the smaller grain size (<8 microns) of olivine suggests they may be related to CM or CO chondrites. Therefore, we cannot exclude the possibility that the AOA originated from a unique carbonaceous chondrite.

Evaluation of olivine refractories for TES

NASA Astrophysics Data System (ADS)

Gay, B. M.; Cochrane, R. L.; Palmour, H., III; Paisley, M. J.

1982-02-01

The principal objectives of this program are to (1) experimentally determine the degree of improvement in thermal and mechanical performance that can be obtained with an olivine thermal storage brick made of domestic materials using advanced processing techniques compared with state-of-the-art as represented by commercial European bricks, (2) conduct an assessment of existing German ceramic process technology and determine its adaptability to domestic raw materials and manufacturing practices, and (3) investigate, on a limited basis, method for further improvement of domestic-olivine brick. To date, accomplishments include (1) installation of improved, computer-based instrumentation, (2) the use of this system to determine performance characteristics of a set of heat storage refractories under cyclic use conditions, (3) acquisition of the services of a knowledgeable European consultant, (4) continued lab-scale process/property optimization studies, and (5) comparative testing of olivine-based and magnesite-based heat storage refractories in the calorimetric test facility at Purdue University.

Oxygen evolution from olivine M n1 -xMxP O4 (M =Fe ,Ni,Al,Mg) delithiated cathode materials

NASA Astrophysics Data System (ADS)

Snydacker, David H.; Wolverton, C.

2017-01-01

Olivine LiMnP O4 is a promising cathode material for Li-ion batteries. One drawback of this material is the propensity of its delithiated phase, MnP O4 , to evolve oxygen gas above approximately 200 °C. During thermal runaway of cells, this oxygen gas can burn the electrolyte and other cell components and thereby jeopardize safety. Partial substitution of Mn with M =Fe , Ni, Al, or Mg has been used to improve the lithium intercalation kinetics of L ixMnP O4 ; however, the effect of these substitutions on oxygen evolution is not fully documented. In this paper, we calculate phase diagrams and oxygen evolution diagrams for these M n1 -xMxP O4 delithiated cathode materials. To generate the phase diagrams, we use subregular solid-solution models and fit the energetic parameters of these models to density functional theory calculations of special quasirandom structures. The resulting thermodynamic models describe the effect of mixing on the initial temperature of oxygen evolution and on the cumulative amount of oxygen evolution at elevated temperatures. We find that addition of Fe increases the initial temperature and decreases the cumulative amount of oxygen evolution. M n0.5F e0.5P O4 exhibits an initial temperature 50 °C higher than MnP O4 and releases 70% less oxygen gas at 300 °C. Al is insoluble in MnP O4 , so addition of Al has no affect on the initial temperature. However, Al addition does slightly decrease the amount of oxygen evolution due to an inactive AlP O4 component. Mg and Ni both decrease the initial temperature of oxygen evolution, and therefore may worsen the safety of MnP O4 .

Plug-in hybrid electric vehicle LiFePO4 battery life implications of thermal management, driving conditions, and regional climate

NASA Astrophysics Data System (ADS)

Yuksel, Tugce; Litster, Shawn; Viswanathan, Venkatasubramanian; Michalek, Jeremy J.

2017-01-01

Battery degradation strongly depends on temperature, and many plug-in electric vehicle applications employ thermal management strategies to extend battery life. The effectiveness of thermal management depends on the design of the thermal management system as well as the battery chemistry, cell and pack design, vehicle system characteristics, and operating conditions. We model a plug-in hybrid electric vehicle with an air-cooled battery pack composed of cylindrical LiFePO4/graphite cells and simulate the effect of thermal management, driving conditions, regional climate, and vehicle system design on battery life. We estimate that in the absence of thermal management, aggressive driving can cut battery life by two thirds; a blended gas/electric-operation control strategy can quadruple battery life relative to an all-electric control strategy; larger battery packs can extend life by an order of magnitude relative to small packs used for all-electric operation; and batteries last 73-94% longer in mild-weather San Francisco than in hot Phoenix. Air cooling can increase battery life by a factor of 1.5-6, depending on regional climate and driving patterns. End of life criteria has a substantial effect on battery life estimates.

Dehydration Rate of Olivines with Application to Magma Ascent Rate

NASA Astrophysics Data System (ADS)

Plank, T. A.; Ferriss, E.; Walker, D.; Newcombe, M. E.

2017-12-01

The physics of magma transport and eruption are highly sensitive to the decompression rate, for which few measurements exist. There is great promise, however, in being able to use olivine dehydration to clock the ascent of magmas and xenoliths prior to eruption. Every olivine phenocryst we have measured is zoned in water (H) as a consequence of decompression-driven-degassing and diffusion through the olivine. A major impediment to exploiting this crystal clock, however, is the appropriate diffusivity to use. Published laboratory measurements vary by > 5 orders of magnitude. In order to better define the dehydration rates operating in natural olivines, we conducted laboratory experiments using the whole-block method [1], which allows a finely-resolved time series of H profiles in 3 crystallographic directions using the same sample for all dehydration steps. Starting materials consisted of an untreated olivine from the 1959 Kilauea Iki eruption, and a San Carlos olivine first hydrated in a piston cylinder at NNO, 800°C and 1 GPa for 17.5 hours, just enough to saturate the proton-polaron (p-p) mechanism [2]. Samples were dehydrated at 1 atm, NNO-2.6 and 1000 and 800°C in 6-7 time steps over 8-68 total hours. Both samples show rapid movement of different FTIR absorption bands during the first few hours at 800°C, at the p-p rate. Water loss then converges to a rate intermediate between p-p and proton-Mg-vacancy (p-v) rates for both crystals. In San Carlos, water loss from the 3600 cm-1 band (Si-vacancy defect) speeds up after 20 hours, while the 3525 cm-1 band (Ti-clinohumite defect) slows down, until both are dehydroxylating at a rate of 20% p-p:80% p-v. The apparent diffusivity of these bands is > 4 orders of magnitude faster than the same bands in synthetic forsterite [3]. The Iki olivine dehydrates at a constant rate from 3-8 hrs at 1000°C, at 12% p-p: 88% p-v. Both crystals show very similar diffusivity along [100] at 1000°C (logD -10.5 m2/s). This study thus

The solubility of olivine in basaltic liquids - An ionic model

NASA Technical Reports Server (NTRS)

Herzberg, C. T.

1979-01-01

A model is presented which enables the temperature at which olivine is in equilibrium with any alkali-depleted basaltic compound to be calculated to within + or - 30 C. It is noted that the error increases substantially when applied to terrestrial basalts which contain several weight percent alkalis. In addition the model predicts and quantifies the reduced activity of SiO4(4-) monomers due to increasing SiO2 concentrations in the melt. It is shown that the coordination of alumina in melts which precipitate olivine only appears to be dominantly octahedral, while titanium acts as a polmerizing agent by interconnecting previously isolated SiO4(4-) monomers. It is concluded that the model is sufficiently sensitive to show that there are small repulsive forces between Mg(2+) and calcium ions which are in association with normative diopside in the melt.

Structural and Morphological Tuning of LiCoPO4 Materials Synthesized by Solvo-Thermal Methods for Li-Cell Applications

PubMed Central

Manzi, Jessica; Curcio, Mariangela; Brutti, Sergio

2015-01-01

Olivine-type lithium metal phosphates (LiMPO4) are promising cathode materials for lithium-ion batteries. LiFePO4 (LFP) is commonly used in commercial Li-ion cells but the Fe3+/Fe2+ couple can be usefully substituted with Mn3+/Mn2+, Co3+/Co2+, or Ni3+/Ni2+, in order to obtain higher redox potentials. In this communication we report a systematic analysis of the synthesis condition of LiCoPO4 (LCP) using a solvo-thermal route at low temperature, the latter being a valuable candidate to overcome the theoretical performances of LFP. In fact, LCP shows higher working potential (4.8 V vs. 3.6 V) compared to LFP and similar theoretical capacity (167 mAh·g−1). Our goal is to show the effect of the synthesis condition of the ability of LCP to reversibly cycle lithium in electrochemical cells. LCP samples have been prepared through a solvo-thermal method in aqueous-non aqueous solvent blends. Different Co2+ salts have been used to study the effect of the anion on the crystal growth as well as the effect of solution acidity, temperature and reaction time. Materials properties have been characterized by Fast-Fourier transform infrared spectroscopy, X-ray diffraction and scanning electron microscopies. The correlation between structure/morphology and electrochemical performances has been investigated by galvanostatic charge-discharge cycles. PMID:28347117

Enhanced electrochemical properties of LiFePO4 (LFP) cathode using the carboxymethyl cellulose lithium (CMC-Li) as novel binder in lithium-ion battery.

PubMed

Qiu, Lei; Shao, Ziqiang; Wang, Daxiong; Wang, Wenjun; Wang, Feijun; Wang, Jianquan

2014-10-13

Novel water-based binder CMC-Li is synthesized using cotton as raw material. The mechanism of the CMC-Li as a binder is reported. Electrochemical properties of batteries cathodes based on commercially available lithium iron phosphate (LiFePO4, LFP) and CMC-Li as a water-soluble binder are investigated. CMC-Li is a novel lithium-ion binder. Compare with conventional poly(vinylidene fluoride) (PVDF) binder, and the battery with CMC-Li as the binder retained 97.8% of initial reversible capacity after 200 cycles at 176 mAh g(-1), which is beyond the theoretical specific capacity of LFP. Constant current charge-discharge test results demonstrate that the LFP electrode using CMC-Li as the binder has the highest rate capability, follow closely by that using PVDF binder. The batteries have good electrochemical property, outstanding pollution-free and excellent stability. Copyright © 2014 Elsevier Ltd. All rights reserved.

Sintering polycrystalline olivine and polycrystalline clinopyroxene containing trace amount of graphite from natural crystals

NASA Astrophysics Data System (ADS)

Tsubokawa, Yumiko; Ishikawa, Masahiro

2017-09-01

Graphite-bearing polycrystalline olivine and polycrystalline clinopyroxene with submicron to micron grain size were successfully sintered from a single crystal of naturally occurring olivine (Fo88-92Fa12-8: Mg1.76-1.84Fe0.16-0.24SiO4) and a single crystal of naturally occurring clinopyroxene (Di99Hed1: Ca0.92Na0.07Mn0.01Mg0.93Fe0.01Al0.06Si2O6). The milled powders of both these crystals were sintered under argon gas flow at temperatures ranging from 1130 to 1350 °C for 2 h. As the sintering temperature increased, the average grain size of olivine increased from 0.2 to 1.4 µm and that of clinopyroxene increased from 0.1 to 2.4 µm. The porosity of sintered samples remained at an almost-constant volume of 2-5% for olivine and 3-4% for clinopyroxene. The samples sintered from powders milled with ethanol exhibited trace amount of graphite, identified via Raman spectroscopy analysis. As the sintering temperature increased, the intensity of the graphite Raman peak decreased, compared with both olivine and clinopyroxene peaks. The carbon content of the sintered samples was estimated to be a few hundred ppm. The in-plane size ( L a ) of graphite in the sintered olivine was estimated to be <15 nm. Our experiments demonstrate new possibilities for preparing graphite-bearing silicate-mantle mineral rocks, and this method might be useful in understanding the influence of the physical properties of graphite on grain-size-sensitive rheology or the seismic velocity of the Earth's mantle.[Figure not available: see fulltext.

Fabrication and Characterization of 3D-Printed Highly-Porous 3D LiFePO4 Electrodes by Low Temperature Direct Writing Process

PubMed Central

Cheng, Xingxing; Li, Bohan; Chen, Zhangwei; Mi, Shengli; Lao, Changshi

2017-01-01

LiFePO4 (LFP) is a promising cathode material for lithium-ion batteries. In this study, low temperature direct writing (LTDW)-based 3D printing was used to fabricate three-dimensional (3D) LFP electrodes for the first time. LFP inks were deposited into a low temperature chamber and solidified to maintain the shape and mechanical integrity of the printed features. The printed LFP electrodes were then freeze-dried to remove the solvents so that highly-porous architectures in the electrodes were obtained. LFP inks capable of freezing at low temperature was developed by adding 1,4 dioxane as a freezing agent. The rheological behavior of the prepared LFP inks was measured and appropriate compositions and ratios were selected. A LTDW machine was developed to print the electrodes. The printing parameters were optimized and the printing accuracy was characterized. Results showed that LTDW can effectively maintain the shape and mechanical integrity during the printing process. The microstructure, pore size and distribution of the printed LFP electrodes was characterized. In comparison with conventional room temperature direct ink writing process, improved pore volume and porosity can be obtained using the LTDW process. The electrochemical performance of LTDW-fabricated LFP electrodes and conventional roller-coated electrodes were conducted and compared. Results showed that the porous structure that existed in the printed electrodes can greatly improve the rate performance of LFP electrodes. PMID:28796182

High-pressure, high-temperature Raman spectroscopy of Ca 2GeO 4 (olivine form): some insights on anharmonicity

NASA Astrophysics Data System (ADS)

Gillet, Philippe; Guyot, Francois; Malezieux, Jean-Marie

1989-12-01

High pressure (up to 2.7 GPa) and high temperature (up to 1000 K) Raman spectra of Ca 2GeO 4 (olivine form) have been recorded. Measurements of the pressure- and temperature-induced frequency shifts of 14 modes have been performed. The classical mode Gruneisen parameter and a corresponding parameter related to temperature variation are calculated. For the high frequency modes (GeO stretching) we calculate these parameters with local tetrahedral elastic parameters. From these parameters anharmonic parameters are calculated for each Raman active mode. The effect of anharmonicity on the specific heat is calculated and compared with calorimetric data. Taking anharmonicity into account leads to a departure from the Dulong and Petit limit of the order of 2% at 1000 K and more than 6% at 2000 K, in good accord with experimental data. We propose that, eventually, such effects might be significant in the calculations of thermodynamic properties of mantle silicates like forsterite and its polymorphs.

Geochemistry of Pallasite Olivines and the Origin of Main-Group Pallasites

NASA Technical Reports Server (NTRS)

Mittlefehldt, D. W.; Rumble, D., III

2006-01-01

Main-group pallasites (PMG) are mixtures of iron-nickel metal and magnesian olivine thought to have been formed at the core-mantle boundary of an asteroid [1]. Some have anomalous metal compositions (PMG-am) and a few have atypically ferroan olivines (PMG-as) [2]. PMG metal is consistent with an origin as a late fractionate of the IIIAB iron core [2]. Most PMG olivines have very similar Fe/Mg ratios, likely due to subsolidus redox reaction with the metal [3]. In contrast, minor and trace elements show substantial variation, which may be explained by either: (i) PMG were formed at a range of depths in the parent asteroid; the element variations reflect variations in igneous evolution with depth, (ii) the pallasite parent asteroid was chemically heterogeneous; the heterogeneity partially survived igneous processing, or (iii) PMG represent the core-mantle boundaries of several distinct parent asteroids [4, 5]. We have continued doing major, minor and trace elements by EMPA and INAA on a wider suite of PMG olivines, and have begun doing precise oxygen isotope analyses to test these hypotheses. Manganese is homologous with Fe(2+), and can be used to distinguish between magmatic and redox processes as causes for Fe/Mg variations. PMG olivines have a range in molar 1000*Mn/Mg of 2.3-4.6 indicating substantial igneous fractionation in olivines with very similar Fe/Mg (0.138-0.148). The Mg-Mn-Fe distributions can be explained by a fractional crystallization-reduction model; higher Mn/Mg ratios reflect more evolved olivines while Fe/Mg is buffered by redox reactions with the metal. There is a positive association between Mn/Mg and Sc content that is consistent with igneous fractionation. However, most PMG olivines fall within a narrow Mn/Mg range (3.0-3.6), but these show a substantial range in Sc (1.00-2.29 micro-g/g). Assuming fractional crystallization, this Sc range could have resulted from approx.65% crystallization of an ultramafic magma. This is inconsistent with

Towards High Capacity Li-ion Batteries Based on Silicon-Graphene Composite Anodes and Sub-micron V-doped LiFePO4 Cathodes

NASA Astrophysics Data System (ADS)

Loveridge, M. J.; Lain, M. J.; Johnson, I. D.; Roberts, A.; Beattie, S. D.; Dashwood, R.; Darr, J. A.; Bhagat, R.

