bluuebunny/crossref_metadata_2025_split huggingface dataset:
Carbon-Coated Aluminium Current Collectors for New Li-Ion Battery Generation
Authors: Bizot Chloé , Blin Marie-Anne , Guichard Pierre , Soudan Patrick , Lestriez Bernard , Gaubicher Joël , Poizot Philippe 
Published: May 2020

Since 2015, ARMOR has been designing and producing coated current collectors for lithium-ion batteries and super-capacitors. The En’Safe® technology (represented in Figure 1) uses a thin conductive coating made of carbon and polymer deposited on a metallic substrate. The presence of this thin layer results in lower contact resistance and improved adhesion between the substrate and the electrode which ultimately allows for improved power performances and better cyclability of these energy storage systems (1).
At the industrial scale, the deployment of high-voltage positive material (such as LiNi0,5Mn1,5O4) for new Li-ion battery generation is still facing many issues. Indeed, the different cell components of the positive side can suffer from degradation when polarized at high voltage and high performances are still not achieved. According to our extended investigation, the use of imide-based lithium supporting salts (LiTFSI or LiFSI) is very promising for next generation battery as it is much safer than LiPF6 and enable to stabilize the positive electrode/electrolyte interface, However, traditional aluminium current collector suffers from severe oxidation from 3.7 V vs. Li+/Li in such media.
In this contribution, we will present the new challenges facing ARMOR coated current collectors for next generation lithium-ion batteries with special emphasis on aluminium stability when polarized at high voltage in Al3+-complexing electrolyte media. We will show that the ARMOR coating effectively suppresses aluminium oxidation without any additive or change in solvent. In addition, we are also developing novel aluminium coatings stable enough up to 5 V vs. Li+/Li in order to ensure a high electronic conduction and a long time life of the positive current collector.
(1) C. Busson et al., Journal of Power Sources 406 (2018) 7.

Figure 1
Electrolyte, Solvation Shell and Interphase for Ca and Mg Metal Anode Based Batteries
Authors: Forero-Saboya Juan , Ponrouch Alexandre 
Published: May 2020

Various metals have been used as battery anodes in electrochemical cells ever since the birth of the batteries with Volta’s pile and in the first commercialized primary (Zn/MnO2, Leclanché 1866) and secondary (Pb/acid, Planté 1859) batteries. Li-MoS2 cells, employing Li metal anodes, with specific energies two to three times higher than both Ni/Cd and Pb/acid cells, were withdrawn from the market due to safety issues related to dendrites growth. Instead, electrodeposition of Mg and Ca appears to be less prone to dendrite formation.[1,2] Pioneering work by Aurbach et al. in the early 1990’s showed a surface-film controlled electrochemical behavior of Ca and Mg metal anodes in electrolytes with conventional organic solvents.[3,4] The lack of metal plating was attributed to the poor divalent cation migration through the passivation layer.
Nevertheless, recent demonstration of Ca and Mg plating and stripping in the presence of a passivation layer or an artificial interphase [2,5,6] has paved the way for assessment of new electrolyte formulations with high resilience towards oxidation. However, several challenges remain to be tackled for the development of Ca and Mg based batteries.[7,8] Among these, the need for reliable electrochemical test protocols, mass transport limitations and high desolvation energies (due to strong cation-solvent and cation–anion interactions) are implied.[9, 10] Here, the reliability of electrochemical set-ups involving multivalent chemistries is discussed, and a systematic investigation on the impact of the electrolyte formulation on the cation solvation structure and transport is presented.

