Thin hybrid electrolyte based on garnet-type lithium-ion conductor Li7La3Zr2O12 for 12 V-class bipolar batteries

Yoshima, Kazuomi; Harada, Yasuhiro; Takami, Norio

doi:10.1016/j.jpowsour.2015.10.031

Cited by 67 publications

(67 citation statements)

References 37 publications

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“…Since then, researches have been conducted on the influence of synthetic methods, carbon coating, La-doping, unique microstructure, modified conductive agent super-p, and new types of electrolytes for low-temperature electrochemical performance 9,15–19 . References 9,15–19 indicated that the appropriate particle size, large specific surface area, fewer contact points between particles, and high electrode conductivity could effectively enhance the low-temperature electrochemical performance to a certain extent. However, the mechanisms for the electrochemical performance of the LTO electrode decreasing at low temperatures were rarely explored.…”

Section: Introductionmentioning

confidence: 99%

Mechanisms of the decrease in low-temperature electrochemical performance of Li4Ti5O12-based anode materials

Huang

Yang

Mao

2017

Sci Rep

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The electrochemical performances of Li4Ti5O12 (LTO) and Li4Ti5O12-rutile TiO2 (LTO–RTO) composite electrodes at low temperatures were evaluated. The electrochemical performance of both electrodes decreased at low temperatures; regardless, the LTO–RTO electrode performed better than the LTO electrode. First, high viscosity and low ion conductivity of liquid electrolytes at low temperatures significantly reduce electrochemical performance. Second, cycling at low temperatures changes the crystal structure of LTO–based electrodes, impeding lithium ion diffusion and even causing the diffusion path to change from easy to difficult. However, changes in the crystal structure of the LTO–RTO electrode were not sufficient to change this path; thus, diffusion continued along the 8a-16c-8a pathway. Finally, from the perspective of dynamics, aggravation of a side reaction, increase in charge transfer resistance and polarization, and decrease in lithium ion diffusion at low temperatures reduce the electrochemical performance of LTO–based anode materials. However, the activation energy based on lithium ion diffusion is lower in the LTO–RTO electrode than the LTO electrode. The results confirmed that the electrochemical performance of the LTO–RTO electrode was better than that of the LTO electrode at low temperatures.

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Section: Introductionmentioning

confidence: 99%

Mechanisms of the decrease in low-temperature electrochemical performance of Li4Ti5O12-based anode materials

Huang

Yang

Mao

2017

Sci Rep

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“…The values of self-discharge rate for LTO/LMFP cell may be Performance of fabricated 12 V-class bipolar LTO/LMFP battery.-We performed a preliminary fabrication of a small-size 12 V-class bipolar LTO-based battery using LiMn 0.8 Fe 0.2 PO 4 cathode and the LLZ-based hybrid solid electrolyte. 10 We have been developing large-size bipolar batteries and enhanced the performance by improvements of the electrode materials. Table I summaries the specification of the fabricated 12 V-class bipolar LTO/LMFP battery.…”

Section: Resultsmentioning

confidence: 99%

“…4,5 The organic liquid electrolyte consisted of a mixture of propylene carbonate (PC) and diethylcarbonate (DEC) solvent (1:2 by volume) containing 1.2 mol dm −3 lithium hexafluorophosphate (LiPF 6 ). The LLZ-based hybrid solid electrolyte with PAN-based gel polymer electrolyte prepared by the method described in a previous report 10 consisted of 96 wt% LLZ, 0.8 wt% PAN, • C using dried Li 2 CO 3 (99% purity), La 2 O 3 (99.99% purity, pre-dried at 900…”

Section: Mgmentioning

confidence: 99%

12 V-Class Bipolar Lithium-Ion Batteries Using Li₄Ti₅O₁₂Anode for Low-Voltage System Applications

Takami

Yoshima

Harada

2016

J. Electrochem. Soc.

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A combination of a Li 4 Ti 5 O 12 (LTO) anode and 4 V-class cathodes has been electrochemically studied with a view to its adoption for 12 V-class bipolar batteries. Five series-connected LTO/LiMn 0.85 Fe 0.1 Mg 0.05 PO 4 (LMFP) cells harmonized well with a useable voltage range of 12 V lead-acid batteries, which is suitable for low-voltage system applications. The LMFP cathode had excellent cycle life performance during high-temperature cycling at 60 • C and over-discharge cycling tests. In the case of the LTO/Al and the LMFP/Al electrode using an Al current collector in a hybrid solid electrolyte consisting of a cubic garnet-type Li 7 La 3 Zr 2 O 12 and a gel polymer, lithium insertion and extraction occurred smoothly without irreversible reactions in the potential range of 1 to 4.5 V vs. Li/Li + . The thin hybrid solid electrolyte with thickness of a few micrometer exhibited not only high-rate discharge but also a low self-discharge for practical use. It was demonstrated that the fabricated 12 V-class bipolar LTO/LMFP battery with a capacity of 102 mAh had the average discharge voltage of 12.5 V, the energy density of 90 Wh kg −1 , and the output power density of 1500 W kg −1 for 10 s. The 12 V-class bipolar LTO/LMFP battery is expected to be suitable for low-voltage systems. Lithium-ion batteries using Li 4 Ti 5 O 12 (LTO) anode realize high power, long life, and safety for automotive and stationary power applications because the LTO electrode has the advantages of nano-size particle, no lithium plating at quick-charging and in low-temperature conditions, outstanding safety for internal short-circuit, and thermal stability under high-temperature conditions. 1-5 There have recently been growing expectations, that the LTO-based lithium-ion batteries will be an excellent match for low-voltage system applications such as 12 V start-stop systems for vehicles 5 and the replacement of lead-acid batteries for stationary power supply.6,7 The start-stop batteries will be stressed by repeated starting and out-put high-power for cold-cranking operation. The LTO-based batteries may solve these problems and have good voltage harmonization with lead-acid batteries. 12 V-class batteries consisting of five series-connected LTO-based cells with LiMn 2 O 4 cathode have already been applied to start-stop vehicle systems. 5 We have been developing olivine LiMn 1-x Fe x PO 4 (LMFP) materials as promising cathodes for large-scale 12 V-class batteries in view of the excellent safety and life performance because the LMFP has high thermal stability compared to that of 4 V-class cathodes such as LiCoO 2 , LiNi 1/3 Co 1/3 Mn 1/3 O 2 , and LiMn 2 O 4 .8 Lithium-ion cells with a combination of the LMFP cathode and the LTO anode exhibited a voltage plateau of about 2.5 V for Mn 3+ /Mn 2+ redox, excellent safety, and high-energy density compared to LTO/LMO cell, indicating the possibility of promising batteries for 12 V lead-acid replacement batteries and stationary power sources. 8,9 We have focused recently on bipolar battery technologie...