2016-11-01

Lithium iron phosphate, LiFePO4 (LFP) has demonstrated promising performance as a cathode material in lithium ion batteries (LIBs), by overcoming the rate performance issues from limited electronic conductivity. Nano-sized vanadium-doped LFP (V-LFP) was synthesized using a continuous hydrothermal process using supercritical water as a reagent. The atomic % of dopant determined the particle shape. 5 at. % gave mixed plate and rod-like morphology, showing optimal electrochemical performance and good rate properties vs. Li. Specific capacities of >160 mAh g-1 were achieved. In order to increase the capacity of a full cell, V-LFP was cycled against an inexpensive micron-sized metallurgical grade Si-containing anode. This electrode was capable of reversible capacities of approximately 2000 mAh g-1 for over 150 cycles vs. Li, with improved performance resulting from the incorporation of few layer graphene (FLG) to enhance conductivity, tensile behaviour and thus, the composite stability. The cathode material synthesis and electrode formulation are scalable, inexpensive and are suitable for the fabrication of larger format cells suited to grid and transport applications.

Towards High Capacity Li-ion Batteries Based on Silicon-Graphene Composite Anodes and Sub-micron V-doped LiFePO4 Cathodes.

PubMed

Loveridge, M J; Lain, M J; Johnson, I D; Roberts, A; Beattie, S D; Dashwood, R; Darr, J A; Bhagat, R

2016-11-29

Lithium iron phosphate, LiFePO 4 (LFP) has demonstrated promising performance as a cathode material in lithium ion batteries (LIBs), by overcoming the rate performance issues from limited electronic conductivity. Nano-sized vanadium-doped LFP (V-LFP) was synthesized using a continuous hydrothermal process using supercritical water as a reagent. The atomic % of dopant determined the particle shape. 5 at. % gave mixed plate and rod-like morphology, showing optimal electrochemical performance and good rate properties vs. Li. Specific capacities of >160 mAh g -1 were achieved. In order to increase the capacity of a full cell, V-LFP was cycled against an inexpensive micron-sized metallurgical grade Si-containing anode. This electrode was capable of reversible capacities of approximately 2000 mAh g -1 for over 1 50 cycles vs. Li, with improved performance resulting from the incorporation of few layer graphene (FLG) to enhance conductivity, tensile behaviour and thus, the composite stability. The cathode material synthesis and electrode formulation are scalable, inexpensive and are suitable for the fabrication of larger format cells suited to grid and transport applications.

Porous α-Fe2O3 nanostructures and their lithium storage properties as full cell configuration against LiFePO4

NASA Astrophysics Data System (ADS)

Veluri, P. S.; Shaligram, A.; Mitra, S.

2015-10-01

A two step approach for synthesis of porous α-Fe2O3 nanostructures has been realized via polyol method by complexing iron oxalate with ethylene glycol. Crystalline Fe2O3 samples with different porosities are obtained by calcination of Fe-Ethylene glycol complex at various temperatures. The as-prepared porous Fe2O3 structures exhibit promising lithium storage performance at high current rates. It is observed that the calcination temperature and the resultant porosity have a significant effect on capacity and cycling stability. Samples calcined at high temperature (600 °C) demonstrates stable cycle life with capacity retention of 1077 mAh g-1 at 500 mA g-1 current rate after 50 charge-discharge cycles. Samples calcined at temperatures of 500 and 600 °C display stable cycle life and high rate capability with reversible capacity of 930 mAh g-1 and 688 mAh g-1 at 5 A g-1, respectively. Impregnation of electrodes with electrolyte before cell fabrication shows enhanced electrochemical performance. The viability of Fe2O3 porous nanostructures as prospective anode material examined against commercial LiFePO4 cathode shows promising electrochemical performance.

Shock-produced olivine glass: First observation

USGS Publications Warehouse

Jeanloz, R.; Ahrens, T.J.; Lally, J.S.; Nord, G.L.; Christie, J.M.; Heuer, A.H.

1977-01-01

Transmission electron microscope (TEM) observations of an experimentally shock-deformed single crystal of natural peridot, (Mg0.88Fe 0.12SiO4 recovered from peak pressures of about 56 ?? 109 pascals revealed the presence of amorphous zones located within crystalline regions with a high density of tangled dislocations. This is the first reported observation ofolivine glass. The shocked sample exhibits a wide variation in the degree of shock deformation on a small scale, and the glass appears to be intimately associated with the highest density of dislocations. This study suggests that olivine glass may be formed as a result of shock at pressures above about 50 to 55 ?? 109 pascals and that further TEM observations of naturally shocked olivines may demonstrate the presence of glass.

Well-dispersed LiFePO4 nanoparticles anchored on a three-dimensional graphene aerogel as high-performance positive electrode materials for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Tian, Xiaohui; Zhou, Yingke; Tu, Xiaofeng; Zhang, Zhongtang; Du, Guodong

2017-02-01

A three-dimensional graphene aerogel supporting LiFePO4 nanoparticles (LFP/GA) has been synthesized by a hydrothermal process. The morphology and microstructure of LFP/GA were investigated by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and thermal gravimetric analysis. The electrochemical properties were evaluated by constant-current charge/discharge tests, cyclic voltammetry and electrochemical impedance spectroscopy. Well-distributed LFP nanoparticles are anchored on both sides of graphene and then assemble into a highly porous three-dimensional aerogel architecture. Conductive graphene networks provide abundant paths to facilitate the transfer of electrons, while the aerogel structures offer plenty of interconnected open pores for the storage of electrolyte to enable the fast supply of Li ions. The LFP and graphene aerogel composites present superior specific capacity, rate capability and cycling performance in comparison to the pristine LFP or LFP supported on graphene sheets and are thus promising for lithium-ion battery applications.

Exogenic olivine on Vesta from Dawn Framing Camera color data

NASA Astrophysics Data System (ADS)

Nathues, Andreas; Hoffmann, Martin; Schäfer, Michael; Thangjam, Guneshwar; Le Corre, Lucille; Reddy, Vishnu; Christensen, Ulrich; Mengel, Kurt; Sierks, Holger; Vincent, Jean-Baptist; Cloutis, Edward A.; Russell, Christopher T.; Schäfer, Tanja; Gutierrez-Marques, Pablo; Hall, Ian; Ripken, Joachim; Büttner, Irene

2015-09-01

In this paper we present the results of a global survey of olivine-rich lithologies on (4) Vesta. We investigated Dawn Framing Camera (FC) High Altitude Mapping Orbit (HAMO) color cubes (∼60 m/pixel resolution) by using a method described in Thangjam et al. (Thangjam, G., Nathues, A., Mengel, K., Hoffmann, M., Schäfer, M., Reddy, V., Cloutis, E.A., Christensen, U., Sierks, H., Le Corre, L., Vincent, J.-B, Russell, C.T. [2014b]. Meteorit. Planet. Sci. arXiv:1408.4687 [astro-ph.EP]). In total we identified 15 impact craters exhibiting olivine-rich (>40 wt.% ol) outcrops on their inner walls, some showing olivine-rich material also in their ejecta and floors. Olivine-rich sites are concentrated in the Bellicia, Arruntia and Pomponia region on Vesta's northern hemisphere. From our multi-color and stratigraphic analysis, we conclude that most, if not all, of the olivine-rich material identified is of exogenic origin, i.e. remnants of A- or/and S-type projectiles. The olivine-rich lithologies in the north are possibly ejecta of the ∼90 km diameter Albana crater. We cannot draw a final conclusion on their relative stratigraphic succession, but it seems that the dark material (Nathues, A., Hoffmann, M., Cloutis, E.A., Schäfer, M., Reddy, V., Christensen, U., Sierks, H., Thangjam, G.S., Le Corre, L., Mengel, K., Vincent, J.-B., Russell, C.T., Prettyman, T., Schmedemann, N., Kneissl, T., Raymond, C., Gutierrez-Marques, P., Hall, I. Büttner, I. [2014b]. Icarus (239, 222-237)) and the olivine-rich lithologies are of a similar age. The origin of some potential olivine-rich sites in the Rheasilvia basin and at crater Portia are ambiguous, i.e. these are either of endogenic or exogenic origin. However, the small number and size of these sites led us to conclude that olivine-rich mantle material, containing more than 40 wt.% of olivine, is basically absent on the present surface of Vesta. In combination with recent impact models of Veneneia and Rheasilvia (Clenet, H., Jutzi

New Insights on the Rheology of Olivine Deformed under Lithospheric Temperature Conditions

NASA Astrophysics Data System (ADS)

Cordier, P.; Demouchy, S. A.; Mussi, A.; Tommasi, A.

2014-12-01

Rheology of mantle rocks at lithospheric temperatures remains poorly constrained, since most experimental studies on creep mechanisms of olivine single crystals ((MgFe)2SiO4, Pbnm) and polycrystalline olivine aggregates were performed at high-temperatures (T >> 1200oC). In this study, we report results from deformation experiments on oriented single crystals of San Carlos olivine and polycrystalline olivine aggregate at temperatures relevant of the uppermost mantle (ranging from 800o to 1090oC) in tri-axial compression. The experiments were carried out at a confining pressure of 300 MPa in a high-resolution gas-medium mechanical testing apparatus at various constant strain rates (from 7 x 10-6 s-1 to 1 x 10-4 s-1). Mechanical tests show that mantle lithosphere is actually weaker than previously inferred from the extrapolation of high-temperature experiments. In this study, we present characterization of dislocation microstructures based on transmission electron microscopy and electron tomography. It is shown that below 1000°C, dislocation activity is restricted to [001] glide with a strong predominance of {110} as glide planes. We observe recovery mechanisms which suggest that the mechanical properties observed in laboratory experiments represent an upper bound for the actual behavior of olivine under lithospheric mantle conditions. Moreover, the drastic reduction in slip system activity observed questions the ability of deforming olivine aggregates in the ductile regime at such temperatures. We show that ductility is preserved thanks to the activation of alternative deformation mechanisms in grain boundaries involving disclinations.

Graphite|LiFePO4 lithium-ion battery working at the heat engine coolant temperature

NASA Astrophysics Data System (ADS)

Lewandowski, Andrzej; Kurc, Beata; Swiderska-Mocek, Agnieszka; Kusa, Natalia

2014-11-01

Electrochemical properties of the graphite anode and the LiFePO4 cathode, working together with the 1 M LiPF6 in TMS (sulpholane) at 90 °C have been studied. The general aim of the investigation was to demonstrate a potential application for a Li-ion cell working in the cooling system of a car heat engine (90 °C). Electrodes were characterized with the use of electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM) as well as galvanostatic charging/discharging tests. SEM images of both electrodes after charging/discharging processes were covered with a film (electrochemical SEI formation). The charge transfer resistance at 90 °C, Rct, of the C6Li|Li+ anode and the LiFePO4 cathode was 24 Ω and 110 Ω, respectively. Reversible capacity of the LiC6 anode after 10-20 cycles, at a low current rate was close to the theoretical value of 370 mAh g-1 however an increasing current rate decreased to ca. 200 mAh g-1 (for 1C). The reversibility of the process was close to 95%. The capacity of the LiFePO4 cathode was ca. 150 mAh g-1, almost independent of the current rate and close to the theoretical value of 170 mAh g-1.

Effect of Sulfur on Siderophile Element Partitioning Between Olivine and Martian Primary Melt

NASA Technical Reports Server (NTRS)

Usui, T.; Shearer, C. K.; Righter, K.; Jones, J. H.

2011-01-01

Since olivine is a common early crystallizing phase in basaltic magmas that have produced planetary and asteroidal crusts, a number of experimental studies have investigated elemental partitioning between olivine and silicate melt [e.g., 1, 2, 3]. In particular, olivine/melt partition coefficients of Ni and Co (DNi and DCo) have been intensively studied because these elements are preferentially partitioned into olivine and thus provide a uniquely useful insight into the basalt petrogenesis [e.g., 4, 5]. However, none of these experimental studies are consistent with incompatible signatures of Co [e.g., 6, 7, 8] and Ni [7] in olivines from Martian meteorites. Chemical analyses of undegassed MORB samples suggest that S dissolved in silicate melts can reduce DNi up to 50 % compared to S-free experimental systems [9]. High S solubility (up to 4000 ppm) for primitive shergottite melts [10] implies that S might have significantly influenced the Ni and Co partitioning into shergottite olivines. This study conducts melting experiments on Martian magmatic conditions to investigate the effect of S on the partitioning of siderophile elements between olivine and Martian primary melt.

Abiotic methane formation during experimental serpentinization of olivine

PubMed Central

2016-01-01

Fluids circulating through actively serpentinizing systems are often highly enriched in methane (CH4). In many cases, the CH4 in these fluids is thought to derive from abiotic reduction of inorganic carbon, but the conditions under which this process can occur in natural systems remain unclear. In recent years, several studies have reported abiotic formation of CH4 during experimental serpentinization of olivine at temperatures at or below 200 °C. However, these results seem to contradict studies conducted at higher temperatures (300 °C to 400 °C), where substantial kinetic barriers to CH4 synthesis have been observed. Here, the potential for abiotic formation of CH4 from dissolved inorganic carbon during olivine serpentinization is reevaluated in a series of laboratory experiments conducted at 200 °C to 320 °C. A 13C-labeled inorganic carbon source was used to unambiguously determine the origin of CH4 generated in the experiments. Consistent with previous high-temperature studies, the results indicate that abiotic formation of CH4 from reduction of dissolved inorganic carbon during the experiments is extremely limited, with nearly all of the observed CH4 derived from background sources. The results indicate that the potential for abiotic synthesis of CH4 in low-temperature serpentinizing environments may be much more limited than some recent studies have suggested. However, more extensive production of CH4 was observed in one experiment performed under conditions that allowed an H2-rich vapor phase to form, suggesting that shallow serpentinization environments where a separate gas phase is present may be more favorable for abiotic synthesis of CH4. PMID:27821742

Abiotic methane formation during experimental serpentinization of olivine.

PubMed

McCollom, Thomas M

2016-12-06

Fluids circulating through actively serpentinizing systems are often highly enriched in methane (CH 4 ). In many cases, the CH 4 in these fluids is thought to derive from abiotic reduction of inorganic carbon, but the conditions under which this process can occur in natural systems remain unclear. In recent years, several studies have reported abiotic formation of CH 4 during experimental serpentinization of olivine at temperatures at or below 200 °C. However, these results seem to contradict studies conducted at higher temperatures (300 °C to 400 °C), where substantial kinetic barriers to CH 4 synthesis have been observed. Here, the potential for abiotic formation of CH 4 from dissolved inorganic carbon during olivine serpentinization is reevaluated in a series of laboratory experiments conducted at 200 °C to 320 °C. A 13 C-labeled inorganic carbon source was used to unambiguously determine the origin of CH 4 generated in the experiments. Consistent with previous high-temperature studies, the results indicate that abiotic formation of CH 4 from reduction of dissolved inorganic carbon during the experiments is extremely limited, with nearly all of the observed CH 4 derived from background sources. The results indicate that the potential for abiotic synthesis of CH 4 in low-temperature serpentinizing environments may be much more limited than some recent studies have suggested. However, more extensive production of CH 4 was observed in one experiment performed under conditions that allowed an H 2 -rich vapor phase to form, suggesting that shallow serpentinization environments where a separate gas phase is present may be more favorable for abiotic synthesis of CH 4 .

Towards High Capacity Li-ion Batteries Based on Silicon-Graphene Composite Anodes and Sub-micron V-doped LiFePO4 Cathodes

PubMed Central

Loveridge, M. J.; Lain, M. J.; Johnson, I. D.; Roberts, A.; Beattie, S. D.; Dashwood, R.; Darr, J. A.; Bhagat, R.