References

1. M. Matsui, J. Power Sources, 196 (2011) 7048.
2. A. Ponrouch, C. Frontera, F. Bardé, M.R. Palacín, Nat. Mater., 15 (2016) 169.
3. D. Aurbach, R. Skaletsky, Y. Gofer, J. Electrochem. Soc.138 (1991) 3536.
4. Z. Lu, A. Schechter, M. Moshkovich, D. Aurbach, J. Electroanal. Chem. 466 (1999) 203.
5. D. Wang, X. Gao, Y. Chen, L. Jin, C. Kuss, P. G. Bruce, Nat. Mater. 17 (2018) 16.
6. S.-B. Son, T. Gao, S. P. Harvey, K. X. Steirer, A. Stokes, A. Norman, C. Wang, A. Cresce, K. Xu, C. Ban, Nat. Chem. 10 (2018) 532.
7. A. Ponrouch, M.R. Palacín, Current Opinion in Electrochemistry 9 (2018) 1.
8. A. Ponrouch, J. Bitenc, R. Dominko, N. Lindahl, P. Johansson, M.R. Palacin, Energy Storage Materials 20 (2019) 253.
9. D. S. Tchitchekova, D. Monti, P. Johansson, F. Bardé, A. Randon-Vitanova, M. R. Palacı́n, A. Ponrouch, J. Electrochem. Soc., 164 (2017) A1384.
10. J. D. Forero-Saboya, E. Marchante, R. B. Araujo, D. Monti, P. Johansson, A. Ponrouch, J. Phys. Chem. C (2019).
High-Capacity Mn-Based Cation-Disordered Rocksalt Cathodes
Authors: Lun Zhengyan , Ouyang Bin , Clément Raphaële J. , Kwon Deok-Hwang , Ceder Gerbrand 
Published: May 2020

The discovery of Li-excess cation-disordered rocksalt (DRX) cathodes greatly enlarges the design space beyond the layered NCM-type rocksalt chemistries. More importantly, this new strategy enables high capacity Co and Ni-free cathodes, which is a requirement for the Li-ion industry to grow to the Terra-Wh scale that is needed for the growing electric vehicle and utility applications. Mn-based DRX oxyfluorides are especially promising owing to their large energy densities and good cyclabilities as well as the low cost and earth abundance of Mn.
Herein, we synthesize, characterize, electrochemically test and model four well-chosen compositions within the Li–Mn–O–F DRX chemical space with different Li content and F content: Li1.333Mn(III)0.667O1.333F0.667(HLF67), Li1.333Mn(III)0.5Mn(IV)0.167O1.5F0.5(HLF50), Li1.333Mn(III)0.333Mn(IV)0.333O1.667F0.333(HLF33), and Li1.25Mn(II)0.167Mn(III)0.583O1.333F0.667(LLF67). While all compositions tested achieve higher than 200 mAh/g initial capacity the material with high Li-excess (1.333 per formula unit, Li
x
Mn2-x
O2-y
F
y
) and moderate fluorination (0.333 per formula unit) achieves 349 mAh/g initial capacity and 1068 Wh/kg specific energy. Higher fluorination (0.667 per formula unit) can activate Mn2+/Mn4+redox and thereby balance capacity with cycle life, achieving 256 mAh/g (822 Wh/kg) initial capacity (specific energy) with more than 85% retained after 30 cycles even upon charging to 5.0V. It can be concluded that the Li-site distribution plays a more important role than the metal-redox capacity in determining the initial capacity, whereas the metal-redox capacity is more closely related to the cyclability of the materials. We apply these insights and generate a capacity map of the Li–Mn–O–F chemical space, Li
x
Mn2-x
O2-y
F
y
(1.167 ≤ x ≤ 1.333, 0 ≤ y ≤ 0.667), which predicts both the accessible Li capacity and Mn-redox capacity. This map allows to design compounds which balance high capacity with good cyclability.
Reference
Lun, Zhengyan, et al. "Design principles for high-capacity Mn-based cation-disordered rocksalt cathodes.” Chem (2019), DOI: 10.1016/j.chempr.2019.10.001, in press.
Aluminum Ion Species Transport in Pure and Additive Modulated Deep Eutectic Solvents (DES) Electrolytes
Authors: Suarez Sophia , Paterno Domenec 
Published: May 2020

