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All sourcesNASA NTRSDOE OSTI
NASA NTRS2011

Use of Additives to Improve Performance of Methyl Butyrate-Based Lithium-Ion Electrolytes

This work addresses the need for robust rechargeable batteries that can operate well over a wide temperature range. To this end, a number of electrolyte formulations have been developed that incorporate the use of electrolyte additives to improve the high-temperature resilience, low-temperature power capability, and life characteristics of methyl butyrate-based electrolyte solutions. These electrolyte additives include mono-fluoroethylene carbonate (FEC), lithium oxalate, vinylene carbonate (VC), and lithium bis(oxalato)borate (LiBOB), which have been shown to result in improved high-temperature resilience of all carbonate-based electrolytes. Improved performance has been demonstrated of Li-ion cells with methyl butyrate-based electrolytes, including 1.20M LiPF6 in EC+EMC+MB (20:20:60 v/v %); 1.20M LiPF6 in EC+EMC+MB (20:20:60 v/v %) + 2% FEC; 1.20M LiPF6 in EC+EMC+MB (20:20:60 v/v %) + 4% FEC; 1.20M LiPF6 in EC+EMC+MB (20:20:60 v/v %) + lithium oxalate; 1.20M LiPF6 in EC+EMC+MB (20:20:60 v/v %) + 2% VC; and 1.20M LiPF6 in EC+EMC+MB (20:20:60 v/v %) + 0.10M LiBOB. These electrolytes have been shown to improve performance in MCMB-LiNiCoO2 and graphite-LiNi1/3Co1/3Mn1/3O2 experimental Li-ion cells. A number of LiPF6-based mixed carbonate electrolyte formulations have been developed that contain ester co-solvents, which have been optimized for operation at low temperature, while still providing reasonable performance at high temperature. For example, a number of ester co-solvents were investigated, including methyl propionate (MP), ethyl propionate (EP), methyl butyrate (MB), ethyl butyrate (EB), propyl butyrate (PB), and butyl butyrate (BB) in multi-component electrolytes of the following composition: 1.0M LiPF6 in ethylene carbonate (EC) + ethyl methyl carbonate (EMC) + X (20:60:20 v/v %) [where X = ester co-solvent]. ["Optimized Car bon ate and Ester-Based Li-Ion Electrolytes", NASA Tech Briefs, Vol. 32, No. 4 (April 2008), p. 56.] Focusing upon improved rate capability at low temperatures (i.e., 20 to 40 C), this approach was optimized further, resulting in the development of 1.20M LiPF6 in EC+EMC+MP (20:20:60 v/v %) and 1.20M LiPF6 in EC+EMC+EB (20:20:60 v/v %), which were demonstrated to operate well over a wide temperature range in MCMB-LiNiCoAlO2 and Li4Ti5O12(-)LiNiCoAlO2 prototype cells.

Smart, Marshall C.↗
NASA NTRS2006

Mixed-Salt/Ester Electrolytes for Low-Temperature Li+ Cells

Electrolytes comprising, variously, LiPF6 or LiPF6 plus LiBF4 dissolved at various concentrations in mixtures of alkyl carbonates and alkyl esters have been found to afford improved low-temperature performance in rechargeable lithium-ion electrochemical cells. These and other electrolytes have been investigated in a continuing effort to extend the lower limit of operating temperatures of such cells. This research at earlier stages, and the underlying physical and chemical principles, were reported in numerous previous NASA Tech Briefs articles, the most recent being Ester-Based Electrolytes for Low-Temperature Li-Ion Cells (NPO-41097), NASA Tech Briefs, Vol. 29, No. 12 (December 2005), page 59. The ingredients of the solvent mixtures include ethylene carbonate (EC), ethyl methyl carbonate (EMC), methyl butyrate (MB), and methyl propionate (MP). The electrolytes were placed in Li-ion cells containing carbon anodes and LiNi0.8Co0.2O2 cathodes, and the electrical performances of the cells were measured over a range of temperatures down to 60 C. The electrolytes that yielded the best low-temperature performances were found to consist, variously, of 1.0 M LiPF6 + 0.4 M LiBF4 or 1.4 LiPF6 in 1EC + 1EMC + 8MP or 1EC + 1EMC + 8MB, where the concentrations of the salts are given in molar units and the proportions of the solvents are by relative volume.