2016-01-01

Lithium iron phosphate, LiFePO4 (LFP) has demonstrated promising performance as a cathode material in lithium ion batteries (LIBs), by overcoming the rate performance issues from limited electronic conductivity. Nano-sized vanadium-doped LFP (V-LFP) was synthesized using a continuous hydrothermal process using supercritical water as a reagent. The atomic % of dopant determined the particle shape. 5 at. % gave mixed plate and rod-like morphology, showing optimal electrochemical performance and good rate properties vs. Li. Specific capacities of >160 mAh g−1 were achieved. In order to increase the capacity of a full cell, V-LFP was cycled against an inexpensive micron-sized metallurgical grade Si-containing anode. This electrode was capable of reversible capacities of approximately 2000 mAh g−1 for over 150 cycles vs. Li, with improved performance resulting from the incorporation of few layer graphene (FLG) to enhance conductivity, tensile behaviour and thus, the composite stability. The cathode material synthesis and electrode formulation are scalable, inexpensive and are suitable for the fabrication of larger format cells suited to grid and transport applications. PMID:27898104

NiO and Fe/Mn in Fo-rich olivines from OIB, MORB, and mantle peridotites

NASA Astrophysics Data System (ADS)

Li, H.; Baker, M.; Hofmann, A. E.; Clague, D.; Stolper, E.

2006-12-01

Olivines from mantle peridotites have a narrow range of NiO (0.36±0.03 [1σ] wt%), but NiO of olivines in basalts suggest NiO in mantle olivines is actually more variable: e.g., Hawaiian phenocrysts (Fo>90) have NiO >0.55%, and olivines from continental flood basalts can have >0.5% NiO. At the other end of the spectrum, some basaltic suites (e.g., Iceland, MORBs) have Fo>90 olivines with NiO >0.2%. Partial melting calculations on peridotites show it is difficult to generate liquids that crystallize Fo>90 olivines with >0.4% NiO without resorting to complex processes. Hypotheses to explain the variability of NiO in mantle-derived olivines include (1) reaction of peridotite with silica-rich melts of eclogite results in decreasing modal abundance of olivine and increasing NiO in olivine [1,2]; (2) magmas with NiO-rich olivines come from sources enriched in NiO due to a core-derived component [3]. [4] proposed that high Fe/Mn of Hawaiian vs. Icelandic and MORB lavas reflect a core-derived component in their sources. Possible core incorporation is poorly constrained but FeO and NiO are expected to increase by such processes, leading to correlations between NiO and Fe/Mn in mantle rocks with significant core-derived components. We present high-precision analyses of Fo-rich olivines from OIBs, MORBs, komatiites, and mantle peridotites, focusing on NiO contents and Fe/Mn ratios. Our goal is to test hypotheses to explain elevated NiO of Fo-rich olivines in basalts. Olivines are Fo85.1-93.4; more were analyzed, but we focused on this range to avoid complications due to decreasing NiO in olivine with crystallization. Errors (1σ) are 0.01 wt% in NiO and 1.5 in Fe/Mn (wt). Our data show several features: (1) NiO contents and Fe/Mn ratios of Fo>88 olivines are positively correlated, with the low end of the trend (NiO ~0.23%, Fe/Mn ~61) defined by MORB and Iceland and the high end of the trend (NiO ~0.55%, Fe/Mn ~80) by Reunion and Hawaii. Between these end points, there is a

Artificial meteor ablation studies: Olivine

NASA Technical Reports Server (NTRS)

Blanchard, M. B.; Cunningham, G. G.

1973-01-01

Artificial meteor ablation was performed on a Mg-rich olivine sample using an arc-heated plasma of ionized air. Experimental conditions simulated a meteor traveling about 12 km/sec at an altitude of 70 km. The mineral content of the original olivine sample was 98% olivine (including traces of olivine alteration products) and 2% chromite. Forsterite content of the original olivine was Fo-89. After ablation, the forsterite content had increased to Fo-94 in the recrystallized olivine. In addition, lamella-like intergrowths of magnetite were prevalent constituents. Wherever magnetite occurred, there was an increase in Mg and a corresponding decrease in Fe for the recrystallized olivine. The Allende fusion crust consisted of a recrystallized olivine, which was more Mg-rich and Fe-deficient than the original meteorite's olivine, and abundant magnetite grains. Although troilite and pentlandite were the common opaque mineral constituents in this meteorite, magnetite was the principal opaque mineral found in the fusion crust.

Conformal Coating Strategy Comprising N-doped Carbon and Conventional Graphene for Achieving Ultrahigh Power and Cyclability of LiFePO4.

PubMed

Zhang, Kan; Lee, Jeong-Taik; Li, Ping; Kang, Byoungwoo; Kim, Jung Hyun; Yi, Gi-Ra; Park, Jong Hyeok

2015-10-14

Surface carbon coating to improve the inherent poor electrical conductivity of lithium iron phosphate (LiFePO4, LFP) has been considered as most efficient strategy. Here, we also report one of the conventional methods for LFP but exhibiting a specific capacity beyond the theoretical value, ultrahigh rate performance, and excellent long-term cyclability: the specific capacity is 171.9 mAh/g (70 μm-thick electrode with ∼10 mg/cm(2) loading mass) at 0.1 C (17 mA/g) and retains 143.7 mAh/g at 10 C (1.7 A/g) and 95.8% of initial capacity at 10 C after 1000 cycles. It was found that the interior conformal N-C coating enhances the intrinsic conductivity of LFP nanorods (LFP NR) and the exterior reduced graphene oxide coating acts as an electrically conducting secondary network to electrically connect the entire electrode. The great electron transport mutually promoted with shorten Li diffusion length on (010) facet exposed LFP NR represents the highest specific capacity value recorded to date at 10 C and ultralong-term cyclability. This conformal carbon coating approach can be a promising strategy for the commercialization of LFP cathode in lithium ion batteries.

Synchrotron X-Ray Diffraction Studies of Olivine from Comet Wild 2

NASA Technical Reports Server (NTRS)

2008-01-01

We have analyzed a collection of the Comet Wild 2 coma grains returned by the NASA Stardust Mission, using micro-area Laue diffraction equipment. The purpose of the diffraction experiment is to permit the structure refinement of olivine including site occupancies. In addition to the intrinsic importance of the olivine structures for revealing the thermal history of Wild 2 materials, we wish to test reports that olivine recovered after hypervelocity capture in silica aerogel has undergone a basic structural change due to capture heating [1]. The diffraction equipment placed at beam line BL- 4B1 of PF, KEK was developed with a micropinhole and an imaging plate (Fuji Co. Ltd.) using the Laue method combined with polychromatic X-ray of synchrotron radiation operated at energy of 2.5 GeV. The incident beam is limited to 1.6 m in diameter by a micropinhole set just upstream of the sample [2, 3]. It is essential to apply a microbeam to obtain diffracted intensities with high signal to noise ratios. This equipment has been successfully applied to various extraterrestrial materials, including meteorites and interplanetary dust particles [4]. The Laue pattern of the sample C2067,1,111,4 (Fig. 1) was successfully taken on an imaging plate after a 120 minute exposure (Fig. 2).

The Surface Coating of Commercial LiFePO4 by Utilizing ZIF-8 for High Electrochemical Performance Lithium Ion Battery

NASA Astrophysics Data System (ADS)

Xu, XiaoLong; Qi, CongYu; Hao, ZhenDong; Wang, Hao; Jiu, JinTing; Liu, JingBing; Yan, Hui; Suganuma, Katsuaki

2018-03-01

The requirement of energy-storage equipment needs to develop the lithium ion battery (LIB) with high electrochemical performance. The surface modification of commercial LiFePO4 (LFP) by utilizing zeolitic imidazolate frameworks-8 (ZIF-8) offers new possibilities for commercial LFP with high electrochemical performances. In this work, the carbonized ZIF-8 (CZIF-8) was coated on the surface of LFP particles by the in situ growth and carbonization of ZIF-8. Transmission electron microscopy indicates that there is an approximate 10 nm coating layer with metal zinc and graphite-like carbon on the surface of LFP/CZIF-8 sample. The N2 adsorption and desorption isotherm suggests that the coating layer has uniform and simple connecting mesopores. As cathode material, LFP/CZIF-8 cathode-active material delivers a discharge specific capacity of 159.3 mAh g-1 at 0.1C and a discharge specific energy of 141.7 mWh g-1 after 200 cycles at 5.0C (the retention rate is approximate 99%). These results are attributed to the synergy improvement of the conductivity, the lithium ion diffusion coefficient, and the degree of freedom for volume change of LFP/CZIF-8 cathode. This work will contribute to the improvement of the cathode materials of commercial LIB.[Figure not available: see fulltext.

Site-specific hydration and dehydration of San Carlos olivine

NASA Astrophysics Data System (ADS)

Ferriss, E.; Plank, T. A.; Walker, D.

2016-12-01

Hydrogen incorporation and diffusion in olivine is critical to understanding fundamental Earth processes such as mantle rheology, plate tectonics, melt generation and magma ascent. Interpreting measured H profiles in olivine requires a more comprehensive understanding of H point defect reactions than currently exists because H diffusivity (D) ranges over 6 orders of magnitude, from slow diffusing H incorporated as (4H+)Si­ [1] to rapid `proton-polaron' bulk H diffusion [2]. Here we present the first experiments on H diffusing into and then out of Fe-bearing olivine using the whole-block method [3], which allows a finely-resolved time series of H profiles in 3 crystallographic directions using the same sample for all dehydration steps. A piece of nearly-dry, oriented San Carlos olivine was hydrated in a piston cylinder apparatus using H2O and solid buffers of Ni/NiO and San Carlos olivine and enstatite at 800 °C and 10 kbar for 17.5 hours, just long enough to saturate the `proton-polaron' mechanism. The sample was then dehydrated in a CO/CO2 gas-mixing furnace at 800°C and 10-14 bar fO2 for total heating times of 1, 3, 7, 13, 19, 43, and 68 hrs, at which point most, but not all, of the H had left the crystal. FTIR profiles at 1, 3, and 7 hours show bulk H profiles consistent with `proton-polaron' diffusion. Later the pace of dehydration slowed, and in several cases the bulk H profile shape differed from what would be expected during simple diffusive loss. The small peak at 3600 cm-1, (4H+)Si, remained essentially unchanged throughout all experiments. The peak at 3573 cm-1, (Ti4+)Mg(2H+)Mg, was initially present but tiny, grew to become the largest peak after hydration, and then during dehydration returned to its initial height. The apparent diffusivity of this peak during hydration and the initial stages of dehydration is 4 orders of magnitude faster than the same peak in synthetic forsterite [2]. Peaks at 3542, 3525, 3489, and 3480 cm-1 were not present

Structural and chemical alteration of crystalline olivine under low energy He+ irradiation

NASA Astrophysics Data System (ADS)

Demyk, K.; Carrez, Ph.; Leroux, H.; Cordier, P.; Jones, A. P.; Borg, J.; Quirico, E.; Raynal, P. I.; d'Hendecourt, L.

2001-03-01

We present the results of irradiation experiments on crystalline olivine with He+ ions at energies of 4 and 10 keV and fluences varying from 5 1016 to 1018 ions/cm2. The aim of these experiments is to simulate ion implantation into interstellar grains in shocks in the ISM. Irradiated samples were analysed by transmission electron microscopy (TEM). The irradiation causes the amorphization of the olivine, at all He+ fluences considered. The thickness of the amorphized region is 40 +/- 15 nm and 90 +/- 10 nm for the 4 keV and 10 keV experiments, respectively. The amorphization of the olivine occurs in conjunction with an increase in the porosity of the material due to the formation of bubbles. In addition, the amorphized layer is deficient in oxygen and magnesium. We find that the O/Si and Mg/Si ratios decrease as the He+ fluence increases. These experiments show that the irradiation of dust in supernova shocks can efficiently alter the dust structure and composition. Our result are consistent with the lack of crystalline silicates in the interstellar medium and also with the compositional evolution observed from olivine-type silicates around evolved stars to pyroxene-type silicates around protostars.

Assessing δ18O heterogeneity in Icelandic olivine crystals

NASA Astrophysics Data System (ADS)

Bar Rasmussen, M.; Halldorsson, S. A.; Martin, W.; Gibson, S. A.; Hilton, D. R.

2017-12-01

δ18O systematics of Icelandic basalts are notably distinct from MORB-sourced basalts. This difference has previously been attributed to interaction with low δ18O meteoric water in the crust or slight heterogeneity within the Icelandic mantle [1]. Studies addressing this issue have mostly involved batch mineral laser-fluorination analysis which cannot resolve any intra-mineral δ18O variability that might be present due to shallow-level processes, e.g. crustal contamination [2]. We present a study of olivine crystals found in basalts covering the neovolcanic rift and flank zones as well as older Tertiary crust, in which we couple in-situ δ18O-measurements with major and trace elements using SIMS, high-precision EMP and LA ICP-MS. Most samples have previously been analysed for 3He/4He which ranges from 6.7 to 47.8 RA, the largest span reported for any oceanic island [3]. Our analysed olivine grains, range in Fo# between 79.9 to 91.8 with limited intra-grain variability. Independent of Fo#, we observe a variation in δ18O(Ol) of >3 ‰ across Iceland, with most crystals plotting below the expected depleted mantle-value ( 5.1 ± 0.2‰ [4]). The lowest δ18O(Ol) of +2.77 ‰, is found in crystals with Fo# 86 from central Iceland, closest to the inferred plume head [3]. Trace element ratios for these olivine grains (e.g. Zn/Fe) strongly indicate a peridotitic mantle source, which implies a shallow (likely crustal) origin of low δ18O(Ol) for this region. In contrast, olivine crystals from the South Iceland Volcanic Zone (a region of active rift propagation and transitional to alkalic volcanism) display trace element ratios that are indicative of a greater amount of pyroxenite in their melt source region. The δ18O(Ol) of these samples vary significantly (from +3.45 to +4.98 ‰) which, together with their elevated 3He/4He values, implies entrainment of a lower δ18O mantle-source by a less-degassed mantle plume source. Further modelling will be performed to evaluate

Olivine on Earth

NASA Image and Video Library

2012-10-30

The semi-precious gem peridot is a variety of olivine. NASA Curiosity rover shows the diffraction signature, or fingerprint, of the mineral olivine, shown here on Earth in the form of tumbled crystals.

Recognition of battery aging variations for LiFePO4 batteries in 2nd use applications combining incremental capacity analysis and statistical approaches

NASA Astrophysics Data System (ADS)

Jiang, Yan; Jiang, Jiuchun; Zhang, Caiping; Zhang, Weige; Gao, Yang; Guo, Qipei

2017-08-01

To assess the economic benefits of battery reuse, the consistency and aging characteristics of a retired LiFePO4 battery pack are studied in this paper. The consistency of battery modules is analyzed from the perspective of the capacity and the internal resistance. Test results indicate that battery module parameter dispersion increases along with battery aging. However, battery modules with better capacity consistency doesn't ensure better resistance consistency. Then the aging characteristics of the battery pack are analyzed and the main results are as follow: (1) Weibull and normal distribution are feasible to fit the capacity and resistance distribution of battery modules respectively; (2) SOC imbalance is the dominating factor in the capacity fading process of the battery pack; (3) By employing the incremental capacity (IC) and IC peak area analysis, a consistency evaluation method representing the aging mechanism variations of the battery modules is proposed and then an accurate battery screening strategy is put forward. This study not only provides data support for evaluating economic benefits of retired batteries but also presents a method to recognize the battery aging variations, which is helpful for rapid evaluation and screening of retired batteries for 2nd use.

Olivine weathering in soil, and its effects on growth and nutrient uptake in Ryegrass (Lolium perenne L.): a pot experiment.