The need for safe, low cost, high energy and density storage devices is ubiquitous the world over. Satisfying this need requires various energy storage and conversion applications, one of which is the aluminum ion batteries. One problem with expansion in their development and commercialization is the availability of optimized electrolytes. Recently, deep eutectic solvents (DES) have gained attention as electrolytes for energy storage devices. These solvents are similar to ionic liquids, but are generally cheaper and easier to prepare. Additionally, they are known to dissolve metal oxides which plague AIBs operation, and their solubility is dependent on the hydrogen bond donor. Because of their inherent tunability, we studied the effect of AlCl3 concentration (1:1 – 1.7:1 molar ratio), amide type (acetamide (AA), butyramide (BA), propionamide (PA)), viscosity reducing additive type and concentration, on the aluminum ion species and transport in AlCl3:amide DES electrolytes using multi-Nuclear (1H, 27Al) Magnetic Resonance (NMR) and AC Impedance Spectroscopy techniques, as a function of temperature. Below are a few noteworthy observations.
Firstly, for both AlCl3:PA and AlCl3:BA DES electrolytes, a maximum in ionic conductivity was observed at the 1.3:1 molar ratio. For AlCl3:AA DES the maximum occurred at the 1.5:1 molar ratio. secondly, the 27Al spectra the 1:1 molar ratio DES electrolytes showed three well resolved peaks at about 101, 88 and 74 ppm, assigned to [AlCl2(amide)2]+, AlCl4
-, and [AlCl2(amide)2]+ respectively. An example of this is shown in Figure 1 for the 1.0:1 (left) AlCl3:PA. With increasing AlCl3 concentration, the narrow well resolved peaks gave way to broadened, asymmetric spectra with two to three visible but not separated peaks. This is also shown in Figure 1 (right) for the 1.3:1 (right) AlCl3:PA. A fourth peak also appeared for DES electrolytes which could be due to free AlCl3:amide species.

Figure 1. 27Al variable temperature spectra for 1.0:1 (left) and 1.3:1 (right) AlCl3:Propionamide (PA).
Thirdly, like the spectra, the 27Al T1 data for the pure DES electrolytes were very dependent on salt concentration and the species type. For the 1:1 molar ratio electrolyte, the AlCl2(amide)+ species had the longest T1, while the AlCl2(amide)2
+had the shortest. Fourthly, with the inclusion of additives such as propylene carbonate (PC) both the 1H and 27Al T1increased, indicating increasing local ion dynamics possibly through the reduction of bulk viscosity effects and Coulombic interactions. In addition to this, PC also caused additional resolution of the [AlCl2(amide)2]+ species - which was not observed in the pure DES. These results and more will be expounded upon in our presentation.

Figure 1
Towards Dry and Contaminant Free Ca(BF4)2 Based Electrolyte for Ca Metal Anode Based Batteries
Authors: Forero-Saboya Juan , Ponrouch Alexandre 
Published: May 2020

Divalent metal batteries have gained much attention recently given the high gravimetric capacities of calcium and magnesium metal electrodes (1340 and 2000 mAh/g respectively), and thus, holding promise as high energy density next-generation battery technologies. Although calcium metal possesses lower reduction potential (-2.76 V vs SHE) than magnesium (-2.38 V vs SHE), the development of calcium metal batteries has been hampered by the lack of electrolytes allowing for reversible electrodeposition. After the first demonstration of reversible calcium plating/stripping in and organic electrolyte based on Ca(BF4)2 in carbonate solvents [1], the attention devoted to calcium-based batteries have substantially increased. Recently, other electrolyte systems allowing for reversible plating/stripping were reported [2–4].
One of the crucial parameters to consider in the devolvement of divalent metal batteries is the presence of undesired impurities, particularly water, as it will affect greatly the surface chemistry of the calcium metal anode and prevent electrodeposition. As normally alkaline-earth metal salts are more hygroscopic that their alkaline counterparts, obtaining ultra-dry electrolytes is a key challenge which needs to be addressed. In the case of commercial Ca(BF4)2, most likely synthesised in aqueous solution, the water content is usually as high as 30wt%.
In the present study we evaluate different drying methods and report on their effect on the stability of the BF4
- anion. The performance of the differently dried electrolytes with regard to the calcium electrodeposition is evaluated and discussed. An anhydrous synthetic route of Ca(BF4)2 will also be presented and compared to the commercially available salt.

