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All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Materials Data on LiClO4 by Materials Project

LiClO4 crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. Li is bonded to six O atoms to form LiO6 octahedra that share corners with six equivalent ClO4 tetrahedra and edges with two equivalent LiO6 octahedra. There are a spread of Li–O bond distances ranging from 2.03–2.44 Å. There are three inequivalent O sites. In the first O site, O is bonded in a trigonal planar geometry to two equivalent Li and one Cl atom. The O–Cl bond length is 1.47 Å. In the second O site, O is bonded in a bent 150 degrees geometry to one Li and one Cl atom. The O–Cl bond length is 1.45 Å. In the third O site, O is bonded in a distorted T-shaped geometry to two equivalent Li and one Cl atom. The O–Cl bond length is 1.46 Å. Cl is bonded to four O atoms to form ClO4 tetrahedra that share corners with six equivalent LiO6 octahedra. The corner-sharing octahedra tilt angles range from 40–53°.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Li7CuAs4ClO14 by Materials Project

Li7CuAs4O14Cl is Chalcostibite-derived structured and crystallizes in the monoclinic Cc space group. The structure is three-dimensional. there are seven inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded in a 6-coordinate geometry to five O2- and one Cl1- atom. There are a spread of Li–O bond distances ranging from 2.09–2.82 Å. The Li–Cl bond length is 2.61 Å. In the second Li1+ site, Li1+ is bonded to four O2- and one Cl1- atom to form distorted LiClO4 trigonal bipyramids that share a cornercorner with one LiClO5 octahedra, corners with four AsO4 tetrahedra, and an edgeedge with one CuO6 octahedra. The corner-sharing octahedral tilt angles are 89°. There are a spread of Li–O bond distances ranging from 1.97–2.23 Å. The Li–Cl bond length is 2.40 Å. In the third Li1+ site, Li1+ is bonded in a 5-coordinate geometry to four O2- and one Cl1- atom. There are a spread of Li–O bond distances ranging from 1.99–2.43 Å. The Li–Cl bond length is 2.60 Å. In the fourth Li1+ site, Li1+ is bonded in a 4-coordinate geometry to three O2- and one Cl1- atom. There are a spread of Li–O bond distances ranging from 1.96–2.06 Å. The Li–Cl bond length is 2.47 Å. In the fifth Li1+ site, Li1+ is bonded in a 4-coordinate geometry to four O2- atoms. There are a spread of Li–O bond distances ranging from 1.96–2.40 Å. In the sixth Li1+ site, Li1+ is bonded to five O2- and one Cl1- atom to form distorted LiClO5 octahedra that share corners with four AsO4 tetrahedra, a cornercorner with one LiClO4 trigonal bipyramid, an edgeedge with one CuO6 octahedra, and an edgeedge with one AsO4 tetrahedra. There are a spread of Li–O bond distances ranging from 2.00–2.42 Å. The Li–Cl bond length is 2.43 Å. In the seventh Li1+ site, Li1+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Li–O bond distances ranging from 2.16–2.60 Å. Cu2+ is bonded to six O2- atoms to form distorted CuO6 octahedra that share corners with six AsO4 tetrahedra, an edgeedge with one LiClO5 octahedra, and an edgeedge with one LiClO4 trigonal bipyramid. There are a spread of Cu–O bond distances ranging from 1.95–2.54 Å. There are four inequivalent As5+ sites. In the first As5+ site, As5+ is bonded to four O2- atoms to form AsO4 tetrahedra that share a cornercorner with one LiClO5 octahedra, a cornercorner with one CuO6 octahedra, a cornercorner with one AsO4 tetrahedra, and corners with two equivalent LiClO4 trigonal bipyramids. The corner-sharing octahedra tilt angles range from 50–56°. There are a spread of As–O bond distances ranging from 1.69–1.78 Å. In the second As5+ site, As5+ is bonded to four O2- atoms to form AsO4 tetrahedra that share a cornercorner with one CuO6 octahedra, corners with two equivalent LiClO5 octahedra, a cornercorner with one AsO4 tetrahedra, and a cornercorner with one LiClO4 trigonal bipyramid. The corner-sharing octahedra tilt angles range from 52–62°. There