Smart, Marshall↗
NASA NTRS2000

Electrolytes for Li-Ion Cells in Low Temperature Applications

Prototype AA-size lithium-ion cells have been demonstrated to operate effectively at temperatures as low as -30 to -40 C. These improvements in low temperature cell performance have been realized by the incorporation of ethylene carbonate-based electrolytes which possess low melting, low viscosity cosolvents, such as methyl acetate, ethyl acetate, gamma-butyrolactone, and ethyl methyl carbonate. The cells containing a 0.75M LiPF6 EC+DEC+DMC+EMC (1:1:1:1) electrolyte displayed the best performance at -30 C (> 90% of the room temperature capacity at approximately C/15 rate), whereas, at -40 C the cells with the 0.75M LiPF6 EC+DEC+DMC+MA (1:1:1:1) and 0.75M LiPF6 EC+DEC+DMC+EA (1:1:1:1) electrolytes showed superior performance.

Smart, M. C.↗
NASA NTRS2001

Performance of Li-Ion Cells Under Battery Voltage Charge Control

A study consisting of electrochemical characterization and Low-Earth-Orbit (LEO) cycling of Li-Ion cells from three vendors was initiated in 1999 to determine the cycling performance and to infuse the new technology in the future NASA missions. The 8-cell batteries included in this evaluation are prismatic cells manufactured by Mine Safety Appliances Company (MSA), cylindrical cells manufactured by SAFT and prismatic cells manufactured by Yardney Technical Products, Inc. (YTP). The three batteries were cycle tested in the LEO regime at 40% depth of discharge, and under a charge control technique that consists of battery voltage clamp with a current taper. The initial testing was conducted at 20 C; however, the batteries were cycled also intermittently at low temperatures. YTP 20 Ah cells consisted of mixed-oxide (Co and Ni) positive, graphitic carbon negative, LIPF6 salt mixed with organic carbonate solvents. The battery voltage clamp was 32 V. The low temperature cycling tests started after 4575 cycles at 20 C. The cells were not capable of cycling. at low temperature since the charge acceptance at battery level was poor. There was a cell in the battery that showed too high an end-of-charge (EOC) voltage thereby limiting the ability to charge the rest of the cells in the battery. The battery has completed 6714 cycles. SAFT 12 Ah cells consisted of mixed-oxide (Co and NO positive, graphitic carbon negative, LiPF6 salt mixed with organic carbonate solvents. The battery voltage clamp was for 30.8 V. The low temperature cycling tests started after 4594 cycles at 20 C. A cell that showed low end of discharge (EOD) and EOC voltages and three other cells that showed higher EOC voltages limited the charge acceptance at the selected voltage limit during charge. The cells were capable of cycling at 10 C and 0 C but the charge voltage limit had to be increased to 34.3 V (4.3 V per cell). The low temperature cycling may have induced poor chargeability since the voltage had to be increased to achieve the required charge input. The battery has completed 6226 cycles. MSA 10 Ah cells consisted of Co oxide positive, graphitic carbon negative, LiPF6 salt mixed with organic carbonate solvents. The battery voltage clamp was 30.8 V. The low temperature cycling tests were started after 2182 cycles at 20 C. The cells were capable of cycling at 10 C and 0 C. Like SAFT, the voltage limit on charge had to be increased to 36 V (4.5 V per cell). There was a cell (cell S/N 13) in the battery that showed poor performance features such as low EOD voltage and high EOC voltage. The battery has completed 3441 cycles. A reconditioning procedure that consisted of C15 charge to a taper current of C/100 and C/20 discharge improved the voltage behavior of SAFT and MSA cells with no significant effect on YTP cells. We have demonstrated that the charge operation with VT clamp at battery rather than at cell level is feasible for onboard Li-Ion battery operation.