PubMed

ten Berge, Hein F M; van der Meer, Hugo G; Steenhuizen, Johan W; Goedhart, Paul W; Knops, Pol; Verhagen, Jan

2012-01-01

Mineral carbonation of basic silicate minerals regulates atmospheric CO(2) on geological time scales by locking up carbon. Mining and spreading onto the earth's surface of fast-weathering silicates, such as olivine, has been proposed to speed up this natural CO(2) sequestration ('enhanced weathering'). While agriculture may offer an existing infrastructure, weathering rate and impacts on soil and plant are largely unknown. Our objectives were to assess weathering of olivine in soil, and its effects on plant growth and nutrient uptake. In a pot experiment with perennial ryegrass (Lolium perenne L.), weathering during 32 weeks was inferred from bioavailability of magnesium (Mg) in soil and plant. Olivine doses were equivalent to 1630 (OLIV1), 8150, 40700 and 204000 (OLIV4) kg ha(-1). Alternatively, the soluble Mg salt kieserite was applied for reference. Olivine increased plant growth (+15.6%) and plant K concentration (+16.5%) in OLIV4. At all doses, olivine increased bioavailability of Mg and Ni in soil, as well as uptake of Mg, Si and Ni in plants. Olivine suppressed Ca uptake. Weathering estimated from a Mg balance was equivalent to 240 kg ha(-1) (14.8% of dose, OLIV1) to 2240 kg ha(-1) (1.1%, OLIV4). This corresponds to gross CO(2) sequestration of 290 to 2690 kg ha(-1) (29 10(3) to 269 10(3) kg km(-2).) Alternatively, weathering estimated from similarity with kieserite treatments ranged from 13% to 58% for OLIV1. The Olsen model for olivine carbonation predicted 4.0% to 9.0% weathering for our case, independent of olivine dose. Our % values observed at high doses were smaller than this, suggesting negative feedbacks in soil. Yet, weathering appears fast enough to support the 'enhanced weathering' concept. In agriculture, olivine doses must remain within limits to avoid imbalances in plant nutrition, notably at low Ca availability; and to avoid Ni accumulation in soil and crop.

Olivine Weathering in Soil, and Its Effects on Growth and Nutrient Uptake in Ryegrass (Lolium perenne L.): A Pot Experiment

PubMed Central

ten Berge, Hein F. M.; van der Meer, Hugo G.; Steenhuizen, Johan W.; Goedhart, Paul W.; Knops, Pol; Verhagen, Jan

2012-01-01

Mineral carbonation of basic silicate minerals regulates atmospheric CO2 on geological time scales by locking up carbon. Mining and spreading onto the earth's surface of fast-weathering silicates, such as olivine, has been proposed to speed up this natural CO2 sequestration (‘enhanced weathering’). While agriculture may offer an existing infrastructure, weathering rate and impacts on soil and plant are largely unknown. Our objectives were to assess weathering of olivine in soil, and its effects on plant growth and nutrient uptake. In a pot experiment with perennial ryegrass (Lolium perenne L.), weathering during 32 weeks was inferred from bioavailability of magnesium (Mg) in soil and plant. Olivine doses were equivalent to 1630 (OLIV1), 8150, 40700 and 204000 (OLIV4) kg ha−1. Alternatively, the soluble Mg salt kieserite was applied for reference. Olivine increased plant growth (+15.6%) and plant K concentration (+16.5%) in OLIV4. At all doses, olivine increased bioavailability of Mg and Ni in soil, as well as uptake of Mg, Si and Ni in plants. Olivine suppressed Ca uptake. Weathering estimated from a Mg balance was equivalent to 240 kg ha−1 (14.8% of dose, OLIV1) to 2240 kg ha−1 (1.1%, OLIV4). This corresponds to gross CO2 sequestration of 290 to 2690 kg ha−1 (29 103 to 269 103 kg km−2.) Alternatively, weathering estimated from similarity with kieserite treatments ranged from 13% to 58% for OLIV1. The Olsen model for olivine carbonation predicted 4.0% to 9.0% weathering for our case, independent of olivine dose. Our % values observed at high doses were smaller than this, suggesting negative feedbacks in soil. Yet, weathering appears fast enough to support the ‘enhanced weathering’ concept. In agriculture, olivine doses must remain within limits to avoid imbalances in plant nutrition, notably at low Ca availability; and to avoid Ni accumulation in soil and crop. PMID:22912685

Cotectic proportions of olivine and spinel in olivine-tholeiitic basalt and evaluation of pre-eruptive processes

USGS Publications Warehouse

Roeder, Peter; Gofton, Emma; Thornber, Carl

2006-01-01

The volume %, distribution, texture and composition of coexisting olivine, Cr-spinel and glass has been determined in quenched lava samples from Hawaii, Iceland and mid-oceanic ridges. The volume ratio of olivine to spinel varies from 60 to 2800 and samples with >0·02% spinel have a volume ratio of olivine to spinel of approximately 100. A plot of wt % MgO vs ppm Cr for natural and experimental basaltic glasses suggests that the general trend of the glasses can be explained by the crystallization of a cotectic ratio of olivine to spinel of about 100. One group of samples has an olivine to spinel ratio of approximately 100, with skeletal olivine phenocrysts and small (<50 μm) spinel crystals that tend to be spatially associated with the olivine phenocrysts. The large number of spinel crystals included within olivine phenocrysts is thought to be due to skeletal olivine phenocrysts coming into physical contact with spinel by synneusis during the chaotic conditions of ascent and extrusion. A second group of samples tend to have large olivine phenocrysts relatively free of included spinel, a few large (>100 μm) spinel crystals that show evidence of two stages of growth, and a volume ratio of olivine to spinel of 100 to well over 1000. The olivine and spinel in this group have crystallized more slowly with little physical interaction, and show evidence that they have accumulated in a magma chamber.

The existence of a temperature-driven solid solution in LixFePO4 for 0 <= x <= 1

NASA Astrophysics Data System (ADS)

Delacourt, Charles; Poizot, Philippe; Tarascon, Jean-Marie; Masquelier, Christian

2005-03-01

Lithium-ion batteries have revolutionized the powering of portable electronics. Electrode reactions in these electrochemical systems are based on reversible insertion/deinsertion of Li+ ions into the host electrode material with a concomitant addition/removal of electrons into the host. If such batteries are to find a wider market such as the automotive industry, less expensive positive electrode materials will be required, among which LiFePO4 is a leading contender. An intriguing fundamental problem is to understand the fast electrochemical response from the poorly electronic conducting two-phase LiFePO4/FePO4 system. In contrast to the well-documented two-phase nature of this system at room temperature, we give the first experimental evidence of a solid solution LixFePO4 (0 <= x <= 1) at 450 °C, and two new metastable phases at room temperature with Li0.75FePO4 and Li0.5FePO4 composition. These experimental findings challenge theorists to improve predictive models commonly used in the field. Our results may also lead to improved performances of these electrodes at elevated temperatures.

Annealing behaviour of ion tracks in olivine, apatite and britholite

NASA Astrophysics Data System (ADS)

Afra, B.; Lang, M.; Bierschenk, T.; Rodriguez, M. D.; Weber, W. J.; Trautmann, C.; Ewing, R. C.; Kirby, N.; Kluth, P.

2014-05-01

Ion tracks were created in olivine from San Carlos, Arizona (95% Mg2SiO4), apatite (Ca5(PO4)3(F,Cl,O)) from Durango, Mexico, and synthetic silicates with the apatite structure: Nd8Sr2(SiO4)6O2 and Nd8Ca2(SiO4)6O2 using 1.6 and 2.2 GeV Au ions. The morphology and annealing behaviour of the tracks were investigated by means of synchrotron based small angle X-ray scattering in combination with ex situ annealing. Tracks in olivine annealed above ∼400 °C undergo a significant change in track radius due to recrystallisation of the damage tracks. At temperatures higher than 620 °C, the scattering images indicate fragmentation of the track cylinders into smaller subsections. Ion tracks were annealed at elevated temperatures up to 400 °C in the Durango and Ca-britholite, and up to 560 °C in Sr-britholite. While there was a significant change in the track radii in the Durango apatite, tracks in the two synthetic samples remained almost unchanged.

Differential voltage analysis as a tool for analyzing inhomogeneous aging: A case study for LiFePO4|Graphite cylindrical cells

NASA Astrophysics Data System (ADS)

Lewerenz, Meinert; Marongiu, Andrea; Warnecke, Alexander; Sauer, Dirk Uwe

2017-11-01

In this work the differential voltage analysis (DVA) is evaluated for LiFePO4|Graphite cylindrical cells aged in calendaric and cyclic tests. The homogeneity of the active lithium distribution and the loss of anode active material (LAAM) are measured by the characteristic shape and peaks of the DVA. The results from this analysis exhibit an increasing homogeneity of the lithium-ion distribution during aging for all cells subjected to calendaric aging. At 60 °C, LAAM is found additionally and can be associated with the deposition of dissolved Fe from the cathode on the anode, where it finally leads to the clogging of pores. For cells aged under cyclic conditions, several phenomena are correlated to degradation, such as loss of active lithium and local LAAM for 100% DOD. Moreover, the deactivation of certain parts of anode and cathode due to a lithium-impermeable covering layer on top of the anode is observed for some cells. While the 100% DOD cycling is featured by a continuous LAAM, the LAAM due to deactivation by a covering layer of both electrodes starts suddenly. The homogeneity of the active lithium distribution within the cycled cells is successively reduced with deposited passivation layers and with LAAM that is lost locally at positions with lower external pressure on the electrode.

Cr, Mn, and Ca distributions for olivine in angritic systems: Constraints on the origins of Cr-rich and Ca-poor core olivine in angrite LEW87051

NASA Technical Reports Server (NTRS)

Mikouchi, T.; Mckay, G.; Le, L.

1994-01-01

Angrite meteorites are a type of basaltic achondrites that are noted for their very old cyrstallization ages (4.55 b.y.) and unusual chemical and mineralogical properties. In spite of great interest, only four angrites have been found. LEW87051 is the smallest one which weighs 0.6 g. It is a porphyritic rock with coarse subhedral to euhedral olivines set in a fine-grained groundmass which clearly represents a crystallized melt. The largest uncertainty about the petrogenesis of LEW87051 is the relationship between the large olivine crystals and the groundmass. Prinz et al. suggests that olivines are xenocrysts, while McKay et al. proposed a fractional cyrstallization model based on experimental studies. However, the crystals have Cr-rich and Ca-poor cores which do not match experimental olivines. Although Jurewicz and McKay tried to explaine the zoning of the rim by diffusion, some features are not explained. There also exists a definite composition boundary of Fe(2+) and MnO between the core and the rim. To clarify the origin of these olivines, we have performed experiments using LEW87051 analogs to measure the effects of oxygen fugacity on distribution coefficients of various elements in an angritic system.

Internal Stratigraphy of the Palisades Sill Olivine Zone: An Olivine Slurry Emplaced in a Hot Sill

NASA Astrophysics Data System (ADS)

Haddad, J. R.; Naslund, H. R.

2017-12-01

The Palisades Sill is a 300 m thick Jurassic-Triassic sill-like sheet formed from a quartz-normative tholeiitic magma. Three geochemical reversals within the sill are the result of magma chamber recharges. This study focuses on the reversal at 10 m height, widely considered to be the result of the emplacement of an olivine-rich slurry (Husch 1990, Gorring 1995). Major and trace elements were determined for 35 samples from the olivine layer and adjacent sill spanning 10 m of stratigraphic height. Samples were collected from outcrops near the Ross Dock Picnic Area in Fort Lee, NJ. Mineral compositions were determined for 21 thin sections using an electron microprobe (EMP). Bulk rock chemistry shows that the base of the olivine layer is between 2.5 and 3.25 m above the base of sampling. This is indicated by a marked reversal in Mg#, which jumped from 64.2 to 68.6; Al2O3, Co, Ni, Sc, Cs, Dy, and La also show clear reversals at the same interval. This is further collaborated by the formation of a ledge in the outcrop. Bulk chemistry and olivine composition show no systematic changes within the olivine layer. EMP analyses of augites reveals that below the 2.5 m height, crystals are typically strongly zoned, average rim Mg#= 67, core Mg#= 82. Above the 2.5 m layer, core Mg# are similar, but average rim Mg#=75. The plagioclase/augite ratio remains relatively constant through the olivine layer, but the ratio of olivine to plagioclase+augite is quite variable, suggesting that the olivine-slurry was emplaced as an inhomogeneous mixture of olivine + magma. Similar tholeiitic sills on Victoria Island, Canada, contain olivine-rich basal layers in which the olivine to plagioclase+augite ratio systematically increases, and the olivine composition becomes systematically more Fe-rich, from the base to the top of the layer. Comparisons between these otherwise similar basal olivine-rich layers, suggests that sills like the Palisades, which represents the injection of an olivine

SAXS study of ion tracks in San Carlos olivine and Durango apatite

NASA Astrophysics Data System (ADS)

Afra, B.; Rodriguez, M. D.; Lang, M.; Ewing, R. C.; Kirby, N.; Trautmann, C.; Kluth, P.

2012-09-01

Ion tracks were generated in crystalline San Carlos olivine (Mg,Fe)2SiO4 and Durango apatite Ca10(PO4)6F2 using different heavy ions (58Ni, 101Ru, 129Xe, 197Au, and 238U) with energies ranging between 185 MeV and 2.6 GeV. The tracks and their annealing behavior were studied by means of synchrotron based small angle X-ray scattering in combination with in situ annealing. Track radii vary as a function of electronic energy loss but are very similar in both minerals. Furthermore, the annealing behavior of the track radii has been investigated and preliminary results reveal a lower recovery rate of the damaged area in olivine compared with apatite.

Olivine Instability: An Experimental View of Mechanism of Deep Earthquakes

NASA Astrophysics Data System (ADS)

Long, H.; Weidner, D.; Li, L.; Chen, J.; Wang, L.

2007-12-01

Olivine (¦Á-(Mg,Fe)2SiO4) is the major constituent of the upper mantle and the ocean lithosphere. In subduction zone, where the earthquakes happen, the rheology of slab is mainly controlled by that of olivine. Several different mechanisms for deep focus earthquakes have been suggested, which include olivine instability (Bridgman, 1936; Orowan, 1960; Post, 1977; Ogawa, 1987; Hobbs and Ord, 1988; Kao and Chen, 1995), shear-induced melting (Griggs, 1954, 1972; Griggs and Handin, 1960; Griggs and Baker, 1969), phase transformation (Bridgman, 1945; Benioff, 1963; Meade and Jeanloz, 1989), dehydration of hydrous specimens (Meade and Jeanloz, 1991), and olivine metastability-induced anticrack (Green and Houston, 1995). Since the low temperature of the ¡°cold¡± slab, which can be as low as 600¡ãC in transition zone, olivine may still exist there and thus its shear instability may still be the possible mechanism for the deep-focus earthquakes. In our experimental study on deformation of San Carlos olivine at subduction zone conditions carried out on a D-DIA apparatus, Sam85 at X17B2, NSLS, we observed that the transitional temperature between regimes of insensitive to temperature and sensitive to temperature can be as high as 900¡ãC or even higher for the annealed polycrystal olivine sample, while that for unannealed sample can be as low as 450¡ãC. Our results for the unannealed sample are consistent to the result of Raterron et al (2004), which is concluded from the relaxation experiments. The annealed and unannealed olivine can be present the natural olivine in non-fault systems and that in pre-existing fault systems in subduction zone, respectively. We therefore propose a new olivine instability model with a ¡°sandwich¡± formation for the deep focus earthquakes: In this model the pre-existing fault system is surrounded by the no-fault systems. When the slab dives down, the olivine in both systems undergoes a stress- build-up process and can hold very high

Li-ion diffusion kinetics in LiCoPO 4 thin films deposited on NASICON-type glass ceramic electrolytes by magnetron sputtering

NASA Astrophysics Data System (ADS)

Xie, J.; Imanishi, N.; Zhang, T.; Hirano, A.; Takeda, Y.; Yamamoto, O.

LiCoPO 4 thin films were deposited on Li 1+ x+ yAl xTi 2- xSi yP 3- yO 12 (LATSP) solid electrolyte by radio frequency magnetron sputtering and were characterized by X-ray diffraction and scanning electron microscope. The films show a (1 1 1) preferred orientation upon annealing and are chemically stable with LATSP up to 600 °C in air. An all-solid-state Li/PEO 18-Li(CF 3SO 2) 2N/LATSP/LiCoPO 4/Au cell was fabricated to investigate the electrochemical performance and Li-ion chemical diffusion coefficients, D˜Li , of the LiCoPO 4 thin films. The potential dependence of D˜Li values of the LiCoPO 4 thin film was investigated by potentiostatic intermittent titration technique and was compared with those of the LiFePO 4 thin film. These results showed that the intercalation mechanism of Li-ion in LiCoPO 4 is different from that in LiFePO 4.