are a spread of As–O bond distances ranging from 1.69–1.80 Å. In the third As5+ site, As5+ is bonded to four O2- atoms to form AsO4 tetrahedra that share a cornercorner with one LiClO5 octahedra, corners with two equivalent CuO6 octahedra, and a cornercorner with one AsO4 tetrahedra. The corner-sharing octahedra tilt angles range from 63–74°. There are a spread of As–O bond distances ranging from 1.71–1.83 Å. In the fourth As5+ site, As5+ is bonded to four O2- atoms to form AsO4 tetrahedra that share corners with two equivalent CuO6 octahedra, a cornercorner with one AsO4 tetrahedra, a cornercorner with one LiClO4 trigonal bipyramid, and an edgeedge with one LiClO5 octahedra. The corner-sharing octahedra tilt angles range from 48–59°. There are a spread of As–O bond distances ranging from 1.70–1.81 Å. There are fourteen inequivalent O2- sites. In the first O2- site, O2- is bonded in a trigonal planar geometry to one Li1+, one Cu2+, and one As5+ atom. In the second O2- site, O2- is bonded to three Li1+ and one As5+ atom to form distorted OLi3As tetrahedra that share corners with five OLi3As tetrahedra, a cornercorner with one OLi2CuAs trigonal pyramid, an edgeedge with one OLi3As tetrahedra, and an edgeedge with one ClLi5 trigonal bipyramid. In the third O2- site, O2- is bonded in a trigonal planar geometry to one Li1+, one Cu2+, and one As5+ atom. In the fourth O2- site, O2- is bonded to two Li1+, one Cu2+, and one As5+ atom to form distorted OLi2CuAs trigonal pyramids that share corners with six OLi3As tetrahedra, a cornercorner with one ClLi5 trigonal bipyramid, and corners with two equivalent OLi2CuAs trigonal pyramids. In the fifth O2- site, O2- is bonded to two Li1+, one Cu2+, and one As5+ atom to form distorted OLi2CuAs tetrahedra that share corners with six OLi3As tetrahedra, corners with two equivalent ClLi5 trigonal bipyramids, and corners with two OLi2CuAs trigonal pyramids. In the sixth O2- site, O2- is bonded to three Li1+ and one As5+ atom to form distorted OLi3As tetrahedra that share corners with four OLi3As tetrahedra, corners with two equivalent ClLi5 trigonal bipyramids, a cornercorner with one OLi2CuAs trigonal pyramid, and an edgeedge with one OLi3As tetrahedra. In the seventh O2- site, O2- is bonded in a 2-coordinate geometry to two Li1+ and two As5+ atoms. In the eighth O2- site, O2- is bonded to three Li1+ and one As5+ atom to form distorted OLi3As tetrahedra that share corners with two OLi3As tetrahedra, corners with two equivalent ClLi5 trigonal bipyramids, a cornercorner with one OLi2CuAs trigonal pyramid, and edges with two OLi3As tetrahedra. In the ninth O2- site, O2- is bonded in a distorted trigonal non-coplanar geometry to two Li1+ and one As5+ atom. In the tenth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+ and two As5+ atoms. In the eleventh O2- site, O2- is bonded to two Li1+, one Cu2+, and one As5+ atom to form distorted OLi2CuAs trigonal pyramids that share corners with five OLi3As tetrahedra, corners with two equivalent ClLi5 trigonal bipyramids, and corners with two equivalent OLi2CuAs trigonal pyramids. In the twelfth O2- site, O2- is bonded in a 4-coordinate geometry to two Li1+, one Cu2+, and one As5+ atom. In the thirteenth O2- site, O2- is bonded to three Li1+ and one As5+ atom to form OLi3As tetrahedra that share corners with six OLi3As tetrahedra, corners with three OLi2CuAs trigonal pyramids, and an edgeedge with one ClLi5 trigonal bipyramid. In the fourteenth O2- site, O2- is bonded to three Li1+ and one As5+ atom to form OLi3As tetrahedra that share corners with three OLi3As tetrahedra, corners with three OLi2CuAs trigonal pyramids, and an edgeedge with one ClLi5 trigonal bipyramid. Cl1- is bonded to five Li1+ atoms to form distorted ClLi5 trigonal bipyramids that share corners with six OLi3As tetrahedra, corners with three OLi2CuAs trigonal pyramids, and edges with three OLi3As tetrahedra.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Li10B14Cl2O25 by Materials Project