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“…[5][6][7][8][9][10][11][12][13] With increasing interest in portable and flexible electronics,c onsiderable efforts have been investedi nt he fabrication of solid-state microbatteries that can be implemented in wearable or implantable devices. [16][17][18][19][20] In general, large-scale energy storage devices,f or example, for EV applications,r equire high-voltage and high-energy battery modules that possess numerous unit cells connected in series. [16][17][18][19][20] In general, large-scale energy storage devices,f or example, for EV applications,r equire high-voltage and high-energy battery modules that possess numerous unit cells connected in series.…”

Section: Introductionmentioning

confidence: 99%

“…[14,15] In addition to enhanced safety and reliability,ASSBs have the potential to deliver higher (volumetric) energy density,i nc omparison to that of conventional LIBs with liquid electrolytes, because ASSBs can be devised andf abricated based on the bipolar design. [16][17][18] The bipolar design can significantly reduce the number of unnecessary components and parts forp ackaging and electricalc onnections, and therefore, it can lead to an increasei nt he volumetric energy density of the battery system, while simultaneously enabling easy build-up of the total The use of solid electrolytes provides at echnical solution to address the safety issues of lithium-ion batteries ande nables a bipolar designo fh igh-voltage and high-energyb attery modules. Traditional LIBs with liquid electrolytes are constructed in the monopolar design:1 )each current collector (plate) acts as either ap ositive or negative pole;2 )each unit cell should be sealed and packaged due to the fluidic nature of the liquid electrolyte used;a nd 3) multiple unit cells are connected in series through externalw iring.…”

Section: Introductionmentioning

confidence: 99%

Multilayered, Bipolar, All‐Solid‐State Battery Enabled by a Perovskite‐Based Biphasic Solid Electrolyte

et al. 2018

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The use of solid electrolytes provides a technical solution to address the safety issues of lithium-ion batteries and enables a bipolar design of high-voltage and high-energy battery modules. The bipolar design avoids unnecessary components and parts for packaging and electrical connection; therefore, it facilitates an increase in the volumetric energy density of the battery, while enabling easy build-up of total output voltage. Herein, the design and construction of a multilayered, bipolar-type, all-solid-state battery (ASSB) from a biphasic solid electrolyte (BSE) based on inorganic Li La TiO perovskite and poly(ethylene oxide) (PEO) are reported. A flexible and freestanding BSE membrane exhibits high Li conductivity of about 1.2×10 S cm , and shows enhanced electrochemical/thermal stability, in comparison to a PEO-only solid electrolyte. A single-layered ASSB assembled with a BSE shows promising electrochemical performance, as evidenced by a high reversible capacity of about 123 mA h g and excellent cycling stability over 100 cycles. Furthermore, a proof-of-concept bipolar ASSB comprising three unit cells connected in series is constructed by using the BSE membrane and Al/Cu-cladded bipolar plates. The bipolar ASSB shows high thermal stability and operates reversibly without any internal short circuit or current leakage during charge-discharge cycles; this demonstrates that BSEs provide a promising approach to the design and fabrication of bipolar ASSBs with improved safety and high energy density.

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Thin hybrid electrolyte based on garnet-type lithium-ion conductor Li7La3Zr2O12 for 12 V-class bipolar batteries

Cited by 67 publications

References 37 publications

Mechanisms of the decrease in low-temperature electrochemical performance of Li4Ti5O12-based anode materials

Mechanisms of the decrease in low-temperature electrochemical performance of Li4Ti5O12-based anode materials

12 V-Class Bipolar Lithium-Ion Batteries Using Li₄Ti₅O₁₂Anode for Low-Voltage System Applications

Multilayered, Bipolar, All‐Solid‐State Battery Enabled by a Perovskite‐Based Biphasic Solid Electrolyte

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Thin hybrid electrolyte based on garnet-type lithium-ion conductor Li7La3Zr2O12 for 12 V-class bipolar batteries

Cited by 67 publications

References 37 publications

Mechanisms of the decrease in low-temperature electrochemical performance of Li4Ti5O12-based anode materials

Mechanisms of the decrease in low-temperature electrochemical performance of Li4Ti5O12-based anode materials

12 V-Class Bipolar Lithium-Ion Batteries Using Li4Ti5O12Anode for Low-Voltage System Applications

Multilayered, Bipolar, All‐Solid‐State Battery Enabled by a Perovskite‐Based Biphasic Solid Electrolyte

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Product

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12 V-Class Bipolar Lithium-Ion Batteries Using Li₄Ti₅O₁₂Anode for Low-Voltage System Applications