Moessbauer spectra of olivine-rich achondrites - Evidence for preterrestrial redox reactions

NASA Technical Reports Server (NTRS)

Burns, R. G.; Martinez, S. L.

1991-01-01

Moessbauer spectral measurements at 4.2 K were made on several ureilites and the two shergottites found in Antarctica, as well as two ureilite falls, three SNC meteorite falls, and two finds in order to distinguish products of preterrestrial redox reactions from phases formed during oxidative weathering on the earth. The spectra indicated that several ureilites contain major proportions of metallic iron, much of which resulted from preterrestrial carbon-induced reduction of ferrous iron in the outermost 10-100 microns of olivine grains in contact with carbonaceous material in the ureilites. The cryptocrystalline nature of these Fe inclusions in olivine renders the metal extremely vulnerable to aerial oxidation, even in ureilites collected as falls. It is inferred that the nanophase ferric oxides or oxyhydroxides identified in Brachina and Lafayette were produced by terrestrial weather of olivines before the meteorites were found. The absence of goethite in two olivine-bearing Antarctic shergottites suggests that the 2 percent ferric iron determined in their Moessbauer spectra also originated from oxidation on Mars.

Olivine-Rich Troctolite from the Southwest Indian Ridge: Constrains on Melt-Rock Reaction beneath Mid-Ocean Ridges

NASA Astrophysics Data System (ADS)

Yang, A. Y.

2017-12-01

The origin of olivine-rich troctolite, which have been recovered in the plutonic sample suites from the fast-spreading East Pacific Rise, and slow-spreading Mid-Atlantic Ridge and Central Indian Ridge, has been highly debated. They can form either by fractionation of primitive mid-ocean ridge basalt (MORB) melts or by melt migrating through pre-existing (possibly mantle) olivine matrix, thus recording valuable information of magmatic process at mantle-crust transition. This study presents in situ major and trace element study on the olivine-rich troctolite first reported from the ultraslow-spreading Southwest Indian Ridge (SWIR), together with a series of samples from peridotite, gabbro to basalt from an amagmatic segment at 53°E during Dayangyihao Cruises, to investigate the magmatic processes occurred at mantle-crust transition and origin of olivine-rich troctolite. The olivine in the troctolite shows cumulate textures with interstitial clinopyroxene, plagioclase and minor spinel, which is cross-cut by an olivine gabbro vein. Olivine in the troctolite show only mildly decreasing NiO contents (from 0.31-0.25 wt.%) with decreasing Fo (from 86 to 81), and even olivine in the gabbro have NiO up to 0.24 wt.% with Fo of 75. The Fo vs. Ni correlation of olivine is shifted to uniquely higher NiO at a certain Fo compared to the trends defined by either olivine from other lower oceanic crust (LOC) cumulates worldwide or olivine compositions from classic fractionation model for primitive MORB magma. Interstitial clinopyroxene in the troctolite have high Mg# (88-90), Cr2O3 (up to 1.51 wt.%) and TiO2 contents (up to 1.01 wt.%) with Eu/Eu* from 0.4-0.6. Such high-Ti-Cr-Mg# clinopyroxene is rare among global LOC cumulates, and cannot result from simple fractionation of MORB magma. The mineral compositions in the olivine-rich troctolite could be modeled by reaction between a primitive olivine matrix and a highly evolved melt (with 2.4 wt.% TiO2), and such a melt composition is

Soft-contact conductive carbon enabling depolarization of LiFePO4 cathodes to enhance both capacity and rate performances of lithium ion batteries

NASA Astrophysics Data System (ADS)

Ren, Wenju; Wang, Kai; Yang, Jinlong; Tan, Rui; Hu, Jiangtao; Guo, Hua; Duan, Yandong; Zheng, Jiaxin; Lin, Yuan; Pan, Feng

2016-11-01

Conductive nanocarbons generally are used as the electronic conductive additives to contact with active materials to generate conductive network for electrodes of commercial Li-ion batteries (LIBs). A typical of LiFePO4 (LFP), which has been widely used as cathode material for LIBs with low electronic conductivity, needs higher quantity of conductive nanocarbons to enhance the performance for cathode electrodes. In this work, we systematically studied three types of conductive nanocarbons and related performances in the LFP electrodes, and classify them as hard/soft-contact conductive carbon (named as H/SCC), respectively, according to their crystallite size, surface graphite-defect, specific surface area and porous structure, in which SCC can generate much larger contact area with active nano-particles of cathode materials than that of HCC. It is found that LFP nanocrystals wrapped in SCC networks perform significantly enhanced both capacity and rate performance than that in HCC. Combined experiments with multiphysics simulation, the mechanism is that LFP nanoparticles embedded in SCC with large contact area enable to generate higher depolarized effects with a relatively uniform current density vector (is) and lithium flux vector (NLi) than that in HCC. This discovery will guide us to how to design LIBs by selective using conductive carbon for high-performance LIBs.

Deformation of olivine under mantle conditions: An in situ high-pressure, high-temperature study using monochromatic synchrotron radiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hilairet, Nadège; Wang, Yanbin; Sanehira, Takeshi

2012-03-15

Polycrystalline samples of San Carlos olivine were deformed at high-pressure (2.8-7.8 GPa), high-temperature (1153 to 1670 K), and strain rates between 7.10{sup -6} and 3.10{sup -5} s{sup -1}, using the D-DIA apparatus. Stress and strain were measured in situ using monochromatic X-rays diffraction and imaging, respectively. Based on the evolution of lattice strains with total bulk strain and texture development, we identified three deformation regimes, one at confining pressures below 3-4 GPa, one above 4 GPa, both below 1600 K, and one involving growth of diffracting domains associated with mechanical softening above {approx}1600 K. The softening is interpreted as enhancedmore » grain boundary migration and recovery. Below 1600 K, elasto-plastic self-consistent analysis suggests that below 3-4 GPa, deformation in olivine occurs with large contribution from the so-called 'a-slip' system [100](010). Above {approx}4 GPa, the contribution of the a-slip decreases relative to that of the 'c-slip' [001](010). This conclusion is further supported by texture refinements. Thus for polycrystalline olivine, the evolution in slip systems found by previous studies may be progressive, starting from as low as 3-4 GPa and up to 8 GPa. During such a gradual change, activation volumes measured on polycrystalline olivine cannot be linked to a particular slip system straightforwardly. The quest for 'the' activation volume of olivine at high pressure should cease at the expense of detailed work on the flow mechanisms implied. Such evolution in slip systems should also affect the interpretation of seismic anisotropy data in terms of upper mantle flow between 120 and 300 km depth.« less

Olivine-rich asteroids in the near-Earth space

NASA Astrophysics Data System (ADS)

Popescu, Marcel; Perna, D.; Barucci, M. A.; Fornasier, S.; Doressoundiram, A.; Lantz, C.; Merlin, F.; Belskaya, I. N.; Fulchignoni, M.

2018-06-01

In the framework of a 30-night spectroscopic survey of small near-Earth asteroids (NEAs), we present new results regarding the identification of olivine-rich objects. The following NEAs were classified as A-type using visible spectra obtained with 3.6-m New Technology Telescope: (293726) 2007 RQ17, (444584) 2006 UK, 2012 NP, 2014 YS34, 2015 HB117, 2015 LH, 2015 TB179, 2015 TW144. We determined a relative abundance of 5.4 per cent (8 out of 147 observed targets) A-types at a 100-m size range of NEA population. The ratio is at least five times larger compared with the previously known A-types, which represent less than ˜ 1 per cent of NEAs taxonomically classified. By taking into account that part of our targets may not be confirmed as olivine-rich asteroids by their near-infrared spectra, or they can have a nebular origin, our result provides an upper-limit estimation of mantle fragments at size ranges below 300 m. Our findings are compared with the `battered-to-bits' scenario, claiming that at small sizes the olivine-rich objects should be more abundant when compared with basaltic and iron ones.

Early stage sustainability evaluation of new, nanoscale cathode materials for Li-ion batteries.

PubMed

Hischier, Roland; Kwon, Nam Hee; Brog, Jean-Pierre; Fromm, Katharina M

2018-05-07

We present results of early stage sustainability evaluation of two development strategies for new, nano-scale cathode materials for Li-ion batteries: (i) a new production pathway of existing material (LiCoO2), and (ii) a new nanomaterial (LiMnPO4). Nano-LiCoO2 was synthesized via a single source precursor route at lower temperature with a shorter reaction time, resulting in a smaller grain size and, thereby, a better diffusivity for Li-ions. Nano-LiMnPO4 was synthesized via a wet chemical method. The sustainability potential of these materials has then been investigated (at the laboratory and pilot production scales). The results show that the environmental impact of nano-LiMnPO4 is lower compared to the other examined nanomaterial by several factors, and this regardless of the indicator for the comparison. In contrast to commercial cathode materials, this new material shows, particularly on an energy and capacity basis, results in the same order of magnitude as those of lithium manganese oxide (LiMn2O4), and only slightly higher values than those for lithium iron phosphate (LiFePO4); values that are clearly lower than those for high-temperature LiCoO2. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Vaporization and thermodynamics of forsterite-rich olivine and some implications for silicate atmospheres of hot rocky exoplanets

NASA Astrophysics Data System (ADS)

Costa, Gustavo C. C.; Jacobson, Nathan S.; Fegley, Bruce, Jr.

2017-06-01

We describe an experimental and theoretical study of olivine [Mg2SiO4 (Fo)-Fe2SiO4 (Fa)] vaporization. The vaporization behavior and thermodynamic properties of a fosterite-rich olivine (Fo95Fa5) have been explored by high-temperature Knudsen effusion mass spectrometry (KEMS) from 1750 to 2250 K. The gases observed (in order of decreasing partial pressure) are Fe, SiO, Mg, O2 and O. We measured the solidus temperature (∼2050 K), partial pressures of individual gases, the total vapor pressure, and thermodynamic activities and partial molar enthalpies of MgO, 'FeO', and SiO2 for the Fo95Fa5 olivine. The results are compared to other measurements and models of the olivine system. Our experimental data show olivine vaporizes incongruently. We discuss this system both as a psuedo-binary of Fo-Fa and a psuedo-ternary of MgO-'FeO'-SiO2. Iron/magnesium molar ratios in the sample before (∼0.05) and after (∼0.04) vaporization are consistent with the small positive deviations from ideality of fayalite (γ ∼ 1.17) in olivine of the composition studied (e.g., Nafziger and Muan, 1967). Our data for olivine + melt confirm prior theoretical models predicting fractional vaporization of Fe relative to Mg from molten silicates (Fegley and Cameron, 1987; Schaefer and Fegley, 2009; Ito et al., 2015). If loss of silicate atmospheres occurs from hot rocky exoplanets with magma oceans the residual planet may be enriched in magnesium relative to iron.

Synthesis, characterization and lithium-ion migration dynamics simulation of LiFe1- x T x PO4 (T = Mn, Co, La and Ce) doping cathode material for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Xiao, Yi; Zhang, Fu Chun; Han, Jeong In

2016-11-01

LiFePO4 was doped by metallic cation in Fe sites via ball milling by a solid-state reaction method synthesis, and with very low-level doping of these samples, such as Li0.95T0.05FePO4 (where T = Mn2+, Co2+, La3+, Ce4+). The effects of doping were studied by X-ray diffraction pattern, Raman shift, scanning electronic microscopy and energy-dispersive X-ray spectroscopy as sample characterizations. The results indicate that these dopants have no significant effect on the structure of the material, but considerably improve its electrochemical behavior. First-principles calculations were used to obtain the migration pathway of Li ions along the one-dimensional (010) direction in LiFePO4, and molecular dynamics simulation was used to investigate the lithium-ion diffusion coefficients ( D Li) inside LiFePO4, which were derived from the slope of the mean square displacement versus time plots. The evolution of the structure during the simulation was analyzed by the radial distribution function to obtain the data, and radial distribution functions and mean square displacements were used to confirm the formation of crystalline units and the evolution of structure.

Disequilibrium growth of olivine in mafic magmas revealed by phosphorus zoning patterns of olivine from mafic-ultramafic intrusions

NASA Astrophysics Data System (ADS)

Xing, Chang-Ming; Wang, Christina Yan; Tan, Wei

2017-12-01

Olivine from mafic-ultramafic intrusions rarely displays growth zoning in major and some minor elements, such as Fe, Mg and Ni, due to fast diffusion of these elements at high temperatures. These elements in olivine are thus not useful in deciphering magma chamber processes, such as magma convection, multiple injection and mixing. High-resolution X-ray elemental intensity mapping reveals distinct P zoning patterns of olivine from two mafic-ultramafic intrusions in SW China. Polyhedral olivine grains from lherzolite and dunite of the Abulangdang intrusion show P-rich dendrites similar to those observed in volcanic rocks. Rounded olivine grains from net-textured Fe-Ti oxide ores of the Baima layered intrusion have irregular P-rich patches/bands crosscut and interlocked by P-poor olivine domains. P-rich patches/bands contain 250 to 612 ppm P, much higher than P-poor olivine domains with 123 to 230 ppm P. In electron backscattered diffraction (EBSD) maps, P-rich patches/bands within a single olivine grain have the same crystallographic orientation, indicating that they were remnants of the same crystal. Thus, both P-rich patches/bands and P-poor olivine domains in the same grain show a disequilibrium texture and clearly record two-stage growth. The P-rich patches/bands are likely the remnants of a polyhedral olivine crystal that formed in the first stage, whereas the P-poor olivine domains containing rounded Ti-rich magnetite and Fe-rich melt inclusions may have formed from an Fe-rich ambient melt in the second stage. The complex P zoning of olivine can be attributed to the dissolution of early polyhedral olivine and re-precipitation from the Fe-rich ambient melt. The early polyhedral olivine was in chemical disequilibrium with the ambient melt that may have been developed by silicate liquid immiscibility in a crystal mush. Our study implies that olivine crystals in igneous cumulates with an equilibrium appearance may have experienced disequilibrium growth processes

Reaction mechanism and thermal stability study on cathode materials for rechargeable lithium ion batteries

NASA Astrophysics Data System (ADS)

Fang, Jin

Olivine-type lithium iron phosphate has been a very promising cathode material since it was proposed by Padhi in 1997, low-cost, environmental friendly and stable structure ensure the commercialization of LiFePO 4. In LiFePO4, during charge and discharge process, Li ions are transferred between two phases, Li-poor LialphaFePO 4 and Li-rich Li1-betaFePO4, which implies a significant energy barrier for the new phase nucleation and interface growth, contrary to the fast reaction kinetics experimentally observed. The understanding of the lithiation and delithiation mechanism of this material has spurred a lot of research interests. Many theory models have been proposed to explain the reaction mechanism of LiFePO4, among them, the single phase model claims that the reaction goes through a metastable single phase, and the over potential required to form this single phase is about 30mV, so we studied the driving force to transport lithium ions between Lialpha FePO4 and Li1-betaFePO4 phases and compared the particle sizes effect. Experiment results shows that, the nano-sized (30nm) LiFePO4 has wider solid solution range, lower solid solution formation temperature and faster kinetics than normal LiFePO4 (150nm). Also a 20mV over potential was observed in both samples, either after relaxing the FePO4/LiFePO4 system to equilibrium or transport lithium from one side to the other side, the experiment result is corresponding to theoretical calculation; indicates the reaction might go through single-phase reaction mechanism. The energy and power density of lithium ion battery largely depend on cathode materials. Mn substituted LiFePO4 has a higher voltage than LiFePO4, which results a higher theoretical energy density. Safety issue is one of the most important criterions for batteries, since cathode materials need to maintain stable structure during hundreds of charge and discharge cycles and ranges of application conditions. We have reported that iron-rich compound o-Fe1-yMnyPO4

Discriminating between pyroxenite and peridotite sources for continental flood basalts (CFB) in southern Africa using olivine chemistry

NASA Astrophysics Data System (ADS)