Rao, Gopalakrishna M.↗
NASA NTRS2008

LiGa(OTf)(sub 4) as an Electrolyte Salt for Li-Ion Cells

Lithium tetrakis(trifluoromethane sulfo - nato)gallate [abbreviated "LiGa(OTf)4" (wherein "OTf" signifies trifluoro - methanesulfonate)] has been found to be promising as an electrolyte salt for incorporation into both liquid and polymer electrolytes in both rechargeable and non-rechargeable lithium-ion electrochemical cells. This and other ingredients have been investigated in continuing research oriented toward im proving the performances of rechargeable lithium-ion electrochemical cells, especially at low temperatures. This research at earlier stages, and the underlying physical and chemical principles, were reported in numerous previous NASA Tech Briefs articles. As described in more detail in those articles, lithiumion cells most commonly contain nonaqueous electrolyte solutions consisting of lithium hexafluorophosphate (LiPF6) dissolved in mixtures of cyclic and linear alkyl carbonates, including ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC). Although such LiPF6-based electrolyte solutions are generally highly ionically conductive and electrochemically stable, as needed for good cell performance, there is interest in identifying alternate lithium electrolyte salts that, relative to LiPF6, are more resilient at high temperature and are less expensive. Experiments have been performed on LiGa(OTf)4 as well as on several other candidate lithium salts in pursuit of this interest. As part of these experiments, LiGa(OTf)4 was synthesized by the reaction of Ga(OTf)3 with an equimolar portion of LiOTf in a solvent consisting of anhydrous acetonitrile. Evaporation of the solvent yielded LiGa(OTf)4 as a colorless crystalline solid. The LiGa(OTf)4 and the other salts were incorporated into solutions with PC and DMC. The resulting electrolyte solutions exhibited reasonably high ionic conductivities over a relatively wide temperature range down to 40 C (see figure). In cyclic voltammetry measurements, LiGa(OTf)4 and the other salts exhibited acceptably high electrochemical stability over the relatively wide potential window of 0 to 5 V versus Li+/Li. 13C nuclear-magneticresonance measurements yielded results that suggested that in comparison with the other candidate salts, LiGa(OTf)4 exhibits less ion pairing. Planned further development will include optimization of the salt and solvent contents of such electrolyte solutions and incorporation of LiGa(OTf)4 into gel and solid-state polymer electrolytes. Of the salts, LiGa(OTf)4 is expected to be especially desirable for incorporation into lithium polymer electrolytes, wherein decreased ion pairing is advantageous and the large delocalized anions can exert a plasticizing effect.

Reddy, V. Prakash↗
NASA NTRS2010

Improved Low-Temperature Performance of Li-Ion Cells Using New Electrolytes

As part of the continuing efforts to develop advanced electrolytes to improve the performance of lithium-ion cells, especially at low temperatures, a number of electrolyte formulations have been developed that result in improved low-temperature performance (down to 60 C) of 26650 A123Systems commercial lithium-ion cells. The cell type/design, in which the new technology has been demonstrated, has found wide application in the commercial sector (i.e., these cells are currently being used in commercial portable power tools). In addition, the technology is actively being considered for hybrid electric vehicle (HEV) and electric vehicle (EV) applications. In current work, a number of low-temperature electrolytes have been developed based on advances involving lithium hexafluorophosphate-based solutions in carbonate and carbonate + ester solvent blends, which have been further optimized in the context of the technology and targeted applications. The approaches employed, which include the use of ternary mixtures of carbonates, the use of ester co-solvents [e.g., methyl butyrate (MB)], and optimized lithium salt concentrations (e.g., LiPF6), were compared with the commercial baseline electrolyte, as well as an electrolyte being actively considered for DoE HEV applications and previously developed by a commercial enterprise, namely LiPF6 in ethylene carbonate (EC) + ethyl methyl carbonate (EMC)(30:70%).

