Thermal stability of active electrode material in contact with solid electrolyte

TRON ARTUR,Nosenko Alexander,Mun Junyoung 한국세라믹학회 2022 한국세라믹학회지 Vol.59 No.2

For lithium battery systems including solid-state batteries, the solid electrolytes are playing an important role in enhancing the lithium transportation through the electrode/electrolyte interface resulting in the enhanced electrochemical performance of active materials which can prevent the dendrite formation for long term cycle life. However, the formation of the solid electrolyte fi lm on the materials' surface is carrying on via various types of methods. Especially for oxide-salt-type of solid electrolytes of Li 2 O–M x O y –Li x X y system, these solid electrolyte is forming on the surface of materials via the melt quench- ing technique at above 500 °C that can lead to the unstable and degradation the structure of the active materials resulting in the lower performance compared to the traditional (wet-chemistry or solid stare reaction) formation of solid electrolyte fi lm. In this work, the thermochemical stability of the active material in contact with the solid electrolyte after formation via a high-temperature method is investigated by the thermogravimetric and X-ray diff raction analysis, and galvanostatic charge– discharge and cyclic voltammetry measurements confi rm that the electrochemical degradation can be attributed mainly to the partial destruction of cathode structure and surface oxidation of current collector leading to the lower electrochemical performance. The results suggest that the process formation of solid electrolyte film of the oxide-salt system should not exceed 250–300 °C and is highly relevant to a critical area for the active electrode materials without the degradation of the material structure and decreasing electrochemical performance.

A Solid Electrolyte Potentiometric CO₂ Gas Sensor Composed of Lithium Phosphate as Both the Reference and the Solid Electrolyte Materials

이형근,최낙진,문승언,양우석,김종대 한국물리학회 2012 THE JOURNAL OF THE KOREAN PHYSICAL SOCIETY Vol.61 No.6

A solid electrolyte potentiometric CO₂ gas sensor has been considered as a candidate for miniaturization into a micro-sensor form. However, the solid electrolyte potentiometric CO₂ gas sensor is composed of three components: a reference, a sensing material, and a solid electrolyte. This study reports the fabrication of a solid electrolyte potentiometric CO₂ gas sensor with a native reference material from the solid electrolyte (Li₃PO₄), which means one component of the sensor can be omitted and the fabrication process can be simplified compared to the process for a conventional solid electrolyte potentiometric CO₂ gas sensor. The sensor containing Li₃PO₄, which acted as the reference material as well as the sensing material, showed a comparable response (75 mV/dec at 500 ℃) to CO₂ gas when we compared the sensor with a conventional solid electrolyte CO₂ gas sensor (73 mV/dec at 500 ℃) with a coplanar configuration containing Li₂TiO₃ as the reference material and Li₃PO₄ as the solid electrolyte.

Synthesis and electrochemical performance of (100-x)Li7P3S11-xLi3SI composite solid electrolyte for all-solid-state lithium batteries

정수연,Rajesh Rajagopal,류광선 한국공업화학회 2021 Journal of Industrial and Engineering Chemistry Vol.95 No.-

Li7P3S11 (LPS) solid electrolytes have great advantages, such as high lithium-ion conductivity, and caneasily fabricate to make bulk-type all-solid-state lithium batteries. However, LPS has a disadvantagebecause of large interfacial resistance with lithium, which give a limitation for all-solid-state battery. Inthis study, (100-x)Li7P3S11-x Li3SI (x = 0. 2 and 5) solid electrolyte composites are prepared by mechanicalball milling process. Various physiochemical analysis was carried out to confirm the proper mixing ofLi7P3S1 and Li3SI solid electrolytes. The addition of Li3SI solid electrolyte, effectively influence the ionicconductivity and electrochemical properties of the Li7P3S1 solid electrolyte. The prepared Li7P3S11/Li3SIsolid electrolyte composites are stable against the lithium metal anode even after 100 h chargedischargingprocess and has stable potential window up to 10 V. In particular, 98Li7P3S11-2Li3SI solidelectrolyte based ASSLBs shows the highest capacity, of 110 mA/g at the current density of 7.5 mA g 1(0.05 C). The charge – discharge cycle stability test also proved the Li3SI mixing to Li7P3S11 helped tomaintain the capacity retention value of100 % after 10 cycles. Therefore, the Li3SI into the Li7P3S11electrolyte helps improve the electrochemical performance.