References

1. A. Ponrouch, C. Frontera, F. Bardé, and M. R. Palacín, Nat. Mater., 15, 169–172 (2016).
2. D. Wang et al., Nat. Mater., 17, 16–20 (2017).
3. Z. Li, O. Fuhr, M. Fichtner, and Z. Zhao-Karger, Energy Environ. Sci. (2019).
4. A. Shyamsunder, L. E. Blanc, A. Assoud, and L. F. Nazar, ACS Energy Lett., 4, 2271–2276 (2019).
CrPO4-Type of Compounds As Anode Materials for Na-Ion Batteries
Authors: Yahia Hamdi Ben 
Published: May 2020

To date, research on sodium-ion batteries started to gain more interest. It is mainly motivated by the large abundance of sodium and the hope to produce batteries that are cheaper compared to LIBs and less prone to resource issues and safety concerns [1-3].
During the last three years, our research team has developed several electroactive materials for sodium-ion batteries. Among them, the NASICON- NaFe2-xMx(PO4)(SO4)2 (M=Fe, V, Cr and 0 ≤ x ≤ 1) and the alluaudite- Na2
M
1Fe2(PO4)3 (M=Mn, Fe, Co, Ni) type of compounds. We also discovered recently several compounds crystallizing with the α-CrPO4-type of structure. These phases are very interesting since they contain several vacancies and therefore enable the intercalation of up to three sodium atoms which leads to capacities above 160 mAh/g with very stable cycling at 1C rate. In this paper, we report on the structural and electrochemical properties of the six new M-doped-VPO4 phases (M= Mn, Fe, Co, Ni, Zn, Mg). The crystal structures were solved by the Rietveld method using powder X-ray diffraction (PXRD) data. The electrochemical performances were examined by galvanometric cycling and cyclic voltammetry. The stability of the structure during cycling was followed by ex-situ PXRD experiments.
The cycling performance of the Zn-doped-VPO4 phase is given in Figure 1. Cells embedding (NaPF6:EC:PC) electrolyte and Na-metal were used. Additional details on the other five new phases will be provided during the conference.
Figure 1. Electrochemical performance of the newly prepared Zinc-doped-VPO4 phase at the rate of 1C vs. Na+/Na and the general intercalation mechanism for the α-CrPO4-type of structure.

Reference:

[1] Makino, K.; Katayama, Y.; Miura, T.; Kishi, T., J. Power Sources 2002, 112, 85−89.
[2] Gaubicher, J.; Wurm, C.; Goward, G.; Masquelier, C., Nazar, L., Chem. Mater. 2000, 12, 3240−3242.
[3] Jian, Z.; Zhao, L.; Pan, H.; Hu, Y.-S.; Li, H.; Chen, W., Chen, L., Electrochem. Commun. 2012, 14, 86−89.

Figure 1
Investigation of the Garnet Solid Electrolyte and Lithium Metal Anode Interface
Authors: Brown Zachary Lee , Pasta Mauro 
Published: May 2020

Improving the energy density of lithium-ion batteries by replacing a graphite anode with lithium metal anode is heavily desired.1 The garnet (LLZO) solid electrolytes are promising candidates to protect lithium metal due to their high lithium-ion conductivity and high elastic modulus, however, the interfacial chemistry between LLZO/Li is poorly understood.2-4 In this work, LLZO electrolytes of >98% theoretical density were prepared with Field Assisted Sintering Technology. The solid state electrochemistry of LLZO with lithium and blocking electrodes is characterized using electrochemical impedance spectroscopy. Further, investigation of interfacial phenomena between LLZO and Li metal using a suite of surface characterization techniques will be discussed in detail.