Smart, Marshall C.↗
NASA NTRS2010

Lithium-Ion Electrolytes Containing Phosphorous-Based, Flame-Retardant Additives

Future NASA missions aimed at exploring Mars, the Moon, and the outer planets require rechargeable batteries that can operate over a wide temperature range (-60 to +60 C) to satisfy the requirements of various applications. In addition, many of these applications will require improved safety, due to their use by humans. Currently, the state-of-the-art lithium-ion (Li-ion) system has been demonstrated to operate over a wide range of temperatures (-40 to +40 C); however, abuse conditions can often lead to cell rupture and fire. The nature of the electrolyte can greatly affect the propensity of the cell/battery to catch fire, given the flammability of the organic solvents used within. Li-ion electrolytes have been developed that contain a flame-retardant additive in conjunction with fluorinated co-solvents to provide a safe system with a wide operating temperature range. Previous work incorporated fluorinated esters into multi-component electrolyte formulations, which were demonstrated to cover a temperature range from 60 to +60 C. This work was described in Fluoroester Co-Solvents for Low-Temperature Li+ Cells (NPO-44626), NASA Tech Briefs, Vol. 33, No. 9 (September 2009), p. 37; and Optimized Li-Ion Electrolytes Con tain ing Fluorinated Ester Co-Solvents (NPO-45824), NASA Tech Briefs, Vol. 34, No. 3 (March 2010), p. 48. Other previous work improved the safety characteristics of the electrolytes by adding flame-retardant additives such as triphenyl phosphate (TPhPh), tri-butyl phosphate (TBuPh), triethyl phosphate (TEtPh), and bis(2,2,2-trifluoroethyl) methyl phosphonate (TFMPo). The current work involves further investigation of other types of flame-retardant additives, including tris(2,2,2-trifluoroethyl) phosphate, tris(2,2,2-trifluoroethyl) phosphite, triphenylphosphite, diethyl ethylphosphonate, and diethyl phenylphosphonate added to an electrolyte composition intended for wide operating temperatures. In general, many of the formulations investigated in this study displayed good performance over a wide temperature range, good cycle life characteristics, and are expected to have improved safety characteristics, such as low flammability. Of the electrolytes studied, 1.0 M LiPF6 in EC+EMC+DEP (20:75:5 v/v %) and 1.0 M LiPF6 in EC+EMC+DPP (20:75:5 v/v %) displayed the best operation at low temperatures, whereas the electrolyte containing triphenylphosphite displayed the best cycle life performance compared to the baseline solution. It is anticipated that further improvements can be made to the life characteristics with the incorporation of a SET promoters (such as VC, vinylene carbonate), which will likely inhibit the decomposition of the flame-retardant additives.

Smart, Marshall C.↗
NASA NTRS2011

Li-Ion Cells Employing Electrolytes With Methyl Propionate and Ethyl Butyrate Co-Solvents

Future NASA missions aimed at exploring Mars and the outer planets require rechargeable batteries that can operate at low temperatures to satisfy the requirements of such applications as landers, rovers, and penetrators. A number of terrestrial applications, such as hybrid electric vehicles (HEVs) and electric vehicles (EVs) also require energy storage devices that can operate over a wide temperature range (i.e., -40 to +70 C), while still providing high power capability and long life. Currently, the state-of-the-art lithium-ion system has been demonstrated to operate over a wide range of temperatures (-30 to +40 C); however, the rate capability at the lower temperatures is very poor. These limitations at very low temperatures are due to poor electrolyte conductivity, poor lithium intercalation kinetics over the electrode surface layers, and poor ionic diffusion in the electrode bulk. Two wide-operating-temperature-range electrolytes have been developed based on advances involving lithium hexafluorophosphate-based solutions in carbonate and carbonate + ester solvent blends, which have been further optimized in the context of the technology and targeted applications. The approaches employed include further optimization of electrolytes containing methyl propionate (MP) and ethyl butyrate (EB), which are effective co-solvents, to widen the operating temperature range beyond the baseline systems. Attention was focused on further optimizing ester-based electrolyte formulations that have exhibited the best performance at temperatures ranging from -60 to +60 C, with an emphasis upon improving the rate capability at -20 to -40 C. This was accomplished by increasing electrolyte salt concentration to 1.20M and increasing the ester content to 60 percent by volume to increase the ionic conductivity at low temperatures. Two JPL-developed electrolytes 1.20M LiPF6 in EC+EMC+MP (20:20:60 v/v %) and 1.20M LiPF6 in EC+EMC+EB (20:20:60 v/v %) operate effectively over a wide temperature range in MCMB-LiNiCoAlO2 and Li4Ti5O12-LiNi-CoAlO2 prototype cells. These electrolytes have enabled high rate performance at low temperature (i.e., up to 2.0C rates at -50 C and 5.0C rates at -40 C), and good cycling performance over a wide temperature range (i.e., from -40 to +70 C). Current efforts are focused upon improving the high temperature resilience of the methyl propionatebased system through the use of electrolyte additives, which are envisioned to improve the nature of the solid electrolyte interphase (SEI) layers.

