Analysis of Differences in Electrochemical Performance Between Coin and Pouch Cells for Lithium-Ion Battery Applications

Small coin cell batteries are predominantly used for testing lithium-ion batteries(LIBs)in academia because they require small amounts of material and are easy to assemble.However,insufficient attention is given to difference in cell performance that arises from the differences in format between coin cells used by academic researchers and pouch or cylindrical cells which are used in industry.In this article,we compare coin cells and pouch cells of different size with exactly the same electrode materials,electrolyte,and electrochemical conditions.We show the battery impedance changes substantially depending on the cell format using techniques including Electrochemical Impedance Spectroscopy(EIS)and Galvanostatic Intermittent Titration Technique(GITT).Using full cell NCA-graphite LIBs,we demonstrate that this difference in impedance has important knock-on effects on the battery rate performance due to ohmic polarization and the battery life time due to Li metal plating on the anode.We hope this work will help researchers getting a better idea of how small coin cell formats impact the cell performance and help predicting improvements that can be achieved by implementing larger cell formats.

Constructing a 700 Wh kg^(-1)-level rechargeable lithium-sulfur pouch cell

Lithium–sulfur(Li–S)batteries are considered as highly promising energy storage devices because of their ultrahigh theoretical energy density of 2600 Wh kg^(-1).The highest practical energy density of Li–S batteries reported at pouch cell level has exceeded 500 Wh kg^(-1),which significantly surpasses that of lithium-ion batteries.Herein,a 700 Wh kg^(-1)-level Li–S pouch cell is successfully constructed.The pouch cell is designed at 6 Ah level with high-sulfur-loading cathodes of 7.4 mgScm^(-2),limited anode excess(50μm in thickness),and lean electrolyte(electrolyte to sulfur ratio of 1.7 gelectrolyteg^(-1)S).Accordingly,an ultrahigh specific capacity of 1563 m A h g^(-1)is achieved with the addition of a redox comediator to afford a practical energy density of 695 Wh kg^(-1)based on the total mass of all components.The pouch cell can operate stably for three cycles and then failed due to rapidly increased polarization at the second discharge plateau.According to failure analysis,electrolyte exhaustion is suggested as the key limiting factor.This work achieves a significant breakthrough in constructing high-energy-density Li–S batteries and propels the development of Li–S batteries toward practical working conditions.

Lithium plating-free 1 Ah-level high-voltage lithium-ion pouch battery via ambi-functional pentaerythritol disulfate

Elevating the charge cut-off voltage beyond traditional 4.2 V is a commonly accepted technology to increase the energy density of Li-ion batteries(LIBs) but the risk of Li-dendrites and fire hazard increases as well. The use of ambi-functional additive, which forms stable solid electrolyte interphase(SEI) simultaneously at both cathode and anode, is a key to enabling a dendrites-free and well-working high-voltage LIB. Herein, a novel ambi-functional additive, pentaerythritol disulfate(PEDS), at 1 wt% without any other additive is demonstrated. We show the feasibility and high impacts of PEDS in forming lithium sulfateincorporated robust SEI layers at NCM523 cathode and graphite anode in 1 Ah-level pouch cell under4.4 V, 25 °C and 0.1 C rate, which mitigates the high-voltage instability, metal-dissolution and cracks on NCM523 particles, and prevents Li-dendrites at graphite anode. Improved capacity retention of 83%after 300 cycles is thereby achieved, with respect to 69% with base electrolyte, offering a promising path toward the design of practical high-energy LIBs.