Howarth, Geoffrey H.; Harris, Chris

2017-10-01

Continental Flood Basalts (CFB) result from voluminous outpourings of magma that often precede continental break-up. Notwithstanding the petrogenetic importance of CFBs, the nature of the mantle source for such magmas is contentious, particularly with regard to picrites with Ni-rich olivine phenocrysts. Previous studies have suggested that Ni-rich olivines associated with plume volcanism in regions of thickened (>90 km) lithosphere are related to either source mineralogy differences (peridotite versus pyroxenite) or change in olivine-melt partitioning due to pressure increase. In order to evaluate these two hypotheses, we present trace element data for olivines from the Karoo CFB Tuli and Mwenezi picrites and the Etendeka CFB Horingbaai/LTZ-L type picrites, all of which erupted in regions of thickened (>90 km) lithosphere in southern Africa. Karoo picrite olivines are Ni-rich, Ca- and Mn-poor, and have low (<1.4) 100*Mn/Fe. These compositions are consistent with a pyroxenitic source. Etendeka Horingbaai/LTZ-L picrite olivines do not show Ni-enrichment, but are characterized by high Al and Cr, and high (>1.4) 100*Mn/Fe, which is more consistent with high temperature melting of a dominantly peridotitic source. We also show that the Karoo and Etendeka olivines are characterized by distinct Mn/Zn ratios of <13 and >15, respectively. In addition, bulk rock geochemical data compilations and previously reported olivine δ18O for Karoo and Etendeka CFBs are discussed in order to further constrain source components based on previously described pyroxenite melt geochemical indices such as MgO-CaO systematics, FeO/MnO, Zn/Fe, and FC3MS (FeO/CaO-3*MgO/SiO2). These geochemical indices suggest a pyroxenite-dominated source for Karoo CFBs as well as for Etendeka ferropicrites whereas a peridotite-dominated source is indicated for Etendeka Horingbaai/LTZ-L type picrites analyzed in this study. Based on our data, Ni-enrichment of olivine in plume-related magmas in regions of

New constraints on Xe incorporation mechanisms in olivine from first-principles calculations

NASA Astrophysics Data System (ADS)

Crépisson, Céline; Blanchard, Marc; Lazzeri, Michele; Balan, Etienne; Sanloup, Chrystèle

2018-02-01

Storage of Xe at depth in silicate minerals has recently been proposed to explain the low Xe abundance in the Earth's and Mars' atmospheres compared to other noble gases (the so-called 'Missing Xenon' issue). Evidences for incorporation, and thus reactivity of Xe in olivine at high pressure and high temperature are based on variations in cell parameters and the appearance of a new Raman band. To constrain the, so far only hypothetical, Xe incorporation mechanism in olivine, we theoretically investigated models of Xe-bearing olivine using density functional theory. Three types of incorporation mechanisms are tested: Xe for Si and Xe for Mg substitutions, and interstitial Xe. Xe for Si substitution, implying an oxidation of Xe, is found to be the only mechanism consistent with experimental observations, leading to an increase of cell parameter a and the appearance of a new Raman band around 720-750 cm-1 associated with Xesbnd O stretching vibrations. Raman spectroscopy makes it possible to identify Xe incorporation site, even at low Xe content, due to high Xe polarizability. An estimation of Xe content in olivine, based on present work and previous in situ experimental results, shows that up to 0.4 at.% Xe could be stored in olivine at depth.

Synthesis and characterization of high performance electrode materials for lithium ion batteries

NASA Astrophysics Data System (ADS)

Hong, Jian

Lithium-ion batteries have revolutionized portable electronics. Electrode reactions in these electrochemical systems are based on reversible intercalation of Li+ ions into the host electrode material with a concomitant addition/removal of electrons into the host. If such batteries are to find a wider market such as the automotive industry, less expensive and higher capacity electrode materials will be required. The olivine phase lithium iron phosphate has attracted the most attention because of its low cost and safety (high thermal and chemical stability). However, it is an intriguing fundamental problem to understand the fast electrochemical response from the poorly electronic conducting two-phase LiFePO4/FePO 4 system. This thesis focuses on determining the rate-limit step of LiFePO4. First, a LiFePO4 material, with vanadium substituting on the P-site, was synthesized, and found that the crystal structure change may cause high lithium diffusivity. Since an accurate Li diffusion coefficient cannot be measured by traditional electrochemical method in a three-electrode cell due to the phase transformation during measurement, a new method to measure the intrinsic electronic and ionic conductivity of mixed conductive LiFePO 4 was developed. This was based on the conductivity measurements of mixed conductive solid electrolyte using electrochemical impedance spectroscopy (EIS) and blocking electrode. The effects of ionic/electronic conductivity and phase transformation on the rate performance of LiFePO4 were also first investigated by EIS and other electrochemical technologies. Based on the above fundamental kinetics studies, an optimized LiFePO4 was used as a target to deposit 1mum LiFePO4 thin film at Oak Ridge National Laboratory using radio frequency (RF) magnetron sputtering. Similar to the carbon coated LiFePO4 powder electrode, the carbon-contained RF LiFePO4 film with no preferential orientation showed excellent capacity and rate capability both at 25°C and -20

Comparing olivine single crystal and polycrystal rheology: evidence for supplementary accommodation mechanisms at grain boundaries

NASA Astrophysics Data System (ADS)

Bollinger, C.; Merkel, S.; Raterron, P.; Castelnau, O.; Detrez, F.

2013-12-01

Rheology in the Earth's upper-mantle is mostly constrained by the plastic properties of olivine. Over recent years, several groups have been carrying out deformation experiments on single crystals and polycrystals of olivine at upper mantle pressure (P) and temperature (T). Yet, the rheology of olivine at mantle conditions is still not well constrained. We carried out deformation experiments on San Carlos olivine polycrystals, at P and T ranging from 3 to 8 GPa and 1373 to 1673 K, respectively, and at strain rates ranging from 10-6 to 10-4 s-1, using the D-DIA apparatus installed at the NSLS X17B2 beamline (NY, USA). The deformation rates of the polycrystals are compared to those of single crystals oriented along the soft orientations [110]c, [011]c, [101]c which activate the easiest slip systems (Raterron et al., 2012). This comparison suggests that, in olivine polycrystals deforming in the dislocation creep regime, other relaxation mechanisms need to be considered to account for the observed polycrystal strain rates. This highlights the importance of supplementary mechanisms, such as those occurring at grain boundaries, to properly model olivine aggregates plasticity.

Potential Temperatures of Sources of MORB, OIB and LIPs Based on AL Partitioning Between Olivine and Spinel

NASA Astrophysics Data System (ADS)

Sobolev, A. V.; Batanova, V. G.; Krasheninnikov, S.; Borisov, A.; Arndt, N.; Kuzmin, D.; Krivolutskaya, N.; Sushevskaya, N.

2013-12-01

Knowledge of potential temperatures of convecting mantle is required for the understanding the global processes on the Earth [1]. The common way to estimate these is the reconstruction of primary melt compositions and liquidus temperatures based on the Fe-Mg partitioning between olivine and melt. This approach requires knowledge of the compositions of primitive melts in equilibrium with olivine alone as well as composition of olivine equilibrium with primary melts. This information is in most cases unavailable or of questionable quality. Here we report a new approach to obtain crystallization temperatures of primary melts based on the olivine-spinel Al-Cr geothermometer [2]. The advantages of this approach are: (1) low rate of diffusion of Al in the olivine, which promises to preserve high magmatic temperatures and (2) common presence of spinel in assemblage with high-Mg olivine. In order to decipher influence of elevated Ti concentrations in spinel we have run several experiments at high temperatures (1400-1200 degree C), atmospheric pressure and controled oxygen fugacity. We also analysed over two thousand spinel inclusions and high-Mg host olivines from different MORB, OIB, LIP and Archean komatiites on the JXA-8230 EPMA at ISTerre, Grenoble, France. Concentrations of Al, Ti, Na, P, Zn, Cr, Mn, Ca, Co, Ni were determined with a precision of 10 ppm (2 standard errors) using a newly developed protocol [3]. When available, we also analysed matrix glass and glass inclusions in olivine and found that temperature estimations from olivine-spinel (Al-Cr) and olivine-melt (Fe-Mg) [4] equilibrium match within (+/-30 degree C). The results show contrasting crystallization temperatures of Mg-rich olivine of the same Fo content from different types of mantle-derived magmas, from the lowest (down to 1220 degree C) for MORB to the highest (up to 1550 degree C) for komatiites and Siberian meimechites. These results match predictions from Fe-Mg olivine-melt equilibrium and

Direct synthesis and characterization of mixed-valent Li 0.5$-$δCoPO 4, a Li-deficient derivative of the Cmcm polymorph of LiCoPO 4

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ludwig, Jennifer; Alarcon-Suesca, Carlos; Geprags, Stephan

While the majority of research activities on LiCoPO 4 is focussed on the thermodynamically stable olivine-type Pnma polymorph, the metastable Pna2 1 and Cmcm modifications have recently attracted considerable attention due to their interesting material properties. In this study, we present the first Li-deficient structural derivative of the Cmcm modification with the nominal composition Li 0.5–δCoPO 4. As opposed to the substoichiometric olivine ( Pnma) phases Li xCoPO 4 (x = 0; 2/3), which are exclusively accessible by electrochemical or chemical Li extraction techniques, this is also the first time that a direct soft-chemical synthesis route towards a Li xCoPOmore » 4-type material is accomplished. X-ray and neutron diffraction studies indicate that Cmcm-type Li 0.5–δCoPO 4 shows vacancies on both the Li and Co sites, whereas X-ray absorption spectra demonstrate that the structure features heterovalent Co ions (+2/+3) to compensate for the Li deficit. Magnetic measurements reveal a long-range antiferromagnetic order below 10.5 K. A thorough investigation of the thermal stability using thermogravimetric analysis, differential scanning calorimetry, and temperature-dependent in situ X-ray powder diffraction demonstrates that Li 0.5–δCoPO 4 is metastable and exhibits a complex, multi-step thermal decomposition mechanism. In the first step at 394 °C, it decomposes to α-Co 2P 2O 7 ( P2 1/c) and LiCoPO 4 ( Cmcm) upon O 2 release. The LiCoPO 4 ( Cmcm) intermediate is then irreversibly transformed to olivine-type LiCoPO 4 (Pnma) at 686 °C. Furthermore, the material properties of Li 0.5–δCoPO 4 are further compared to the fully lithiated, isostructural LiCoPO 4 ( Cmcm) phase, for which an improved structure solution as well as Co L 2,3-edge X-ray absorption spectra are reported for the first time.« less

Direct synthesis and characterization of mixed-valent Li 0.5$-$δCoPO 4, a Li-deficient derivative of the Cmcm polymorph of LiCoPO 4

DOE PAGES

Ludwig, Jennifer; Alarcon-Suesca, Carlos; Geprags, Stephan; ...

2017-05-26

While the majority of research activities on LiCoPO 4 is focussed on the thermodynamically stable olivine-type Pnma polymorph, the metastable Pna2 1 and Cmcm modifications have recently attracted considerable attention due to their interesting material properties. In this study, we present the first Li-deficient structural derivative of the Cmcm modification with the nominal composition Li 0.5–δCoPO 4. As opposed to the substoichiometric olivine ( Pnma) phases Li xCoPO 4 (x = 0; 2/3), which are exclusively accessible by electrochemical or chemical Li extraction techniques, this is also the first time that a direct soft-chemical synthesis route towards a Li xCoPOmore » 4-type material is accomplished. X-ray and neutron diffraction studies indicate that Cmcm-type Li 0.5–δCoPO 4 shows vacancies on both the Li and Co sites, whereas X-ray absorption spectra demonstrate that the structure features heterovalent Co ions (+2/+3) to compensate for the Li deficit. Magnetic measurements reveal a long-range antiferromagnetic order below 10.5 K. A thorough investigation of the thermal stability using thermogravimetric analysis, differential scanning calorimetry, and temperature-dependent in situ X-ray powder diffraction demonstrates that Li 0.5–δCoPO 4 is metastable and exhibits a complex, multi-step thermal decomposition mechanism. In the first step at 394 °C, it decomposes to α-Co 2P 2O 7 ( P2 1/c) and LiCoPO 4 ( Cmcm) upon O 2 release. The LiCoPO 4 ( Cmcm) intermediate is then irreversibly transformed to olivine-type LiCoPO 4 (Pnma) at 686 °C. Furthermore, the material properties of Li 0.5–δCoPO 4 are further compared to the fully lithiated, isostructural LiCoPO 4 ( Cmcm) phase, for which an improved structure solution as well as Co L 2,3-edge X-ray absorption spectra are reported for the first time.« less

The effects of pressure, temperature and composition on olivine-liquid exchange coefficients

NASA Astrophysics Data System (ADS)

Matzen, A. K.; Wood, B. J.

2017-12-01

It has recently been observed that there is a correlation between trace element (Ni and Mn) concentrations in olivine (ol) phenocrysts and thickness of the lithosphere on which they were erupted [1]. There are a number of potential explanations for this observation: the mantle may have interacted with the Ni-rich core; the trace element concentrations reflect presence of recycled crust in the mantle; or it arises from melting of peridotite at different temperatures (T) and pressures (P). Discriminating between these hypotheses requires accurate models of olivine-silicate liquid (liq) partitioning. The three variables that control the observed variations in experimentally-derived ol-liq partition coefficients are T, P, and the composition of the silicate liquid (and to a lesser extent the olivine composition). However, experiments cannot unambiguously disentangle the effects of these variables. For olivine-saturated liquids at constant P, any change in T results in the crystallization or dissolution of olivine and thus a change in liquid composition, resulting in a correlation between T and silicate liquid composition (note that changing the bulk composition such that olivine saturation occurs at a different T also results in a correlation with composition and T). Alternatively, P and T can be varied in concert such that liquid and olivine compositions remain approximately constant [e.g., 2], resulting in a correlation between T and P. In an attempt to resolve the conflation of T, P and compositional effects we turned to metal (met)-liq partitioning studies. Experiments show that, unlike most other elements, P has a strong effect on the partitioning of Ni between Fe-rich metal and silicate melt. Assuming that the pressure dependence of K_{D, Ni-Fe}^{met-liq} (0-25 GPa) [3] is driven primarily by the changing activities in the silicate melt, we can approximate the effect that pressure will have on K_{D, Ni-Fe}^{ol-liq} as measured by [2], using Kress and Carmichael

Seismic evidence for olivine phase changes at the 410- and 660-kilometer discontinuities.

PubMed

Lebedev, Sergei; Chevrot, Sébastien; van der Hilst, Rob D

2002-05-17

The view that the seismic discontinuities bounding the mantle transition zone at 410- and 660-kilometer depths are caused by isochemical phase transformations of the olivine structure is debated. Combining converted-wave measurements in East Asia and Australia with seismic velocities from regional tomography studies, we observe a correlation of the thickness of, and wavespeed variations within, the transition zone that is consistent with olivine structural transformations. Moreover, the seismologically inferred Clapeyron slopes are in agreement with the mineralogical Clapeyron slopes of the (Mg,Fe)2SiO4 spinel and postspinel transformations.

Mineralogical Comparison of Olivine in Shergottites and A Shocked L Chondrite: Implications for Shock Histories of Brown Olivine

NASA Technical Reports Server (NTRS)

Takenouchi, A.; Mikouchi, T.; Yamaguchi, A.; Zolensky, M. E.

2015-01-01

Most Martian meteorites are heavily shocked, exhibiting numerous shock features, for example undulatory extinction of olivine and pyroxene, the presence of diaplectic glass ("maskelynite") and the formation of shock melt. Among these shock features, olivine darkening ("brown" olivine) is unique in Martian meteorites because no other meteorite group shows such a feature. Although the presence of brown olivine in shergottites was reported thirty years ago, detailed observation by TEM has not been performed until the NWA 2737 chassignite was discovered, whose olivine is darkened, being completely black in hand specimen. Fe metal nano-particles were found in NWA 2737 olivine which are considered to have been formed by olivine reduction during heavy shock. Subsequently, magnetite nano-particles were also found in other Martian meteorites and the coexistence of Fe metal and magnetite nano-particles was reported in the NWA 1950 shergottite and some Fe metal nano-particles were mantled by magnetite. Therefore, the formation process of nano-particles seems to be complex. Because "brown" olivine is unique to Martian meteorites, they have a potential to constrain their shock conditions. In order to better understand the shock history of Martian meteorites, we compared olivine in several shergottites with that in a highly-shocked L chondrite which contains ringwoodite.