Smart, Marshall C.↗
NASA NTRS2012

Wide Operating Temperature Range Electrolytes for High Voltage and High Specific Energy Li-Ion Cells

A number of electrolyte formulations that have been designed to operate over a wide temperature range have been investigated in conjunction with layered-layered metal oxide cathode materials developed at Argonne. In this study, we have evaluated a number of electrolytes in Li-ion cells consisting of Conoco Phillips A12 graphite anodes and Toda HE5050 Li(1.2)Ni(0.15)Co(0.10)Mn(0.55)O2 cathodes. The electrolytes studied consisted of LiPF6 in carbonate-based electrolytes that contain ester co-solvents with various solid electrolyte interphase (SEI) promoting additives, many of which have been demonstrated to perform well in 4V systems. More specifically, we have investigated the performance of a number of methyl butyrate (MB) containing electrolytes (i.e., LiPF6 in ethylene carbonate (EC) + ethyl methyl carbonate (EMC) + MB (20:20:60 v/v %) that contain various additives, including vinylene carbonate, lithium oxalate, and lithium bis(oxalato)borate (LiBOB). When these systems were evaluated at various rates at low temperatures, the methyl butyrate-based electrolytes resulted in improved rate capability compared to cells with all carbonate-based formulations. It was also ascertained that the slow cathode kinetics govern the generally poor rate capability at low temperature in contrast to traditionally used LiNi(0.80)Co(0.15)Al(0.05)O2-based systems, rather than being influenced strongly by the electrolyte type.

Li-ion Battery↗
NASA NTRS1988

Electrochemical stability of LiMF6 (M = P, As, Sb) in tetrahydrofuran and sulfolane

The electrochemical stability of LiSbF6 and LiPF6 in aprotic organic solvents has been investigated. Electrochemical studies, conductivity measurements, and open-circuit stability tests were conducted on LiSbF6 in tetrahydrofuran and sulfolane. Cyclic voltammetric studies of SbF6(-) were compared with those of AsF6(-) and PF6(-) anions. Sb(V) was reduced to Sb(III), and then to Sb(0). AsF6(-) was reduced to AsF3, while no reduction of PF6(-) was observed. The reduction products of AsF6(-) and SbF6(-) passivated the glassy carbon electrode, presumably due to LiF precipitation. Peak potentials were observed to shift in the positive direction as a function of concentration. This was accounted for on the basis of a follow-up chemical reaction.

Nanjundiah, C.↗
NASA NTRS1998

Development of High Conductivity Lithium-Ion Electrolytes for Low Temperature Cell Applications

NASA has continued interest in developing power sources which are capable of operating at low temperatures (-20 C and below) to enable future missions, such as the Mars Rover and Lander. Thus, under a program sponsored by the Mars Exploration Program, we have been involved in developing Li-ion batteries with improved low temperature performance. To accomplish this task, the focus of the research has been upon the development of advanced electrolyte systems with improved low temperature properties. This had led to the identification of a carbonate-based electrolyte, consisting of 1.0 M LiPF6 in EC + DEC + DMC (33:33:34), which has been shown to have excellent performance at -20 C in Li-ion AA-size prototype cells. Other groups are also actively engaged in developing electrolytes which can result in improved low temperature performance of Li-ion cells, including Polystor, Yardney, and Covalent. In addition to developing cells capable of operation at -20 C, there is continued interest in systems which can successfully operate at even lower temperatures (less than -30 C) and at high discharge rates (greater than C/2). Thus, we are currently focusing upon developing advanced electrolytes which are highly conductive at low temperatures and will result in cells capable of operation at -40 C. One approach to improve the low temperature conductivity of ethylene carbonate-based electrolytes involves adding co-solvents which will decrease the viscosity and extend the liquid range. Candidate solvent additives include formates, acetates, cyclic and aliphatic ethers, lactones, as well as other carbonates. Using this approach, we have prepared a number of electrolytes which contain methyl formate (MF), methyl acetate (MA), ethyl acetate (EA), ethyl proprionate (EP), and 1,2-dimethoxyethane (DME), some of which have been characterized and reported. Other groups have also reported electrolytes based on mixtures of carbonates and acetates. In the present study, electrolytes which have been identified to have good low temperature conductivity and stability were incorporated into lithium-graphite cells for evaluation. Using various electrochemical methods, including ac impedence and DC micropolarization techniques, the film formation characteristics of graphite electrodes in contact with various lectrolyte formulations was investigated.