References

1. Liu J., Bao Z., Cui Y., Dufek E. J., Goodenough J. B., Khalifah P., Li Q., Liaw B. Y., Liu P., Manthiram A., Meng Y. S., Subramanian V. R., Toney M. F., Viswanathan V. V., Whittingham M. S., Xiao J., Xu W., Yang J., Yang X. Q., and Zhang J. G., Energy, 4, 180 (2019).
2. Krauskopf, Hartmann H., Zeier W. G., and Janek J. ACS Appl. Mater. Interfaces, 11, 14463 (2019).
3. Fu K., GongY., LiuB., ZhuY., Xu S., YaoY., Luo W., Wang C., Lacey S. D., DaiJ., ChenY., MoY., WachsmanE., and Hu L. Sci. Advances, 3, e1601659 (2017).
4. Sharafi A., KazyakE., DavisA. L., YuS., Thompson T., SiegelD. J., DasguptaN. P., and Sakamoto J. Chem. Mater.,
29, 7961 (2017).
Engineering Interfaces for Stable Na Metal Solid-State Batteries
Authors: Hatzell Kelsey , Ren Yuxun 
Published: May 2020

Efficient and reversible cycling of alkali metal anodes is a key requirement for achieving high-energy density solid-state batteries [1,2]. While there has been significant interest and research on understanding plating and stripping mechanisms of lithium metal, there has been far less work to understand sodium metal electrode kinetics at solid electrolyte interfaces. Sodium metal is highly reactive with most solid electrolytes which leads to the formation of unstable interphases. These interphases lead to low cycle life and poor power performance. Herein, we study the electrochemical and transport properties of a novel hybrid polymer-Na3SbS4 solid electrolyte. Combining a polymer with a inorganic solid electrolytes provides a way to process thin sodium-ion conducting solid electrolytes at scale and provides a pathway toward tailoring the stability of the solid electrolyte against a alkali metal [3]. A cross-linking approached is utilized to control the structure of the inorganic ionic conductor within the polymer matrix and improve the electrolyte stability. The buried interface is characterized using a suite of in situ imaging techniques to track transformations at the Na-metal interface.
[1]Shen, Fengyu, Marm B. Dixit, Xianghui Xiao, and Kelsey B. Hatzell. "Effect of pore connectivity on Li dendrite propagation within LLZO electrolytes observed with synchrotron X-ray tomography." ACS Energy Letters 3, no. 4 (2018): 1056-1061.
[2]Zaman, Wahid, Nicholas M. Hortance, Marm B. Dixit, Vincent De Andrande, and Kelsey Bridget Hatzell. "Visualizing percolation and ion transport in hybrid solid electrolytes for Li-metal batteries." Journal of Materials Chemistry A (2019).
[3]Dixit, Marm B., Wahid Zaman, Yousuf Bootwala, Yanjie Zheng, Marta C. Hatzell, and Kelsey B. Hatzell. "Scalable manufacturing of hybrid solid electrolytes with interface control." ACS applied materials & interfaces (2019).
Non-Destructive, Non-Invasive Noise Measurements for Metallic Lithium Anodes for Lithium Ion Batteries
Authors: Karaoglu Gozde , Uzundal Can Berk , Ulgut Burak 
Published: May 2020