Network topology of olivine-basalt partial melts

NASA Astrophysics Data System (ADS)

Skemer, Philip; Chaney, Molly M.; Emmerich, Adrienne L.; Miller, Kevin J.; Zhu, Wen-lu

2017-07-01

The microstructural relationship between melt and solid grains in partially molten rocks influences many physical properties, including permeability, rheology, electrical conductivity and seismic wave speeds. In this study, the connectivity of melt networks in the olivine-basalt system is explored using a systematic survey of 3-D X-ray microtomographic data. Experimentally synthesized samples with 2 and 5 vol.% melt are analysed as a series of melt tubules intersecting at nodes. Each node is characterized by a coordination number (CN), which is the number of melt tubules that intersect at that location. Statistically representative volumes are described by coordination number distributions (CND). Polyhedral grains can be packed in many configurations yielding different CNDs, however widely accepted theory predicts that systems with small dihedral angles, such as olivine-basalt, should exhibit a predominant CN of four. In this study, melt objects are identified with CN = 2-8, however more than 50 per cent are CN = 4, providing experimental verification of this theoretical prediction. A conceptual model that considers the role of heterogeneity in local grain size and melt fraction is proposed to explain the formation of nodes with CN ≠ 4. Correctly identifying the melt network topology is essential to understanding the relationship between permeability and porosity, and hence the transport properties of partial molten mantle rocks.

Hybrid lithium-ion capacitor with LiFePO4/AC composite cathode - Long term cycle life study, rate effect and charge sharing analysis

NASA Astrophysics Data System (ADS)

Shellikeri, A.; Yturriaga, S.; Zheng, J. S.; Cao, W.; Hagen, M.; Read, J. A.; Jow, T. R.; Zheng, J. P.

2018-07-01

Energy storage devices, which can combine the advantages of lithium-ion battery with that of electric double layer capacitor, are of prime interest. Recently, composite cathodes, which combine a battery material with capacitor material, have shown promise in enhancing life cycle and energy/power performances. Lithium-ion capacitor (LIC), with unique charge storage mechanism of combining a pre-lithiated battery anode with a capacitor cathode, is one such device which has the potential to synergistically incorporate the composite cathode to enhance capacity and cycle life. We report here a hybrid LIC consisting of a lithium iron phosphate (LiFePO4-LFP)/Activated Carbon composite cathode in combination with a hard carbon anode, by integrating the cycle life and capacity enhancing strategies of a dry method of electrode fabrication, anode pre-lithiation and a 3:1 anode to cathode capacity ratio, demonstrating a long cycle life, while elaborating on the charge sharing between the faradaic and non-faradaic mechanism in the battery and capacitor materials, respectively in the composite cathode. An excellent cell capacity retention of 94% (1000 cycles at 1C) and 92% (100,000 cycles at 60C) were demonstrated, while retaining 78% (over 6000 cycles at 2.7C) and 67% (over 70,000 cycles at 43C) of the LFP capacity in the composite cathode.

Crystallization kinetics of olivine-phyric shergottites

NASA Astrophysics Data System (ADS)

Ennis, Megan E.; McSween, Harry Y.

2014-08-01

Crystal size distribution (CSD) and spatial distribution pattern (SDP) analyses are applied to the early crystallizing phases, olivine and pyroxene, in olivine-phyric shergottites (Elephant moraine [EET] 79001A, Dar al Gani [DaG] 476, and dhofar [Dho] 019) from each sampling locality inferred from Mars ejection ages. Trace element zonation patterns (P and Cr) in olivine are also used to characterize the crystallization history of these Martian basalts. Previously reported 2-D CSDs for these meteorites are re-evaluated using a newer stereographically corrected methodology. Kinks in the olivine CSD plots suggest several populations that crystallized under different conditions. CSDs for pyroxene in DaG 476 and EET 79001A reveal single populations that grew under steady-state conditions; pyroxenes in Dho 019 were too intergrown for CSD analysis. Magma chamber residence times of several days for small grains to several months for olivine megacrysts are calculated using the CSD slopes and growth rates inferred from previous experimental data. Phosphorus imaging in olivines in DaG 476 and Dho 019 indicate rapid growth of skeletal, sector-zoned, or patchy cores, probably in response to delayed nucleation, followed by slow growth, and finally rapid dendritic growth with back-filling to form oscillatory zoning in rims. SPD analyses indicate that olivine and pyroxene crystals grew or accumulated in clusters rather than as randomly distributed grains. These data reveal complex solidification histories for Martian basalts, and are generally consistent with the formation at depth of olivine megacryst cores, which were entrained in ascending magmas that crystallized pyroxenes, small olivines, and oscillatory rims on megacrysts.

Unusual olivine and pyroxene composition in interplanetary dust and unequilibrated ordinary chondrites

NASA Technical Reports Server (NTRS)

Klock, W.; Mckay, D. S.; Thomas, K. L.; Palme, H.

1989-01-01

The presence, in both a number of interplanetary dust particles (IDPs) and in meteorite matrices, of olivine and orthopyroxene grains, low in FeO but containing up to 5 wt pct MnO, is reported. The majority of olivines and pyroxenes in meteorites contain less than 0.5 wt pct MnO. The presence of these low-iron, manganese-enriched (LIME) olivines and pyroxenes in IDPs and meteorites may indicate a link between the origin and history of IDPs and the matrix material of primitive meteorites. The origin of the LIME silicates could be explained by condensation from a gas of solar composition. Forsterite is the first major silicate phase to condense from a solar nebula gas, and Mn, which is not stable as a metal under solar nebula conditions, would condense at about 1100 K as Mn2SiO4 in solid solution with forsterite.

H Diffusion in Olivine and Pyroxene from Peridotite Xenoliths and a Hawaiian Magma Speedometer

NASA Technical Reports Server (NTRS)

Peslier, A. H.; Bizimis, M.

2014-01-01

Hydrogen is present as a trace element in olivine and pyroxene and its content distribution in the mantle results from melting and metasomatic processes. Here we examine how these H contents can be disturbed during decompression. Hydrogen was analyzed by FTIR in olivine and pyroxene of spinel peridotite xenoliths from Salt Lake Crater (SLC) nephelinites which are part of the rejuvenated volcanism at Oahu (Hawaii) [1,2]. H mobility in pyroxene resulting from spinel exsolution during mantle upwelling Most pyroxenes in SLC peridotites exhibit exsolutions, characterized by spinel inclusions. Pyroxene edges where no exsolution are present have less H then their core near the spinel. Given that H does not enter spinel [3], subsolidus requilibration may have concentrated H in the pyroxene adjacent to the spinel exsolution during mantle upwelling. H diffusion in olivine during xenolith transport by its host magma and host magma ascent rates Olivines have lower water contents at the edge and near fractures compared to at their core, while the concentrations of all other chemical elements appear homogeneous. This suggests that some of the initial water has diffused out of the olivine. Water loss from the olivine is thought to occur during host-magma ascent and xenolith transport to the surface [4-6]. Diffusion modeling matches best the data when the initial water content used is that measured at the core of the olivines, implying that mantle water contents are preserved at the core of the olivines. The 3225 cm(sup -1) OH band at times varies independantly of other OH bands, suggesting uneven H distribution in olivine defects likely acquired during mantle metasomatism just prior to eruption and unequilibrated. Diffusion times (1-48 hrs) combined with depths of peridotite equilibration or of magma start of degassing allow to calculate ascent rates for the host nephelinite of 0.1 to 27 m/s.

Cycling and rate performance of Li-LiFePO 4 cells in mixed FSI-TFSI room temperature ionic liquids

NASA Astrophysics Data System (ADS)

Lewandowski, A. P.; Hollenkamp, A. F.; Donne, S. W.; Best, A. S.

A study is conducted of the performance of lithium iron(II) phosphate, LiFePO 4, as a cathode material in a lithium secondary battery that features an ionic liquid electrolyte solution and a metallic lithium anode. The electrolyte solution comprises an ionic liquid of a N-methyl-N-alkyl-pyrrolidinium (alkyl = n-propyl or n-butyl) cation and either the bis(fluorosulfonyl)imide [(FSO 2) 2N -] or bis(trifluoromethanesulfonyl)imide [(F 3CSO 2) 2N -] anion, together with 0.5 mol kg -1 of lithium bis(trifluoromethanesulfonyl)imide salt. For N-methyl-N-propyl-pyrrolidinium bis(fluorosulfonyl)imide, coin cells discharging at rates of C/10 and 4C yield specific capacities of 153 and 110 mAh g -1, respectively, at an average coulombic efficiency of 99.8%. This performance is maintained for over 400 cycles at 50 °C and therefore indicates that these electrolyte solutions support long-term cycling of both LiFePO 4 and metallic lithium while, due to the negligible volatility of ionic liquids, surrounding the lithium in an inherently safe, non-flammable medium.

Experiment and simulation of a LiFePO4 battery pack with a passive thermal management system using composite phase change material and graphite sheets

NASA Astrophysics Data System (ADS)

Lin, Chunjing; Xu, Sichuan; Chang, Guofeng; Liu, Jinling

2015-02-01

A passive thermal management system (TMS) for LiFePO4 battery modules using phase change material (PCM) as the heat dissipation source to control battery temperature rise is developed. Expanded graphite matrix and graphite sheets are applied to compensate low thermal conductivity of PCM and improve temperature uniformity of the batteries. Constant current discharge and mixed charge-discharge duties were applied on battery modules with and without PCM on a battery thermal characteristics test platform. Experimental results show that PCM cooling significantly reduces the battery temperature rise during short-time intense use. It is also found that temperature uniformity across the module deteriorates with the increasing of both discharge time and current rates. The maximum temperature differences at the end of 1C and 2C-rate discharges are both less than 5 °C, indicating a good performance in battery thermal uniformity of the passive TMS. Experiments on warm-keeping performance show that the passive TMS can effectively keep the battery within its optimum operating temperature for a long time during cold weather uses. A three dimensional numerical model of the battery pack with the passive TMS was conducted using ANSYS Fluent. Temperature profiles with respect to discharging time reveal that simulation shows good agreement with experiment at 1C-discharge rate.

Diffusion of Water through Olivine and Clinopyroxene: Implications for Melt Inclusion Fidelity

NASA Astrophysics Data System (ADS)

Plank, T. A.; Lloyd, A. S.; Ferriss, E.

2016-12-01

The maximum H2O concentrations measured in olivine-hosted melt inclusions (MIs) from arc tephra fall within a narrow range of 3-5 wt%. A major question is whether this reflects parental water concentrations or diffusive exchange through the host crystal during storage and ascent. Laboratory experiments have shown that water can diffuse through 500 micron olivine in minutes to days at 1100°C. We have tested these predictions with a natural experiment using volatile (H2O, CO2, S) diffusion along melt embayments to constrain ascent rates during the 1974 eruption of Volcan Fuego to 5-8 minutes from 7 km depth [1]. Thus, olivine-hosted MIs may move from their storage region to the surface during some eruptions rapidly enough to retain almost all of their original water. Only the smallest MIs (< 30 microns) will lose any water during such fast ascent, even for the fastest diffusion mechanism through olivine. We have also assessed the potential for clinopyroxene (cpx) to retain water (as H+) during magma ascent. In the same 1974 Fuego deposits, cpx crystals show H-loss on their rims and even from their interiors. Such diffusive loss in 5-8 minutes requires rapid diffusion of H in cpx, comparable to olivine and melt, and consistent with our recent laboratory experiments dehydrating Fe-bearing cpx [2]. Although H-diffusion is dependent on the site occupancy, all sites may lose H rapidly in cpx with Mg# < 92.5. While cpx and olivine may lose H during ascent and degassing, olivine-hosted MIs stand a better chance of retaining water due to the very low partitioning of water in olivine (D 0.001). The most favorable conditions for faithful retention of parental water concentrations involve a) rapid ascent (< hr.) from H2O-undersaturated reservoirs (prior to major water degassing), b) minerals with low partition coefficients for water, c) large crystals (>500 microns) and large melt inclusions (>50 microns), and 4) rapid post-eruptive cooling (< 1min, clast sizes < 1 cm). The

Phosphorus zoning in olivine of Kilauea Iki lava lake, Hawaii

NASA Astrophysics Data System (ADS)

Fabbrizio, Alessandro; Beckett, John R.; Baker, Michael B.; Stolper, Edward M.

2010-05-01

Kilauea Iki lava lake was formed when the lavas of the 1959 summit eruption of Kilauea volcano ponded in Kilauea Iki pit crater, as described by [1]. The main chamber of this lake has been drilled repeatedly from 1960 to 1981 as the lake has cooled and crystallized and partial descriptions of core can be found in [2-7]. The bulk of the core consists of a gray, olivine-phyric basalt matrix [3]. Rapid diffusion of divalent cations through olivine at magmatic temperatures can delete information on early-formed zoning and thus information on early magmatic history, recorded in olivine during its growth, is often largely lost [8-11]. In the last years many studies [8-11] have shown that natural olivine, terrestrial and extraterrestrial, from several localities and rock types can preserve a complex zoning in P (sometimes associated with Cr and Al). Simple crystallization experiments conducted by [10] and [11] were able to replicate these features (i.e., sector and oscillatory zoning). Here, we describe P, Cr and Al zoning in olivine from the 1981 drilling of Kilauea Iki lava lake hole #1 (KI81-1) [6]. Kα X-ray intensity maps and major and minor element quantitative analyses were obtained using the Caltech JEOL JXA-8200 electron microprobe. We acquired P, Cr, Al, Fe and Ti X-ray maps simultaneously at 15 kV and 400 nA, a beam diameter of 1 μm, pixel spacing of 1-2 μm, and count times of 420-1500 msec/step were used depending on the dimension of the crystal. 15 kV and 40 nA with a beam diameter of 1 μm were used to collect quantitative analyses. P2O5 contents of the Iki olivines range from below detection limit to 0.30 wt%. Zoning in phosphorus, based on X-ray intensity maps, was observed in all olivines we examined. The P zoning patterns of the olivines display several styles. P shows oscillatory zoning comparable to that seen in terrestrial and extraterrestrial igneous olivines and in experimentally grown olivine [8-11]; high P regions, inside the crystals, outline

V/Sc in olivine as a proxy for magma redox conditions

NASA Astrophysics Data System (ADS)

Locmelis, M.; Arevalo, R. D., Jr.; Puchtel, I. S.; Fiorentini, M. L.