Smart, M. C.↗
NASA NTRS2002

Improved low temperature performance of lithium ion cells with quaternary carbonate-based electrolytes

In order to enable future missions involving the exploration of the surface of Mars with Landers and Rovers, NASA desires long life, high energy density rechargeable batteries which can operate well at very low temperature (down to 40(deg)C). Lithium-ion technology has been identified as being the most promising chemistry, due to high gravimetric and volumetric energy densities, as well as, long life characteristics. However, the state-of-art (SOA) technology is not sufficient to meet the needs of many applications that require excellent low temperature capabilities. To further improve this technology, work at JF'L has been focused upon developing electrolytes that result in lithium-ion cells with wider temperature ranges of operation. These efforts have led to the identification of a number of ternary and quaternary, all carbonate-based electrolytes that have been demonstrated to result in improved low temperature performance in experimental three-electrode MCMB carbon/LiNio.sCoo.zOz cells. A number of electrochemical characterization techniques were performed on these cells (i.e., Tafel polarization measurements, linear polarization measurements, and electrochemical impedance spectroscopy (EIS)) to further enhance our understanding of the performance limitations at low temperature. The most promising electrolyte formulations, namely 1 .O M LiPF6EC+DEC+DMC+EMC (1 : 1: 1 :2 v/v) and 1 .O M LiPF6 EC+DEC+DMC+EMC (1 : 1 : 1 :3 v/v), were incorporated into SAFT prototype DD-size (9 Ahr) lithium- cells for evaluation. A number of electrical tests were performed on these cells, including rate characterization as a function of temperature, cycle life characterization at different temperatures, as well as, many mission specific characterization test to determine their viability to enable future missions to Mars. Excellent performance was observed with the prototype DD-size cells over a wide temperature range (-50 to 4OoC), with high specific energy being delivered at very low temperatures (i.e, over 95 WHrKg being delivered at 40(deg)C using a C/10 discharge rate).

Li-ion low temperature electrolytes↗
NASA NTRS2007

Hazards, Safety and Design Considerations for Commercial Lithium-ion Cells and Batteries

This viewgraph presentation reviews the features of the Lithium-ion batteries, particularly in reference to the hazards and safety of the battery. Some of the characteristics of the Lithium-ion cell are: Highest Energy Density of Rechargeable Battery Chemistries, No metallic lithium, Leading edge technology, Contains flammable electrolyte, Charge cut-off voltage is critical (overcharge can result in fire), Open circuit voltage higher than metallic lithium anode types with similar organic electrolytes. Intercalation is a process that places small ions in crystal lattice. Small ions (such as lithium, sodium, and the other alkali metals) can fit in the interstitial spaces in a graphite lattice. These metallic ions can go farther and force the graphitic planes apart to fit two, three, or more layers of metallic ions between the carbon sheets. Other features of the battery/cell are: The graphite is conductive, Very high energy density compared to NiMH or NiCd, Corrosion of aluminum occurs very quickly in the presence of air and electrolyte due to the formation of HF from LiPF6 and HF is highly corrosive. Slides showing the Intercalation/Deintercalation and the chemical reactions are shown along with the typical charge/discharge for a cylindrical cell. There are several graphs that review the hazards of the cells.