Outstanding performances of graphite||NMC622 pouch cells enabled by a non-inert diluent

Although high salt concentration electrolyte(HCE)can construct effective Li F-rich interphase film and solve the interphasial instability issue of graphite anode,its high cost,high viscosity and poor wettability with electrode materials limit its large-scale application.Generally,localized high concentration electrolyte(LHCE)is obtained by introducing an electrochemically inert diluent into HCE to avoid the above-mentioned problems while maintaining the high interphasial stability of HCE with graphite anode.Unlike traditional inert diluents,1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluropropyl ether(TTE)with electrochemical activity is introduced into propylene carbonate(PC)-based HCE to obtain LHCE-2(1 M LiPF_(6),PC:DMC:TTE=1:1:6.1)herein.Experimental and theoretical simulation results show that TTE participates in the oxidation decomposition and film-forming reaction at the NCM622 cathode surface,conducting a cathode electrolyte interphase(CEI)rich in organic fluorides with excellent electron insulation ability,high structural stability and low interphasial impedance.Thanks to the outstanding interphasial properties induced by LHCE-2,the graphite||NMC622 pouch cell reaches a capacity retention of 80%after 500 cycles at 1 C under room temperature.While at sub-zero temperatures,the capacity released by the cell with LHCE-2 electrolyte is significantly higher than that of HCE and conventional EC-based electrolytes.Meanwhile,the LHCE-2 electrolyte inherits the advantages of TTE flame-resistant,thus improving the safety of the battery.

High-Performance Quasi-Solid-State Pouch Cells Enabled by in situ Solidification of a Novel Polymer Electrolyte

Conventional lithium-ion batteries(LIBs)with liquid electrolytes are challenged by their big safety concerns,particularly used in electric vehicles.All-solid-state batteries using solid-state electrolytes have been proposed to significantly improve safety yet are impeded by poor interfacial solid–solid contact and fast interface degradation.As a compromising strategy,in situ solidification has been proposed in recent years to fabricate quasi-solid-state batteries,which have great advantages in constructing intimate interfaces and cost-effective mass manufacturing.In this work,quasi-solid-state pouch cells with high loading electrodes(≥3 m Ah cm^(-2))were fabricated via in situ solidification of poly(ethylene glycol)diacrylate-based polymer electrolytes(PEGDA-PEs).Both single-layer and multilayer quasi-solid-state pouch cells(2.0 Ah)have demonstrated stable electrochemical performance over500 cycles.The superb electrochemical stability is closely related to the formation of robust and compatible interphase,which successfully inhibits interfacial side reactions and prevents interfacial structural degradation.This work demonstrates that in situ solidification is a facile and cost-effective approach to fabricate quasi-solid-state pouch cells with both excellent electrochemical performance and safety.

Tracking gassing behavior in pouch cell by operando on-line electrochemical mass spectrometry

As the rapid development of more powerful and safer lithiumion batteries, the mechanism study of gases evolution is attacking more and more attention in recent years. Especially under overcharge/discharge and/or high-temperature working condition.

Uncovering the degradation mechanism induced by ion-diffusion kinetics in large-format lithium-ion pouch cells

Battery electrochemistry in an actual cell is a complicated behavior influenced by the current density,uniformity,and ion-diffusion distance,etc.The anisotropism of the lithiation/delithiation degree is usually inevitable,and even worse,due to a trend of big-size cell design,typically such as 4680 and blade cells,which accelerated a battery failure during repeat lithiation and delithiation of cathodes.Inspire by that,two big-size pouch cells with big sizes,herein,are selected to reveal the ion-diffusion dependency of the cathodes at different locations.Interestingly,we find that the LiCoO_(2) pouch cell exhibits ~5 A h loss after 120 charge-discharge cycles,but a 15 A h loss is verified in a LiNixMnyCO_(1-x)-yO_(2)(NCM) cell.Synchrotron-based imaging analysis indicates that higher ion-diffusion rates in the LiCoO_(2)than that in the LiNixMnyCO_(1-x)-yO_(2)is the determined factor for the anisotropic cathode fading,which is responsible for a severe mechanical issue of particle damage,such as cracks and even pulverization,in the cathode materials.Meanwhile,we verify the different locations at the near-tab and bottom of the electrode make it worse due to the ion-diffusion kinetics and temperature,inducing a spatially uneven electrochemistry in the big-size pouch cell.The findings give an in-depth insight into pouch cell failure and make a guideline for high-energy cell design and development.