Improving the energy density of all-solidstate batteries by maximizing the contact area between the solid electrolyte and electrode, and stress issues

Rongzhen Zheng,김철 대한기계학회 2023 JOURNAL OF MECHANICAL SCIENCE AND TECHNOLOGY Vol.37 No.8

Solid-state electrolyte batteries are excellent candidates for the development of safe and high-performance lithium batteries. However, the low ionic conductivity and poor interfacial contact of current solid-state electrolytes severely hinder the commercialization of solidstate batteries. Moreover, a higher stress is caused by the use of solid-state electrolytes compared with that in the case of liquid electrolytes. To increase the physical contact area between the solid/solid interfaces of all-solid-state batteries (ASSBs), this study constructed two types of interfaces with sine-curved and trapezoidal shapes to replace the general planar interface and used the Nelder-Mead algorithm to optimize the curved interface and geometric parameters of the battery cells. ASSBs are composed of a sulfide-based LI6PS5Cl solid electrolyte, a lowdensity lithium metal anode, and a high-theoretical-capacity LCO cathode. The optimization results show that the curved interface can achieve a higher energy density than a flat-interface battery. The stress caused by lithium deposition during battery charging was also calculated. The low modulus of the soft solid electrolyte significantly reduced the stress inside the battery.

Recent Development of Bulk-Type Solid-State Rechargeable Lithium Batteries with Sulfide Glass-ceramic Electrolytes

Akitoshi Hayashi,Masahiro Tatsumisago 대한금속·재료학회 2012 ELECTRONIC MATERIALS LETTERS Vol.8 No.2

The recent development of bulk-type solid-state rechargeable lithium batteries with sulfide glass-ceramics as a solid electrolyte was reviewed. Sulfide glasses and glass-ceramics in the system Li2S-P2S5 have an advantage of high conductivity, wide electrochemical window and low grain-boundary resistance. Bulk-type solid-state batteries composed of compressed powder layers of electrode and electrolyte were fabricated with Li2S-P2S5glass-ceramic electrolytes. Formation of a favorable solid-solid interface between electrode and electrolyte is a key to achieving excellent performance in solid-state batteries. The mechanochemical preparation of nano-composite electrodes and surface modification of active materials by softening of the electrolyte, or PLD coating, were useful for increasing the electrode-electrolyte contact area and improving battery performance.

A review of lithium and non-lithium based solid state batteries

Kim, Joo Gon,Son, Byungrak,Mukherjee, Santanu,Schuppert, Nicholas,Bates, Alex,Kwon, Osung,Choi, Moon Jong,Chung, Hyun Yeol,Park, Sam Elsevier 2015 Journal of Power Sources Vol.282 No.-

<P><B>Abstract</B></P> <P>Conventional lithium-ion liquid-electrolyte batteries are widely used in portable electronic equipment such as laptop computers, cell phones, and electric vehicles; however, they have several drawbacks, including expensive sealing agents and inherent hazards of fire and leakages. All solid state batteries utilize solid state electrolytes to overcome the safety issues of liquid electrolytes. Drawbacks for all-solid state lithium-ion batteries include high resistance at ambient temperatures and design intricacies. This paper is a comprehensive review of all aspects of solid state batteries: their design, the materials used, and a detailed literature review of various important advances made in research. The paper exhaustively studies lithium based solid state batteries, as they are the most prevalent, but also considers non-lithium based systems. Non-lithium based solid state batteries are attaining widespread commercial applications, as are also lithium based polymeric solid state electrolytes. Tabular representations and schematic diagrams are provided to underscore the unique characteristics of solid state batteries and their capacity to occupy a niche in the alternative energy sector.</P> <P><B>Highlights</B></P> <P> <UL> <LI> A comprehensive review of all aspects of solid state batteries: design, materials. </LI> <LI> Tabular representations to underscore the characteristics of solid state batteries. </LI> <LI> Solid state electrolytes to overcome the safety issues of liquid electrolytes. </LI> </UL> </P>

Polymethacrylate-<i>comb</i>-copolymer electrolyte for solid-state energy storage devices

Lee, Jae Hun,Lim, Jung Yup,Park, Jung Tae,Lee, Jung Min,Kim, Jong Hak Elsevier 2018 Materials & Design Vol.149 No.-

<P><B>Abstract</B></P> <P>We report a highly ion-conductive polymer electrolyte, based on a poly(2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate)-poly(oxyethylene methacrylate)-comb (PBE-comb) copolymer and the 1-ethyl-3-methylimidazolium dicyanamide (EMIM-DCA) ionic liquid, for use in a solid-state supercapacitor. Selective interactions between the poly(oxyethylene methacrylate) (POEM) chains and the EMIM-DCA induce the formation of a microphase-separated structure, as evidenced by Fourier-transform infrared spectroscopy, transmission electron microscopy, and differential scanning calorimetry. The well-defined nanostructured morphology effectively suppresses the aggregation of EMIM-DCA to provide ion-transport pathways that facilitate the fast diffusion of mobile ions. The capacitance of the solid-state supercapacitor formed with the PBE/EMIM-DCA electrolyte (125.1Fg<SUP>−1</SUP>) was much greater than that of the conventional poly(vinyl alcohol) (PVA)/H<SUB>3</SUB>PO<SUB>4</SUB> electrolyte (39.5Fg<SUP>−1</SUP>) due to its higher ionic conductivity and superior affinity for the electrode. The fast ion-diffusion properties of the PBE/EMIM-DCA electrolyte was confirmed by its high capacitance retention (70%) at a fast scan rate, significantly higher than that observed for the PVA/H<SUB>3</SUB>PO<SUB>4</SUB> electrolyte. Moreover, the supercapacitor composed of the PBE/EMIM-DCA electrolyte showed considerable cycling stability (91.1% after 10,000 charge-discharge cycles). The PBE/EMIM-DCA electrolyte is therefore a promising candidate for use in high-performance solid-state supercapacitors and energy-storage systems.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Highly ion-conductive PBE/EMIM-DCA comb copolymer electrolytes were prepared. </LI> <LI> Solid supercapacitor with PBE/EMIM-DCA showed a high capacitance of 125.1Fg<SUP>−1</SUP>. </LI> <LI> Performance of PBE/EMIM-DCA was superior to conventional PVA/H<SUB>3</SUB>PO<SUB>4</SUB> electrolyte. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