Li10B14O25Cl2 crystallizes in the cubic F23 space group. The structure is three-dimensional. there are two inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded in a 4-coordinate geometry to three equivalent O2- and one Cl1- atom. All Li–O bond lengths are 2.02 Å. The Li–Cl bond length is 2.44 Å. In the second Li1+ site, Li1+ is bonded to four O2- and one Cl1- atom to form distorted LiClO4 trigonal bipyramids that share corners with six BO4 tetrahedra and corners with five equivalent LiClO4 trigonal bipyramids. There are two shorter (2.08 Å) and two longer (2.18 Å) Li–O bond lengths. The Li–Cl bond length is 2.53 Å. There are three inequivalent B3+ sites. In the first B3+ site, B3+ is bonded in a trigonal planar geometry to three equivalent O2- atoms. All B–O bond lengths are 1.38 Å. In the second B3+ site, B3+ is bonded to four O2- atoms to form BO4 tetrahedra that share corners with six BO4 tetrahedra and corners with three equivalent LiClO4 trigonal bipyramids. There is three shorter (1.44 Å) and one longer (1.72 Å) B–O bond length. In the third B3+ site, B3+ is bonded to four O2- atoms to form BO4 tetrahedra that share corners with two equivalent BO4 tetrahedra and corners with four equivalent LiClO4 trigonal bipyramids. There is two shorter (1.48 Å) and two longer (1.49 Å) B–O bond length. There are three inequivalent O2- sites. In the first O2- site, O2- is bonded to four equivalent B3+ atoms to form corner-sharing OB4 tetrahedra. In the second O2- site, O2- is bonded to two Li1+ and two B3+ atoms to form distorted OLi2B2 tetrahedra that share a cornercorner with one ClLi6 octahedra, a cornercorner with one ClLi4 tetrahedra, and corners with seven OB4 tetrahedra. The corner-sharing octahedral tilt angles are 82°. In the third O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+ and two B3+ atoms. There are two inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded to six equivalent Li1+ atoms to form ClLi6 octahedra that share corners with twelve equivalent OLi2B2 tetrahedra. In the second Cl1- site, Cl1- is bonded to four equivalent Li1+ atoms to form ClLi4 tetrahedra that share corners with twelve equivalent OLi2B2 tetrahedra.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on LiH20C8ClO4 by Materials Project

LiC8H20O4Cl is High Pressure Cadmuum Telluride-derived structured and crystallizes in the monoclinic C2/c space group. The structure is zero-dimensional and consists of four LiC8H20O4Cl clusters. Li1+ is bonded to four O2- and one Cl1- atom to form LiClO4 trigonal bipyramids that share corners with four CH3O tetrahedra. There are two shorter (2.12 Å) and two longer (2.14 Å) Li–O bond lengths. The Li–Cl bond length is 2.42 Å. There are four inequivalent C+1.50- sites. In the first C+1.50- site, C+1.50- is bonded to three H1+ and one O2- atom to form CH3O tetrahedra that share a cornercorner with one LiClO4 trigonal bipyramid. All C–H bond lengths are 1.10 Å. The C–O bond length is 1.43 Å. In the second C+1.50- site, C+1.50- is bonded in a distorted trigonal non-coplanar geometry to two H1+ and one O2- atom. There is one shorter (1.10 Å) and one longer (1.11 Å) C–H bond length. The C–O bond length is 1.44 Å. In the third C+1.50- site, C+1.50- is bonded in a distorted trigonal non-coplanar geometry to two H1+ and one O2- atom. Both C–H bond lengths are 1.11 Å. The C–O bond length is 1.44 Å. In the fourth C+1.50- site, C+1.50- is bonded to three H1+ and one O2- atom to form CH3O tetrahedra that share a cornercorner with one LiClO4 trigonal bipyramid. All C–H bond lengths are 1.10 Å. The C–O bond length is 1.44 Å. There are ten inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a single-bond geometry to one C+1.50- atom. In the second H1+ site, H1+ is bonded in a single-bond geometry to one C+1.50- atom. In the third H1+ site, H1+ is bonded in a single-bond geometry to one C+1.50- atom. In the fourth H1+ site, H1+ is bonded in a single-bond geometry to one C+1.50- atom. In the fifth H1+ site, H1+ is bonded in a single-bond geometry to one C+1.50- atom. In the sixth H1+ site, H1+ is bonded in a single-bond geometry to one C+1.50- atom. In the seventh H1+ site, H1+ is bonded in a single-bond geometry to one C+1.50- atom. In the eighth H1+ site, H1+ is bonded in a single-bond geometry to one C+1.50- atom. In the ninth H1+ site, H1+ is bonded in a single-bond geometry to one C+1.50- atom. In the tenth H1+ site, H1+ is bonded in a single-bond geometry to one C+1.50- atom. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted trigonal non-coplanar geometry to one Li1+ and two C+1.50- atoms. In the second O2- site, O2- is bonded in a trigonal non-coplanar geometry to one Li1+ and two C+1.50- atoms. Cl1- is bonded in a single-bond geometry to one Li1+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Complementary Electrolyte Design for Li Metal Batteries in Electric Vehicle Applications