不同放电倍率下软包锂离子电池非均匀生热表征方法

软包锂离子电池非均匀的温度分布严重影响其循环性能、使用寿命和安全性。针对软包锂离子电池生热的建模表征复杂且精度不高的问题,提出了一种基于生热分布因子的软包锂离子电池非均匀生热表征方法。将电池划分成不同区域,并将生热分布因子引入Bernardi生热公式中获取不同区域的生热率;通过传热和优化数值模拟求解电池的温度分布,同时辨识不同区域的生热分布因子,分析了软包电池生热非均匀分布特性;采用三次样条差值法推导了生热分布因子与放电倍率的对应关系,研究了不同放电倍率下生热分布因子的演化规律。实验结果表明,该方法所建立的热模型在2.75 C和3.75 C下的温度估计值的平均绝对百分比误差最大不超过1.55%,该方法能够准确估计电池非均匀的生热率,并实现电池温度分布特性的有效表征。

基于固态电解质膜的软包电池制备与初步表征

固态电池安全性高、可适应高比能正负极,是蓄电池发展的方向,但存在固相界面阻抗大、界面结构稳定性差等问题。为了快速评估固态电池技术在实用型蓄电池中的作用,本文采用流延法制备了在50℃下离子电导率为6.16×10^(-4)S/cm的固态电解质膜。以高镍三元为正极、石墨为负极,制备了质量为1.1214 g、容量为53.44 mAh的微型软包电池和容量为7252.8 mAh的大容量软包电池。微型软包电池实现了5 C高倍率的放电和150次循环,大容量软包电池在放电深度(DOD)为13.78%时,实现了439次循环充放电。以上结果说明固态电解质膜满足在锂离子电池中使用的要求,然而这些电池的界面构筑仍有不足之处。基于本文结果,通过对固态电解质膜材料、电池化成制度等进行改进,有望促进高性能电池的研发。

软包装锂离子电池表面凹坑缺陷检测方法

软包装锂离子电池表面凹坑缺陷对比度低、缺陷区域过小且存在反光,传统方法很难进行准确检测。提出一种基于图像增强和改进DeepLabV3网络的软包装锂离子电池表面凹坑缺陷检测方法。通过分析表面凹坑缺陷图像特征,采用图像增强算法对图像进行预处理,以增强凹坑缺陷对比度。对DeepLabV3网络进行改进,使用ResNet101作为特征提取网络,同时引入位置注意力模块,使得模型更加关注于凹坑缺陷相关特征,提升网络的检测精度。改进后的网络在自制数据集上的平均交并比达到85.98%,缺陷检测准确率达到98.33%。

胖袋榨菜中1株产气微生物的分离和鉴定

胖袋是榨菜货架期常见的质量问题,为了获得引起胖袋的微生物种类和生理生化性质数据,从胖袋榨菜中分离纯化微生物,经过三糖铁、煌绿胆盐肉汤实验筛选出产气菌株,用榨菜污染实验验证,进一步分析菌株的生理生化性质.通过研究确定1株菌株cq8,在煌绿胆盐肉汤培养基中产气,污染袋装榨菜并且抽真空封袋,引起胖袋,经检测气体为CO_(2),H_(2),NH_(3),用16S rRNA基因测序鉴定为阿氏肠杆菌(Enterobacter asburia),它可以代谢精氨酸产气,利用山梨醇,产生蛋白酶使明胶液化,产生过氧化氢酶.