전고체 리튬이차전지의 PEO/LLZO 복합고체전해질 특성

우민홍,김주민,차지혜,정호영,장덕례 조선대학교 공학기술연구원 2019 공학기술논문지 Vol.12 No.1

The PEO/LLZO solid composite electrolyte with high ionic conductivity and low interfacial resistance was prepared by solution casting method. The electrochemical properties such as lithium ion conductivity, lithium ion transference number, electrochemical stability and compatability with lithium metal anode of PEO/LLZO solid composite electrolyte were investigated. The results showed that the addition of LLZO could effectively improve the ionic conductivity, electrochemical stability window, transference number, and compatibility with lithium metal of composite electrolytes. The LLZO 45% content of the PEO/LLZO solid composite electrolyte showed the lowest activation energy and the electrochemical stability at 4.75V (vs Li/Li+). In addition, when the thickness of the PEO/LLZO solid composite electrolyte was 130 μm or more, The behavior of Li+ plating/stripping on lithium symmetric cell was greatly enhanced. The NCM622/Li solid-state lithium ion battery assembled with the PEO/LLZO solid composite electrolytes had good cycling performance. At current rate of 0.5C, the discharge specific capacity remained about 148mAh/g after 100cycles at 60℃.

Non-aqueous quasi-solid electrolyte for use in supercapacitors

채지수,권하나,윤원섭,노광철 한국공업화학회 2018 Journal of Industrial and Engineering Chemistry Vol.59 No.-

Gel electrolytes have attracted increasing attention for use in supercapacitors. An ideal gel electrolyte usually solves several problems, including electrolyte leakage, corrosion of the liquid electrolyte, and electrolyte packing. In this study, to address these issues, tetraethylammonium tetrafluoroborate in propylene carbonate was integrated into a poly(ethylene glycol) dimethacrylate polymer matrix with azobisisobutyronitrile as a thermal initiator. The specific capacitance of this quasi-solid electrolyte was 22% higher than that of the corresponding liquid-based electrolyte at 1 mA cm−2. Further, a supercapacitor wrapped with the quasi-solid electrolyte exhibited energy and power densities of 39 Wh kg−1 and 2.5 kW kg−1, respectively. Notably, the quasi-solid-electrolyte-based supercapacitor was very stable when cycled at a high current density (5 mA cm−2), with only 31% of its initial capacitance lost after 10,000 cycles. Wrapping the supercapacitor with the non-aqueous quasi-solid electrolyte provided a solidified surface, which reduced contact with moisture and oxygen in the air, thereby solving the evaporation problem encountered with liquid electrolytes.

Enhanced ionic conductivity of composite solid electrolyte by directionally ordered structures of linear Li1.3Al0.3Ti1.7(PO4)3

You Li,Mulan Tang,Shuxin Xu,Shuchao Zhang,Yuxin Zhai,Jiarong Yin,Zhengguang Zou 한국공업화학회 2022 Journal of Industrial and Engineering Chemistry Vol.114 No.-

The NASICON-type solid electrolyte structure of Li1.3Al0.3Ti1.7(PO4)3 (LATP) exhibits good electrochemicalperformance and thermal stability, and has been promising as a solid electrolyte. Here, a stable goodstabilityLATP precursor spinning solution was prepared using the sol–gel method for the first time. A linearLATP solid electrolyte with an oriented ordered structure was obtained using improved electrostaticspinning equipment. The sintering process regime of the LATP-ordered construction was determined. Theionic conductivity of the prepared LATP-PEO/LiClO4-PEG composite solid-state electrolyte with anordered structure was as high as 2.05 10-4 Scm1 at room temperature (25 C), one order of magnitudehigher than the ionic conductivity of the LATP composite solid-state electrolyte reported so far. Organicsolid-state electrolytes to protect LATP-ordered structured solid-state electrolytes yield excellent electrochemicalstability in lithium-metal batteries.