Electrochemical Noise measurements have been in the spotlight of electrochemical analysis for measurements on stochastic modes of corrosion since the days of Dawson (Hladky and Dawson Corrosion Science 21(4), (1981),317-322). More recently, electrochemical noise measurements for fuel cells and batteries came up as non-invasive and non-perturbing testing methods that can be used for research(Journal of The Electrochemical Society, 165 (11) A2557-A2562 (2018)) and a potential real-time monitoring tool (Denisov et.al. Fuel Cells 17,(2017),225-237).
Metallic lithium anodes are currently commercially employed for non-rechargeable batteries (e.g LiSOCl2 or LiMnO2). The main hurdle along the way of implementation in rechargeable batteries is the dendrite formation during the charging process (Cheng, et.al. Chem. Rev. 2017, 117, 10403−10473). The formation of dendrites during charging can lead to catastrophic failure of the batteries including thermal runaway. Though studies on avoiding such failures through either modifying the surface of the electrode and/or the kinetics of deposition are underway, however, as indicated by the review: “more smartly designed in situ or operando techniques are urgently needed to track the process in a working cell”.
We have been working on battery noise measurements for the past number of years (Turkish Journal of Chemistry, 42, (2018), 859-868). We have recently shown that the noise of primary Li/MnO2 batteries increase to measurable levels upon suffering a short circuit (Journal of the Electrochemical Society 165(11),(2018),A2557-A2562) and that this is due to the uneven discharge of the metallic lithium anode(Journal of the Electrochemical Society, submitted).
In this contribution, we are going to be reporting electrochemical noise as a truly operando method to study dendrite formation. As the measurement requires no modification to the cell (i.e. no windows in the case or the current collectors, no geometry change, not a half cell) and no perturbation in the applied current or the voltage, it is the ultimate non-invasive and non-perturbing method that has the potential to be used as not only a research tool, but also a real-time implementable sensor that can be commercially deployed.
As shown in the figure below, using a metallic lithium anode, the noise after a charging attempt with a high current does show an increased noise level due to the uneven formation of dendrites.

Figure 1
(Invited) All Solid-State Batteries: From Interface to New-Type Electrolytes
Authors: Sun Andy Xueliang 
Published: May 2020

All-state-state lithium batteries (ASSLBs) have gained worldwide attention because of the high ionic conductivity of SEs, intrinsic safety and improved energy density. In ASSLBs, solid-state electrolyte is a key component. Compared with polymer-based and oxide-based electrolytes, sulfide-based electrolyte generally exhibits the highest ionic conductivity (10-3 ~ 10-2 S/cm) and favorable mechanical property. However, the serious interfacial challenge, bad air stability, narrow electrochemical windows of sulfide-based electrolyte significantly impede development of sulfide-based ASSLBs. Generally, an artificial, uniform and ultrathin interfacial layer is critical to address these challenges. Atomic layer deposition (ALD) and molecular layer deposition (MLD) are unique coating techniques that can realize excellent coverage and conformal deposition with precisely controllable at the nanoscale level due to its self-limiting nature, which are ideal for addressing the challenges of interface in SSLBs.
In this talk, I will demonstrate to apply ALD/MLD to
(i)

stabilize the interface between cathode electrodes and electrolytes and prevent the formation of intrinsically high resistance layers,
(ii)

suppress elemental inter-diffusion during the operation of SSLBs,
(iii)

fabricate facile ionic transportation channels to facilitate ion exchange between different components of SSLBs, and

(iv)

buffer volume changes during cycling of SSLBs [1]
.
In this talk, I will talk about halide-based electrolyte for ASSLBs. Compared with sulfide-based electrolyte, both experimental and theoretical results recently demonstrate that halide-based electrolytes have more advantages including high RT ionic conductivity (>10-3 S cm-1, theoretically possible 10-2 S cm-1), wide electrochemically stable window (possible up to 6 V), high air-stability, good stability toward oxide cathode materials, and even salable water synthesis strategy [2-3].

References:

1. Zhao, X. Sun .Addressing Interfacial Issues in Liquid-based and Solid-State Batteries by Atomic and Molecular Layer Deposition. Joule. 2, 2583-2604(2018).
2. Li, J. Liang, X. Sun, et al., H2O-Mediated Synthesis of Superionic Halide Solid Electrolyte. Angewandte Chemie International Edition, 2019, http://dx.doi.org/10.1002/anie.201909805.
3. Li, J. Liang, X. Sun, et al.,. Air-Stable Li3InCl6 Electrolyte with High Voltage Compatibility for All-Solid-State Batteries. Energy Environ. Sci.,2019, 12, 2665 - 267.