Revealing the Multifunctional Electrocatalysis of Indium-Modulated Phthalocyanine for High-Performance Lithium-Sulfur Batteries

The sluggish kinetics of complicated multiphase conversions and the severe shuttling effect of lithium polysulfides(LiPSs)significantly hinder the applications of Li-S battery,which is one of the most promising candidates for the next-generation energy storage system.Herein,a bifunctional electrocatalyst,indium phthalocyanine self-assembled with carbon nanotubes(InPc@CNT)composite material,is proposed to promote the conversion kinetics of both reduction and oxidation processes,demonstrating a bidirectional catalytic effect on both nucleation and dissolution of Li_(2)S species.The theoretical calculation shows that the unique electronic configuration of InPc@CNT is conducive to trapping soluble polysulfides in the reduction process,as well as the modulation of electron transfer dynamics also endows the dissolution of Li_(2)S in the oxidation reaction,which will accelerate the effectiveness of catalytic conversion and facilitate sulfur utilization.Moreover,the InPc@CNT modified separator displays lower overpotential for polysulfide transformation,alleviating polarization of electrode during cycling.The integrated spectroscopy analysis,HRTEM,and electrochemical study reveal that the InPc@CNT acts as an efficient multifunctional catalytic center to satisfy the requirements of accelerating charging and discharging processes.Therefore,the Li-S battery with InPc@CNT-modified separator obtains a discharge-specific capacity of 1415 mAh g^(-1)at a high rate of 0.5 C.Additionally,the 2 Ah Li-S pouch cells deliver 315 Wh kg^(-1)and achieved 80%capacity retention after 50 cycles at 0.1 C with a high sulfur loading of 10 mg cm^(-2).Our study provides a practical method to introduce bifunctional electrocatalysts for boosting the electrochemical properties of Li-S batteries.

锂硫软包电池容量衰减的失效分析

采用原位与非原位相结合的方法,将锂硫软包电池循环失效的容量损失进行定量化分析,主要包括可逆容量损失和不可逆容量损失。根据表征实验拆分,可逆容量损失主要由电流极化、电解液缺失和电芯极片膨胀导致的容量损失组成,不可逆容量损失主要由负极沉积硫化锂、隔膜黏附多硫化锂和电解液溶解等容量损失组成。通过计算对比,造成锂硫软包电池循环失效的主要因素为锂金属负极的粉化和硫化锂的沉积(约占47%),其次为隔膜黏附多硫化物约25%。可针对造成循环失效的主要因素进行重点改善,提升锂硫电池的循环性能,推动实用化进程。

Modified Indiana Pouch Following Radical Cystectomy

Objective To investigate the indications, operation techniques and clinical effects of a modified technique of Indiana pouch. Methods A modified technique of Indiana pouch was performed on 5 patients following radical cystectomy. Results 5 cases showed satisfactory therapeutic effects with of follow-up range of 6 to 30 months. All patients were continent day and night with easy catherization. The number of micturations was 5 to 6 times in the daytime and 1 to 3 times in the nighttime. Cystography of 4 cases showed that pouches were spheroidic and volumes were between 400 to 500 ml. Conclusion The advantages of the modified Indiana pouch are as follows: easy manipulation; low tension and high volume in pouches; no reflux; satisfactory urinary continence and few complications. Therefore, it is worthy of clinical popularization.

LiFSI-LiPF_(6)电解液在高镍/硅碳锂电池中的应用

高镍/硅碳体系是最具潜力的下一代高能量密度锂离子电池体系,但由于电池循环稳定性差,目前规模化应用受限。研究认为,构建稳定的SEI是提升高镍/硅碳电池容量保持率的关键方法之一。传统电解液中六氟磷酸锂(LiPF_(6))会产生酸腐蚀性产物,不利于SEI的稳定;双氟磺酰亚胺锂(LiFSI)作为一种新秀锂盐被证明有优异的热稳定和成膜性能,会腐蚀正极集流体。研究了LiFSI-LiPF_(6)双盐电解液在高镍/硅碳软包电池中的应用,通过化成、循环和储存测试,评测其电化学性能。结果表明,LiFSI-LiPF_(6)电解液可以降低电池化成产气量和内阻,提升电极稳定性,0.6mol/dm^(3)LiFSI+0.6mol/dm^(3)LiPF_(6)电池循环1000圈后的容量保持率最高,达75.66%,其储存电压降比LiFSI单盐电池少37.64%。