Jeevarajan, Judith↗
NASA NTRS2008

DMAC and NMP as Electrolyte Additives for Li-Ion Cells

Dimethyl acetamide (DMAC) and N-methyl pyrrolidinone (NMP) have been found to be useful as high-temperature-resilience-enhancing additives to a baseline electrolyte used in rechargeable lithium-ion electrochemical cells. The baseline electrolyte, which was previously formulated to improve low-temperature performance, comprises LiPF6 dissolved at a concentration of 1.0 M in a mixture comprising equal volume proportions of ethylene carbonate, diethyl carbonate, and dimethyl carbonate. This and other electrolytes comprising lithium salts dissolved in mixtures of esters (including alkyl carbonates) have been studied in continuing research directed toward extending the lower limits of operating temperatures and, more recently, enhancing the high-temperature resilience of such cells. This research at earlier stages, and the underlying physical and chemical principles, were reported in numerous previous NASA Tech Briefs articles. Although these electrolytes provide excellent performance at low temperatures (typically as low as -40 C), when the affected Li-ion cells are subjected to high temperatures during storage and cycling, there occur irreversible losses of capacity accompanied by power fade and deterioration of low-temperature performance. The term "high-temperature resilience" signifies, loosely, the ability of a cell to resist such deterioration, retaining as much as possible of its initial charge/discharge capacity during operation or during storage in the fully charged condition at high temperature. For the purposes of the present development, a temperature is considered to be high if it equals or exceeds the upper limit (typically, 30 C) of the operating-temperature range for which the cells in question are generally designed.

Smart, Marshall↗
NASA NTRS2008

Optimized Carbonate and Ester-Based Li-Ion Electrolytes

To maintain high conductivity in low temperatures, electrolyte co-solvents have been designed to have a high dielectric constant, low viscosity, adequate coordination behavior, and appropriate liquid ranges and salt solubilities. Electrolytes that contain ester-based co-solvents in large proportion (greater than 50 percent) and ethylene carbonate (EC) in small proportion (less than 20 percent) improve low-temperature performance in MCMB carbon-LiNiCoO2 lithium-ion cells. These co-solvents have been demonstrated to enhance performance, especially at temperatures down to 70 C. Low-viscosity, ester-based co-solvents were incorporated into multi-component electrolytes of the following composition: 1.0 M LiPF6 in ethylene carbonate (EC) + ethyl methyl carbonate (EMC) + X (1:1:8 volume percent) [where X = methyl butyrate (MB), ethyl butyrate EB, methyl propionate (MP), or ethyl valerate (EV)]. These electrolyte formulations result in improved low-temperature performance of lithium-ion cells, with dramatic results at temperatures below 40 C.

Smart, Marshall↗
NASA NTRS2009

Fluoroester Co-Solvents for Low-Temperature Li+ Cells

Electrolytes comprising LiPF6 dissolved in alkyl carbonate/fluoroester mixtures have been found to afford improved low-temperature performance and greater high-temperature resilience in rechargeable lithium-ion electrochemical cells. These and other electrolytes comprising lithium salts dissolved mixtures of esters have been studied in continuing research directed toward extending the lower limit of operating temperatures of such cells. This research at earlier stages, and the underlying physical and chemical principles, were reported in numerous previous NASA Tech Briefs articles. The purpose of the present focus on high-temperature resilience in addition to low-temperature performance is to address issues posed by the flammability of the esters and, at temperatures near the upper end (about 55 C) of their intended operating temperature range, by their high chemical reactivity. As used here, high-temperature resilience signifies, loosely, a desired combination of low flammability of an electrolyte mixture and the ability of a cell that contains the mixture to sustain a relatively small loss of reversible charge/discharge capacity during storage in the fully charged condition at high temperature. The selection of fluoroesters for study as candidate electrolyte solvent components to increase high-temperature resilience was prompted in part by the observation that like other halogenated compounds, fluoroesters have low flammability. The fluoroesters investigated in this study include trifluoroethyl butyrate (TFEB), ethyl trifluoroacetate (ETFA), trifluoroethyl acetate (TFEA), and methyl pentafluoropropionate (MPFP). Solvent mixtures were prepared by mixing these fluoroesters with two other esters: ethylene carbonate (EC) and ethyl methyl carbonate (EMC).