2017-12-01

Although olivine is the most abundant mineral in the upper mantle and a major constituent of most mantle-derived rocks, studies on its trace element chemistry are underrepresented. This is especially the case for komatiites, an ultramafic, olivine-dominated rock type that formed via high degrees of partial melting (up to 50%) of the mantle. Komatiites were mostly emplaced in the Archean and therefore provide a unique perspective on the composition and evolution of the early Earth's mantle. Here, we present the V/Sc compositions of olivines from a global set of Paleo- (3.5-3.3 Ga) and Neo-Archean (2.7 Ga) komatiites analyzed via laser ablation ICP-MS. Vanadium and Sc behave similar during partial melting, but V is redox-sensitive (V2+-V5+) and most compatible in olivine as V2+. Scandium is monovalent (Sc3+) and its compatibility in olivine is not affected by the oxygen fugacity (fO2) of the komatiite lava. Therefore, V/Sc ratios in olivines are potentially indicative of the fO2 of the magma they crystallized from. Our data show that V/Sc ratios measured in Neo-Archean olivines (V/Scmean = 1.0 ± 0.1; 2σm) are significantly lower than in their Paleo-Archean counterparts (V/Scmean = 2.1 ± 0.1; 2σm). Geochemical models show that the elevated V/Sc ratios captured by the Paleo-Archean olivines reflect crystallization from magmas that were 1.6 log units (relative to QFM) more reduced than their Neo-Archean counterparts, and thus contained a higher proportion of V2+. Because assimilation of sedimentary bedrocks can alter the composition of komatiites upon emplacement, it may be argued that the redox states recorded by the olivines do not reflect mantle fO2, but the assimilation of crustal material. However, such an effect is not visible in our data as V/Sc ratios in olivines from localities that show evidence of crustal assimilation do not differ from komatiites that did not assimilate significant amounts of crustal rocks. Rather than a crustal signature, the V

Comparative in situ X-ray Diffraction Study of San Carlos Olivine: Influence of Water on the 410 km Seismic Velocity Jump in Earth’s Mantle

DOE Office of Scientific and Technical Information (OSTI.GOV)

J Chen; H Liu; J Girard

2011-12-31

A comparative study of the equation of states of hydrous (0.4 wt% H{sub 2}O) and anhydrous San Carlos olivine (<30 ppm H2O) was conducted using synchrotron X-rays up to 11 GPa in a diamond anvil cell (DAC) at ambient temperature. Both samples were loaded in the same high-pressure chamber of the DAC to eliminate the possible pressure difference in different experiments. The obtained compression data were fitted to the third-order Birch-Murnaghan equation of state, yielding a bulk modulus K{sub 0} = 123(3) GPa for hydrous olivine and K{sub 0} = 130(4) GPa for anhydrous olivine as K{sub 0}' is fixedmore » at 4.6. Therefore, 0.4 wt% H{sub 2}2O in olivine results in a 5% reduction in bulk modulus. Previous studies reported bulk modulus reduction by water in olivine's high-pressure polymorph (wadsleyite), to which the transformation from olivine gives rise to the seismic discontinuity at 410 km depth. The new data results in a reduction in the magnitude of the discontinuity by 50% in v{sub P} and 30% in v{sub S} (for 1:5 water partitioning between olivine and wadsleyite) with respect to anhydrous mantle. Previous knowledge of the influence of water on this phase transition has been in opposition to a large amount of water [e.g., 200 ppm by Wood (1995)] existing at 410 km depth. Calculation of the seismic velocities based on newly available elasticity data of the hydrous phases indicates that the presence of water is favorable for the mineral composition model (pyrolite) and seismic observations in terms of the magnitude of the 410 km discontinuity.« less

A New Spinel-Olivine Oxybarometer: Near-Liquidus Partitioning of V between Olivine-Melt, Spinel-Melt, and Spinel-Olivine in Martian Basalt Composition Y980459 as a Function of Oxygen Fugacity

NASA Technical Reports Server (NTRS)

Papike, J. J.; Le, L.; Burger, P. V.; Shearer, C. K.; Bell, A. S.; Jones, J.

2013-01-01

Our research on valence state partitioning began in 2005 with a review of Cr, Fe, Ti, and V partitioning among crystallographic sites in olivine, pyroxene, and spinel [1]. That paper was followed by several on QUE94201 melt composition and specifically on Cr, V, and Eu partitioning between pyroxene and melt [2-5]. This paper represents the continuation of our examination of the partitioning of multivalent V between olivine, spinel, and melt in martian olivine-phyric basalts of Y980459 composition [6, 7]. Here we introduce a new, potentially powerful oxybarometer, V partitioning between spinel and olivine, which can be used when no melt is preserved in the meteorite. The bulk composition of QUE94201 was ideal for our study of martian pyroxene-phyric basalts and specifically the partitioning between pyroxene-melt for Cr, V, and Eu. Likewise, bulk composition Y980459 is ideal for the study of martian olivine-phyric basalts and specifically for olivine-melt, spinel-melt, and spinel-olivine partitioning of V as a function of oxygen fugacity.

Olivine Slip-system Activity at High Pressure: Implications for Upper-Mantle Rheology and Seismic Anisotropy (Invited)

NASA Astrophysics Data System (ADS)

Raterron, P.; Castelnau, O.; Geenen, T.; Merkel, S.

2013-12-01

The past decade abounded in technical developments allowing the investigation of materials rheology at high pressure (P > 3 GPa) [1]. This had a significant impact on our understanding of olivine rheology in the Earth asthenosphere, where P is in the range 3 - 13 GPa. A dislocation slip-system transition induced by pressure has been documented in dry Fe-bearing olivine [2]; it induces changes in olivine aggregate lattice preferred orientation (LPO) [3,4], which may explain the seismic velocity anisotropy attenuation observed at depths > 200 km in the upper mantle [5]. Deformation experiments carried out on olivine single crystals at high pressure allowed quantifying the effect of P on individual slip system activities [6]. Integration of these data, together with data on lattice friction arising from computational models (e.g., [7]), into analytical or mean-field numerical models for aggregate plasticity gave insight on the viscosity and LPO of olivine aggregates deformed at geological conditions in the dislocation creep regime [8,9]. We will review these recent findings and their implications for upper mantle rheology and seismic anisotropy. [1] Raterron & Merkel, 2009, J. Sync. Rad., 16, 748 ; [2] Raterron et al., 2009, PEPI, 172, 74 ; [3] Jung et al., 2009, Nature Geoscience, 2, 73 ; [4] Ohuchi et al., 2011, EPSL, 304, 55 ; [5] Mainprice et al., 2005, Nature, 433, 731 ; [6] Raterron et al., 2012, PEPI, 200-201, 105 ; [7] Durinck et al., 2007, EJM, 19, 631 ; [8] Castelnau et al., 2010, C.R. Physique, 11, 304 ; [9] Raterron et al., 2011, PEPI, 188, 26

Few Atomic Layered Lithium Cathode Materials to Achieve Ultrahigh Rate Capability in Lithium-Ion Batteries.

PubMed

Tai, Zhixin; Subramaniyam, Chandrasekar M; Chou, Shu-Lei; Chen, Lingna; Liu, Hua-Kun; Dou, Shi-Xue

2017-09-01

The most promising cathode materials, including LiCoO 2 (layered), LiMn 2 O 4 (spinel), and LiFePO 4 (olivine), have been the focus of intense research to develop rechargeable lithium-ion batteries (LIBs) for portable electronic devices. Sluggish lithium diffusion, however, and unsatisfactory long-term cycling performance still limit the development of present LIBs for several applications, such as plug-in/hybrid electric vehicles. Motivated by the success of graphene and novel 2D materials with unique physical and chemical properties, herein, a simple shear-assisted mechanical exfoliation method to synthesize few-layered nanosheets of LiCoO 2 , LiMn 2 O 4 , and LiFePO 4 is used. Importantly, these as-prepared nanosheets with preferred orientations and optimized stable structures exhibit excellent C-rate capability and long-term cycling performance with much reduced volume expansion during cycling. In particular, the zero-strain insertion phenomenon could be achieved in 2-3 such layers of LiCoO 2 electrode materials, which could open up a new way to the further development of next-generation long-life and high-rate batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Production of 21Ne in depth-profiled olivine from a 54 Ma basalt sequence, Eastern Highlands (37° S), Australia

NASA Astrophysics Data System (ADS)

Matchan, Erin L.; Honda, Masahiko; Barrows, Timothy T.; Phillips, David; Chivas, Allan R.; Fifield, L. Keith; Fabel, Derek

2018-01-01

In this study we investigate the cosmogenic neon component in olivine samples from a vertical profile in order to quantify muogenic 21Ne production in this mineral. Samples were collected from an 11 m thick Eocene basalt profile in the Eastern Highlands of southeastern Australia. An eruption age of 54.15 ± 0.36 Ma (2σ) was determined from 40Ar/39Ar step-heating experiments (n = 6) on three whole-rock samples. A 36Cl profile on the section indicated an apparent steady state erosion rate of 4.7 ± 0.5 m Ma-1. The eruption age was used to calculate in situ produced radiogenic 4He and nucleogenic 3He and 21Ne concentrations in olivine. Olivine mineral separates (n = 4), extracted from the upper two metres of the studied profile, reveal cosmogenic 21Ne concentrations that attenuate exponentially with depth. However, olivine (Fo68) extracted from below 2 m does not contain discernible 21Ne aside from magmatic and nucleogenic components, with the exception of one sample that apparently contained equal proportions of nucleogenic and muogenic neon. Modelling results suggest a muogenic neon sea-level high-latitude production rate of 0.02 ± 0.04 to 0.9 ± 1.3 atoms g-1 a-1 (1σ), or <2.5% of spallogenic cosmogenic 21Ne production at Earth's surface. These data support a key implicit assumption in the literature that accumulation of muogenic 21Ne in olivine in surface samples is likely to be negligible/minimal compared to spallogenic 21Ne.

Compositional Zoning in Kilauea Olivine: A Geochemical Tool for Investigating Magmatic Processes at Hawaiian Volcanoes

NASA Astrophysics Data System (ADS)

Lynn, Kendra J.

Olivine compositions and zoning patterns have been widely used to investigate the evolution of magmas from their source to the Earthfs surface. Modeling the formation of compositional zoning in olivine crystals has been used to retrieve timescales of magma residence, mixing, and transit. This dissertation is composed of three projects that apply diffusion chronometry principles to investigate how zoned olivine phenocrysts record magmatic processes at Hawaiian volcanoes. Olivine phenocrysts from K.lauea, the most active and thoroughly studied volcano in Hawaiei, are used to develop a better understanding of how Hawaiian olivine crystals record magmatic histories. This work begins by examining how crustal processes such as magma mixing and diffusive reequilibration can modify olivine compositions inherited from growth in parental magmas (Chapter 2). Diffusive re-equilibration of Fe-Mg, Mn, and Ni in olivine crystals overprints the chemical relationships inherited during growth, which strongly impacts interpretations about mantle processes and source components. These issues are further complicated by sectioning effects, where small (400 ƒEm along the c-axis) olivine crystals are more susceptible to overprinting compared to large (800 ƒEm) crystals. Olivine compositions and zoning patterns are then used to show that magmas during K.laueafs explosive Keanak.koei Tephra period (1500-1823 C.E.) were mixed and stored in crustal reservoirs for weeks to months prior to eruption (Chapter 3). Fe-Mg disequilibrium between olivine rims and their surrounding glasses show that a late-stage mixing event likely occurred hours to days prior to eruption, but the exact timescale is difficult to quantify using Fe-Mg and Ni diffusion. Lithium, a rapidly diffusing trace element in olivine, is modeled for the first time in a natural volcanic system to quantify this late-stage, short-duration mixing event (Chapter 4). Lithium zoning in olivine records both growth and diffusion processes

The formation of phosphoran olivine and stanfieldite from the pyrometamorphic breakdown of apatite in slags from a prehistoric ritual immolation site (Goldbichl, Igls, Tyrol, Austria)

NASA Astrophysics Data System (ADS)

Schneider, Philipp; Tropper, Peter; Kaindl, Reinhard

2013-04-01

In this study we report P-rich olivine and the tric-calcium phosphate (TCP) stanfieldite in partially molten quartzphyllites from the ritual immolation site at the Goldbichl, near Innsbruck in the Tyrol, Austria. During partial melting, foamy patches of dark glassy material formed at the surface of the rocks and also as layers within the rocks. The pyrometamorphic rocks contain mostly the mineral assemblage olivine + orthopyroxene + plagioclase + spinel + glass. During the investigation of slag samples from this prehistoric ritual immolation site, extremely P-rich, apatite-bearing micro-domains were found. In these domains phosphoran olivine was found whose P contents are approaching the maximum P contents in olivine according to the experimental investigations of Boesenberg and Hewins (Geochim Cosmochim Acta 74:1923-1941, 2010). The textures within these domains indicate strongly disequilibrium conditions. The phosphoran olivines formed due to reactions involving apatite and the mineral assemblage of the quartzphyllites, and coexist with plagioclase and a tri-calcium phosphate phase (TCP) showing stanfieldite Ca4(Mg, Fe2+, Mn2+)5(PO4)6 composition. In terms of its chemical composition, olivine shows a wide range in composition with P ranging from 0.3 to 0.54 a.p.f.u, which corresponds to maximal 23 wt.% P2O5. These are the highest P-contents in olivine reported from rocks so far. The incorporation of P correlates with decreasing Si contents according to the charge balancing scheme 2{{P}^{5+ }}+□{{M}_{1,2 }}=2S{{i}^{4+ }}+{{( {Mg,Fe} )}^{2+ }}{{M}_{1,2 }} . Therefore P can only be incorporated in combination with a vacancy on the M1,2 position. Micro-Raman spectroscopy of phosphoran olivines indicates that these olivines can easily be identified with this method due to the strong signals of the SiO4 and PO4 vibrations. The external vibrations of the M1,2 sites at low wave-numbers are more complex than for P-free olivine. This might be due to the effect of P5+ on

Effect of the Hydrothermal Fluid Composition on the Serpentinization of Olivine and Pyroxene

NASA Astrophysics Data System (ADS)

Daniel, I.; Andreani, M.

2016-12-01

The hydrothermal alteration of ultramafic rocks leads to the serpentinization reaction that mainly forms serpentine and variable amounts of talc, brucite and magnetite, as well as hydrogen and magnesite when carbonate is present in the fluid. The serpentinization kinetics of pyroxene under hydrothermal conditions has been very little studied in comparison with olivine, and both have been evaluated experimentally only in simple aqueous fluids. Here, we have evaluated the effect of the fluid chemistry - aluminum, carbonate and pH on the serpentinization rate of olivine and orthopyroxene at 200 °C, 340 °C and 200 MPa to simulate natural hydrothermal conditions. We used low-pressure diamond-anvil cells (lp-DAC) and time-resolved X-ray diffraction to monitor in situ the progress of serpentinization in twelve experiments. We also performed several complementary long-lasting experiments of several days in particular with orthopyroxene, for which in situ monitoring was not possible. At 340 °C in presence of Al and/or carbonate and at high pH, olivine conversion into lizardite is extremely fast with a half-time reaction t1/2 = 2 hrs only, while orthopyroxene did not react much even after 6 days (11%). In contrast to olivine, orthopyroxene conversion to serpentine was faster without Al (48 % in 6 days). Magnetite was also observed to form in the runs with olivine at 340 °C and moderate pH. In experiments run with orthopyroxene only, we observed the exclusive formation of proto-serpentine instead of lizardite. We propose that the contrasted effect of Al on the serpentinization rate of olivine and orthopyroxene results from the complexation of Al in the solution that reacts differently with the mineral surfaces during their dissolution. The positively charged olivine surface allows the adsorption of the dominant negatively charged Al(OH)4- complex, while the neutral surface of orthopyroxene does not. This adsorption process could facilitate both the dissolution of olivine

Olivine and spinel fabric development in lineated peridotites

NASA Astrophysics Data System (ADS)

German, Lindsey; Newman, Julie; Chatzaras, Vasileios; Kruckenberg, Seth; Stewart, Eric; Tikoff, Basil

2016-04-01

Investigation of olivine and spinel fabrics in lineated harzburgites from the Red Hills peridotite massif, New Zealand, reveals that the spinel grain population records the same orientation of the principal finite strain axes as olivine grains, however, olivine grains generally record stronger fabric anisotropy. Further, olivine crystallographic preferred orientation (CPO) reflects the constrictional kinematic context of these rocks. In these harzburgites, deformed at ~1200 °C and >6 kbar, spinel grains are variably oriented and display weak to no CPO. Shape fabric in spinels, determined using X-ray computed tomography (XRCT) indicates a range of geometries (L>S, L=S and LOlivine grains (mean diameter: 0.13 - 0.27 mm) exhibit evidence for dislocation creep, including subgrains, undulose extinction and a strong shape preferred orientation, with long axes parallel or subparallel to the mean spinel long axis orientation derived from XRCT. Olivine fabric analyses, carried out using Image SXM on grain traces from optical photomicrographs of two mutually perpendicular thin sections from each sample, yield moderately to strongly prolate fabrics (L>S tectonites) for olivine in all samples. CPO, plotted with respect to lineation and foliation as defined by XRCT analyses of spinel grains, is characterized by [100] maxima parallel or subparallel to the lineation; [010] and [001] form girdles perpendicular to the lineation, consistent with the D-type CPO for olivine. Olivine CPO is typically interpreted in the context of deformation conditions (e.g., temperature, stress) based on experimental studies. However, the D-type CPO for olivine is generally associated with deformation at relatively lower temperatures than suggested by the mineral compositions in these rocks. Our data suggest that olivine CPO may not only respond to deformation conditions, but may be controlled by the