Mitigated reaction kinetics between lithium metal anodes and electrolytes by alloying lithium metal with low-content magnesium

Lithium(Li)metal is regarded as a promising anode candidate for high-energy-density rechargeable batteries.Nevertheless,Li metal is highly reactive against electrolytes,leading to rapid decay of active Li metal reservoir.Here,alloying Li metal with low-content magnesium(Mg)is proposed to mitigate the reaction kinetics between Li metal anodes and electrolytes.Mg atoms enter the lattice of Li atoms,forming solid solution due to the low amount(5 wt%)of Mg.Mg atoms mainly concentrate near the surface of Mg-alloyed Li metal anodes.The reactivity of Mg-alloyed Li metal is mitigated kinetically,which results from the electron transfer from Li to Mg atoms due to the electronegativity difference.Based on quantitative experimental analysis,the consumption rate of active Li and electrolytes is decreased by using Mgalloyed Li metal anodes,which increases the cycle life of Li metal batteries under demanding conditions.Further,a pouch cell(1.25 Ah)with Mg-alloyed Li metal anodes delivers an energy density of 340 Wh kg^(-1)and a cycle life of 100 cycles.This work inspires the strategy of modifying Li metal anodes to kinetically mitigate the side reactions with electrolytes.

12.6μm-Thick Asymmetric Composite Electrolyte with Superior Interfacial Stability for Solid-State Lithium-Metal Batteries

Solid-state lithium metal batteries(SSLMBs)show great promise in terms of high-energy-density and high-safety performance.However,there is an urgent need to address the compatibility of electrolytes with high-voltage cathodes/Li anodes,and to minimize the electrolyte thickness to achieve highenergy-density of SSLMBs.Herein,we develop an ultrathin(12.6μm)asymmetric composite solid-state electrolyte with ultralight areal density(1.69 mg cm^(−2))for SSLMBs.The electrolyte combining a garnet(LLZO)layer and a metal organic framework(MOF)layer,which are fabricated on both sides of the polyethylene(PE)separator separately by tape casting.The PE separator endows the electrolyte with flexibility and excellent mechanical properties.The LLZO layer on the cathode side ensures high chemical stability at high voltage.The MOF layer on the anode side achieves a stable electric field and uniform Li flux,thus promoting uniform Li^(+)deposition.Thanks to the well-designed structure,the Li symmetric battery exhibits an ultralong cycle life(5000 h),and high-voltage SSLMBs achieve stable cycle performance.The assembled pouch cells provided a gravimetric/volume energy density of 344.0 Wh kg^(−1)/773.1 Wh L^(−1).This simple operation allows for large-scale preparation,and the design concept of ultrathin asymmetric structure also reveals the future development direction of SSLMBs.

Unraveling high efficiency multi-step sodium storage and bidirectional redox kinetics synergy mechanism of cobalt-doping vanadium disulfide anode