Smart, Marshall↗
NASA NTRS2006

4-Vinyl-1,3-Dioxolane-2-One as an Additive for Li-Ion Cells

Electrolyte additive 4-vinyl-1,3-dioxolane-2-one has been found to be promising for rechargeable lithium-ion electrochemical cells. This and other additives, along with advanced electrolytes comprising solutions of LiPF6 in various mixtures of carbonate solvents, have been investigated in a continuing effort to improve the performances of rechargeable lithium-ion electrochemical cells, especially at low temperatures. In contrast to work by other researchers who have investigated the use of this additive to improve the high-temperature resilience of Li-ion cells, the current work involves the incorporation of 4-vinyl-1,3-dioxolane-2-one into quaternary carbonate electrolyte mixtures, previously optimized for low-temperature applications, resulting in improved low-temperature performance. The benefit afforded by 4-vinyl-1,3- dioxolane-2-one can be better understood in the light of relevant information from a number of prior NASA Tech Briefs articles about electrolytes and additives for such cells. To recapitulate: The loss of performance with decreasing temperature is attributable largely to a decrease of ionic conductivity and the increase in viscosity of the electrolyte. What is needed to extend the lower limit of operating temperature is a stable electrolyte solution with relatively small lowtemperature viscosity, a large electric permittivity, adequate coordination behavior, and appropriate ranges of solubilities of liquid and salt constituents. Whether the anode is made of graphitic or non-graphitic carbon, a film on the surface of the anode acts as a solid/electrolyte interface (SEI), the nature of which is critical to low-temperature performance. Desirably, the surface film should exert a chemically protective (passivating) effect on both the anode and the electrolyte, yet should remain conductive to lithium ions to facilitate intercalation and de-intercalation of the ions into and out of the carbon during discharging and charging, respectively. The additives investigated previously include alkyl pyrocarbonates. Those additives help to improve low-temperature performances by giving rise to the formation of SEIs having desired properties. The formation of the SEIs is believed to be facilitated by products (e.g., CO2) of the decomposition of these additives. These decomposition products are believed to react to form Li2CO3-based films on the carbon electrodes. The present additive, 4-vinyl-1,3-dioxolane-2-one, also helps to improve lowtemperature performance by contributing to the formation of SEIs having desired properties, but probably in a different manner: It is believed that, as part of the decomposition process, the compound polymerizes on the surfaces of carbon electrodes.

Smart, Marshall↗
NASA NTRS2005

Ester-Based Electrolytes for Low-Temperature Li-Ion Cells

Electrolytes comprising LiPF6 dissolved at a concentration of 1.0 M in five different solvent mixtures of alkyl carbonates have been found to afford improved performance in rechargeable lithium-ion electrochemical cells at temperatures as low as -70 C. These and other electrolytes have been investigated in continuing research directed toward extending the lower limit of practical operating temperatures of Li-ion cells. This research at earlier stages, and the underlying physical and chemical principles, were reported in numerous previous NASA Tech Briefs articles, the most recent being Low-EC-Content Electrolytes for Low-Temperature Li-Ion Cells (NPO-30226), NASA Tech Briefs, Vol. 27, No. 1 (January 2003), page 46. The ingredients of the present solvent mixtures are ethylene carbonate (EC), ethyl methyl carbonate (EMC), methyl butyrate (MB), methyl propionate (MP), ethyl propionate (EP), ethyl butyrate (EB), and ethyl valerate (EV). In terms of volume proportions of these ingredients, the present solvent mixtures are 1EC + 1EMC + 8MB, 1EC + 1EMC + 8EB, 1EC + 1EMC + 8MP, 1EC + 1EMC + 8EV, and 1EC + 9EMC. These electrolytes were placed in Liion cells containing carbon anodes and LiNi0.8Co0.2O2 cathodes, and the low-temperature electrical performances of the cells were measured. The cells containing the MB and MP mixtures performed best.

Smart, Marshall↗