In this report a complementary electrolyte system with 0.8 M lithium bis(fluorosulfonylimide) (LiFSI) salt and 2 wt % lithium perchlorate (LiCLO4) additive in fluoroethylene carbonate (FEC)/ethyl methyl carbonate (EMC) solution enables not only stable cycling of lithium metal batteries (LMBs) with practical loading (<30 μm lithium anode, cathode loading > 4 mAh/cm 2 ) but also outstanding degradation stability toward the end of cycle life when compared to the conventional electrolyte. Although the use of LiFSI salt can increase the electrolyte conductivity and lengthen the cycle life of LMBs, the aged lithium anode morphology formed by the sacrificial decomposition of LiFSI is highly porous, leading to an abrupt cell capacity drop toward the end of cycling. Moreover, the inability to stop aluminum corrosion by the LiFSI-based electrolyte also causes cracking of the cathode tab during prolonged cycling. It is observed that a highly porous aged lithium consumed electrolyte at a higher rate, leading to the dry-out of electrolyte solvents. On the contrary, dense aged lithium anode morphology increased the localized current applied on the lithium, causing the formation of lithium dendrite. Thus, porosity control is the key to enhance battery performance. In this complementary system, LiClO 4 was introduced as an advanced additive to not only improve the capacity retention rate but also mitigate the abrupt capacity drop toward the end of cycle life because LiClO 4 acted as a pore astringent reducing the porosity of the aged lithium metal anode to the desired level. Moreover, the addition of LiClO 4 can also suppress the AI corrosion, allowing stable high-voltage cycling of LMBs. The synergistic effect of combining LiFSI salt and a LiClO 4 additive leads to an electrolyte system that can facilitate the application of high-energy LMBs with practical electrode loading.

25 ENERGY STORAGE↗
DOE OSTI2021

Enhanced electro-osmosis in propylene carbonate salt solutions

Properties of solid–liquid interfaces and surface charge characteristics mediate ionic and molecular transport through porous systems, affecting many processes such as separations. Herein, we report experiments designed to probe the electrochemical properties of solid–liquid interfaces using a model system of a single polyethylene terephthalate (PET) pore in contact with aqueous and propylene carbonate solutions of LiClO 4 . First, the existence and polarity of surface charges were inferred from current–voltage curves recorded when a pore was placed in contact with a LiClO4 concentration gradient. Second, the electro-osmotic transport of uncharged polystyrene particles through the PET pore provided information on the polarity and the magnitude of the pore walls’ zeta potential. Our experiments show that the PET pores become effectively positively charged when in contact with LiClO 4 solutions in propylene carbonate, even though in aqueous LiClO 4 , the same pores are negatively charged. Additionally, the electro-osmotic velocity of the particles revealed a significantly higher magnitude of the positive zeta potential of the pores in propylene carbonate compared to the magnitude of the negative zeta potential in water. The presented methods of probing the properties of solid–liquid interfaces are expected to be applicable to a wide variety of solid and liquid systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Manufacturing Cathodes via Dry-Processing for Lithium-Ion Batteries

Conventional lithium-ion battery (LIB) electrodes are prepared through a wet slurry process with n-methyl pyrrolidone solvent, especially for cathodes. The wet slurry process encounters several disadvantages such as binder migration, electrode cracking in thick electrodes, energy intense heat-dry NMP solvent removal, and costly NMP recovery. The cost and energy consumption of coating and drying of electrode are about 11.5 % and > 46 % in LIB manufacturing, respectively. Thereby, it is essential to develop a facile roll-to-roll solvent-free LIB electrode processing for reducing the cost and energy consumption. Recently, the Maxwell-type dry processing (DP) shines new lights on LIB manufacturing, which mainly bases on dry mixing (DM) of electrode component powder followed by calendering into electrode films and laminating onto current collectors, realizing the rapid manufacturing of LIB electrodes in a powder-to-film manner for industries. This report shares some recent progress on the DP from our group. We aim to further advance the manufacturing science of DP by correlating the processing conditions with electrode properties and performance. Particularly, we investigate the effect of DM, and compression on the polytetrafluoroethylene (PTFE) binder fiberization, porosity, mechanical properties, electrical conductivity and electrochemical behaviors of electrodes. The DM study suggests that PTFE fiberization heavily relies on the degree of DM. Insufficient DM results in poor PTFE fiberization while outrageous DM damages the formed PTFE fibers. Both negatively affect the mechanical behaviors of the electrodes and their rate capability. However, moderate DM is highly beneficial. In addition, our study of the porosity impact reveals that LiNi0.8Mn0.1Co0.1O2 (NMC) secondary particles can be broken into primary particles due to compression, especially at low porosity. Those fractured NMC secondary particles exhibit lower modulus. We propose that a moderate porosity of around 32% favors the electronic conductivity, charge transfer impedance and rate capability. The study of the cathodic electrolyte interphase layer of PTFE-based DPed electrode confirms that side reactions of PTFE binder due to the formation of LiF in LiClO4-based electrolyte.