Sodium-based storage devices based on conversion-type metal sulfide anodes have attracted great atten-tion due to their multivalent ion redox reaction ability.However,they also suffer from sodium polysul-fides(NaPSs)shuttling problems during the sluggish Na^(+) redox process,leading to"voltage failure"and rapid capacity decay.Herein,a metal cobalt-doping vanadium disulfide(Co-VS_(2))is proposed to simulta-neously accelerate the electrochemical reaction of VS_(2) and enhance the bidirectional redox of soluble NaPSs.It is found that the strong adsorption of NaPSs by V-Co alloy nanoparticles formed in situ during the conversion reaction of Co-VS_(2) can effectively inhibit the dissolution and shuttle of NaPSs,and ther-modynamically reduce the formation energy barrier of the reaction path to effectively drive the complete conversion reaction,while the metal transition of Co elements enhances reconversion kinetics to achieve high reversibility.Moreover,Co-VS_(2) also produce abundant sulfur vacancies and unsaturated sulfur edge defects,significantly improve ionic/electron diffusion kinetics.Therefore,the Co-VS_(2) anode exhibits ultrahigh rate capability(562 mA h g^(-1) at 5 A g^(-1)),high initial coulombic efficiency(~90%)and 12,000 ultralong cycle life with capacity retention of 90%in sodium-ion batteries(SIBs),as well as impressive energy/power density(118 Wh kg^(-1)/31,250 W kg^(-1))and over 10.000 stable cycles in sodium-ion hybrid capacitors(SIHCs).Moreover,the pouch cell-type SIHC displays a high-energy density of 102 Wh kg^(-1) and exceed 600 stable cycles.This work deepens the understanding of the electrochemical reaction mechanism of conversion-type metal sulfide anodes and provides a valuable solution to the shuttlingofNaPSs inSIBsandSIHCs.

Boosting High-Voltage Practical Lithium Metal Batteries with Tailored Additives

The lithium(Li)metal anode is widely regarded as an ideal anode material for high-energy-density batteries.However,uncontrolled Li dendrite growth often leads to unfavorable interfaces and low Coulombic efficiency(CE),limiting its broader application.Herein,an ether-based electrolyte(termed FGN-182)is formulated,exhibiting ultra-stable Li metal anodes through the incorporation of LiFSI and LiNO3 as dual salts.The synergistic effect of the dual salts facilitates the formation of a highly robust SEI film with fast Li+transport kinetics.Notably,Li||Cu half cells exhibit an average CE reaching up to 99.56%.In particular,pouch cells equipped with high-loading lithium cobalt oxide(LCO,3 mAh cm^(-2))cathodes,ultrathin Li chips(25μm),and lean electrolytes(5 g Ah-1)demonstrate outstanding cycling performance,retaining 80%capacity after 125 cycles.To address the gas issue in the cathode under high voltage,cathode additives 1,3,6-tricyanohexane is incorporated with FGN-182;the resulting high-voltage LCO||Li(4.4 V)pouch cells can cycle steadily over 93 cycles.This study demonstrates that,even with the use of ether-based electrolytes,it is possible to simultaneously achieve significant improvements in both high Li utilization and electrolyte tolerance to high voltage by exploring appropriate functional additives for both the cathode and anode.

改良肌皮瓣法结合眶隔固定术进行眼袋整形的临床效果

目的分析眼袋整形中应用改良肌皮瓣法结合眶隔固定术的临床效果。方法研究对象为2020年3月-2022年4月在台州市椒江微微凯医疗美容门诊部接受眼袋整形的对照组和研究组患者各33例。对照组接受传统肌皮瓣法治疗,观察组行改良肌皮瓣法结合眶隔固定术治疗,对两组的临床治疗效果、手术前后眼部指标、并发症和满意度等进行比较。结果观察组治疗总有效率(96.97%)高于对照组(78.79%);睑袋程度和下睑皱纹评分(1.02±0.11分、3.00±0.15分)低于对照组(1.56±0.15分、4.23±0.36分),皮肤美观度(8.56±1.33分)高于对照组(7.45±1.03分);治疗时间和恢复时间(7.23±1.33 d、30.23±2.36d)短于对照组(8.58±1.56 d、35.56±2.45 d);并发症发生率(6.06%)低于对照组(24.24%);满意度(96.97%)高于对照组(75.76%);数据对比差异均有统计学意义(P<0.05)。结论改良肌皮瓣法结合眶隔固定术应用在眼袋整形中可以明显提高手术效果,降低并发症,并提升患者术后满意度,是一种值得推广的手术方法。