Tao, Runming↗
NASA NTRS1990

12-crown-4 ether-assisted enhancement of ionic conductivity and interfacial kinetics in polyethylene oxide electrolytes

The electrical and electrochemical properties of thin films of polyethylene oxide electrolytes with and without 12-crown-4 ether (12Cr4) are studied as a function of temperature and in the frequency regime from 100 kHz to 0.1 Hz. These measurements were made on electrolytes containing LiCF3SO3, LiBF4, or LiClO4 salts. At a given temperature, the bulk conductivity for a particular salt depends on the 12Cr4 concentration, reaching a maximum for a ratio of 12Cr4 to Li of 0.003.

Nagasubramanian, G.↗
NASA NTRS1990

Effects of 12-Crown-4 ether on the ionic conductivity and electrode kinetics of electrolytes in polyethylene oxide

Results are described of investigations of the electrical and electrochemical properties of thin films of polyethylene oxide (PEO) electrolytes with and without 12-Crown-4 ether (12Cr4) as a function of temperature and in the frequency regime 100 kHz-0.1 Hz. These measurements were made for LiCF3SO3, LiBF4, and LiClO4 salts. At a given temperature, the bulk conductivity, sigma, (S/cm), for a particular salt, depends on the 12Cr4 concentration with sigma reaching a maximum at about 3 mM 12Cr4. Of the three salts studied, the sigma is the highest for PEO/LiBF4 with 3 mM 12Cr4. The ac and dc measurements yield a lower charge transfer resistance for 12Cr4-incorporated samples than for samples without. Plating/stripping of Li occurs at a potential closer to Li(+)/Li for 12Cr4 samples than those without. The conductivities of a thin (about 100 microns) and a thick (400 microns) films are similar.

Nagasubramanian, G.↗
NASA NTRS2002

Solid State Electrolytes Prepared from PEO (360) Silanated Silica

All solid state composite electrolytes were prepared using fumed silica (SiO2) silanated with an oligomeric polyethylene oxide (PEO) silane containing 6-9 ethylene oxide repeat units, a PEO matrix and LiClO4 (8/1 O/Li). The PEO-silane covalently attached to the silica was amorphous, with a T(sub g) that increased from -90 C to -53 C after attachment. The conductivity of films prepared using the PEO-silanated silica increased to approx. 6 x 10(exp -5) S/cm at RT compared with approx. 1 x 10(-5) S/cm for films prepared with unsilanated SiO2.

Maitra, P.↗
NASA NTRS2003

In Situ Raman Microscopy of a Single Graphite Microflake Electrode in a Li(+)-containing Electrolyte

Highly detailed Raman spectra from a single KS-44 graphite microflake electrode as a function of the applied potential have been collected in situ using a Raman microscope and a sealed spectroelectrochemical cell isolated from the laboratory environment. Correlations were found between the Raman spectral features and the various Li(+) intercalation stages while recording in real time Raman spectra during a linear potential scan from 0.7 down ca. 0.0V vs Li/Li(+) at a rate of 0.1 mV/s in a 1M LiClO4 solution in a 1:l (by volume) ethylene carbonate (EC):diethyl carbonate (DEC) mixture. In particular, clearly defined isosbestic points were observed for data collected in the potential range where the transition between dilute phase 1 and phase 4 of lithiated graphite is known to occur, i.e. 0.157 < E < 0.215 vs Li/Li(+). Statistical analysis of the spectroscopic data within this region made it possible to determine independently the fraction of each of the two phases present as a function of potential without relying on coulometric information and then predict, based on the proposed stoichiometry for the transition, a spectrally-derived voltammetric feature.

Shi, Qing-Fang↗