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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.↗

DOE OSTI2025

Toward Stable, High‐Energy, Partially Disordered Mn‐Rich Spinel Cathodes by Revealing and Mitigating Surface Degradation

Mn-rich cathodes balance performance and sustainability but suffer from limited cyclability due to Mn dissolution and cathode-to-anode crosstalk. The Jahn-Teller (J-T) effect of Mn 3+ is often linked to the above phenomena, such as in spinel LiMn 2 O 4 . However, in typical voltage ranges, significant Mn 3+ only appears near the end of discharge, highlighting the need to reassess its role in driving Mn dissolution, structural degradation, and battery performance. Here, the spinel cathode's degree of disorder is tailored to expand the Mn redox range, enabling segmentation into J-T active and less active voltage ranges. Cycling at segmented voltage windows reveals surface degradation mechanisms with and without the major J-T effect. Despite a stronger J-T effect below 3.6 V vs. Li/Li + , Mn dissolution is less significant than above 3.6 V. Expanding the cycling window to 2.0–4.3 V causes severe degradation as the J-T active range induces a tetragonal phase and Mn 2+ -rich surface, driving Mn dissolution and consuming Li-ion inventory in full cells. Reducing electrolyte acidity minimizes Mn 3+ disproportionation, enabling a stable dopant-free Mn-only cathode with a 250 mAh g −1 specific capacity. These findings demonstrate that full cells using Mn-rich cathodes have the potential to avoid the notorious crosstalk problem through electrolyte engineering.

25 ENERGY STORAGE↗

DOE OSTI2020

Imaging the Phase Transformation in Single Particles of Lithium Titanate Anode for Lithium-ion Batteries

Lithium uptake and release in lithium titanate (LTO) anode materials during a discharge and charge cycle is one of the fundamental processes of a Lithium-ion battery (LIB), still not fully understood at the microscopic level.During discharge cycle, LTO undergoes a phase transformation between Li 4 Ti 5 O 12 and Li 7 Ti 5 O 12 states within a cubic crystal lattice. To reveal the details of the microscopic mechanism,it is necessary to track the sequence of phase transformation sat different discharge/charge states under operating conditions.Here we use in-situ Bragg Coherent Diffraction Imaging (BCDI) and in-situ X-ray diffraction (XRD) experiments to examine the lithium insertion-induced materials phase transformation within a single LTO particle anda bulk battery analogue,respectively. BCDI analysis from (111) Bragg peak, shows the two-phase transformation manifesting as a distinct image phase modulation within a single LTO nanoparticle occurring in the middle of the discharge region then subsiding towards the end of the discharge cycle. We observe the biggest phase variation at the two-phase stage,indicating the formation of phase domains of 200 nm in size during the discharge process. Additionally, we also observe a lattice contraction of >0.2% in a single LTO nanoparticle at the (400) Bragg peak measurement, larger than that in the corresponding bulk material. Our observation of this phase transformation at a single particle level has implications for the understanding of the microscopic/mesoscale picture of the phase transformation in anode and cathode LIBs materials.

25 ENERGY STORAGE↗

DOE OSTI2024

CRADA Number NFE-21-08827 with DayLyte, Inc. (CRADA Final Report)

DayLyte Batteries is developing an aqueous Sodium-Air battery made with abundant materials while being half to a third the weight of Li-ion to power electric aircraft, electric vehicles and provide renewable energy on demand. To make this battery practical, DayLyte is developing a thin film ceramic Nasicon solid electrolyte amenable to rapid scaleup as well as a protective coating that will protect the solid electrolyte from 50wt% NaOH during the battery’s end-of-discharge while still allowing Na-ions to pass back and forth. If the thin film solid electrolyte and stable coating can be developed it will open the world to step change in battery performance all while not sacrificing the environment on the way. The project was designed to first focus on making and characterizing the Nasicon membrane followed by measuring its electrochemical performance, then assembling a full cell, optimizing its NaOH stability and then optimize the overall prototype design. Over the past two years, we have significantly improved the Nasicon film uniformity, demonstrated protective ligands that are stable in 50wt% NaOH by measuring no mass change with a quartz crystal microbalance, tested different heating methods like tube furnace and rapid heating and developed glassy carbon coatings on the current collector to prevent Nasicon-current collector alloying. We have found that getting film uniformity as measured by electrochemical impedance spectroscopy (EIS) is difficult because of different factors like surface roughness, deposition uniformity and heat treatment time and uniformity. The glassy carbon coating should significantly reduce the surface roughness and by tuning the coating conditions the film deposition uniformity improves and using an automated heating method should lead to much improved film uniformity.

25 ENERGY STORAGE↗

NASA NTRS1976

Ignition Transients of Large Segmented Solid Rocket Boosters

A model is described which provides a means for analyzing the complexities of ignition transients and pressure peaks of large, high performance, segmented solid rocket boosters. The method accounts for: (1) temporal and spatial development of the flow field set up by the head end igniter discharge, (2) ignition and flame spreading coupled to chamber flow, (3) the steep velocity, pressure, and temperature gradients that occur during the early phases of ignition, and (4) the interactions that produce ignition spikes (i.e., compression of chamber gases during pressurization, erosive burning, and mass added effect of igniter discharge). The technique differs from earlier models in that the flow interactions between the slots and main chamber are accounted for, and the original computer program for monolithic motors is improved. The procedures were used to predict the ignition transients of the current design for the space shuttle booster.

Caveny, L. H.↗

NASA NTRS1977

Evaluation Program for Secondary Spacecraft Cells: Synchronous Orbit Testing of Sealed Nickel Cadmium Cells

Performance data concerning sealed nickel-cadmium cells operating under a synchronous orbit regime are presented. A space satellite maintaining a position over a fixed point on earth as the earth rotates on its axis and revolves about the sun was simulated. Results include: (1) exposure to synchronous orbit testing at a temperature of 40 C yields less than 6 years of life; (2) performance at -20 C presents a low capacity problem; (3) the capacity check, performed at the middle of each show period, provides a temporary red reconditioning effect on the cells in that the end-of-discharge voltages are higher, for approximately 7 to 10 days, following the capacity check than they were 7 to 10 days prior to the capacity check; (4) all the test packs at -20 C and 40 C have either failed or were discontinued because of low capacity; and (5) test packs at temperatures of 0 C and 10 C have delivered the best capacity during life and packs tested at 20 C showed better life capability than packs tested at -20 C and 40 C.

Harkness, J. D.↗

NASA NTRS1984

Charge Control Investigation of Rechargeable Lithium Cells

An ambient temperature rechargeable Li-TiS2 cell was cycled under conditions which simulate aerospace applications. A novel charge/discharge state-of-charge control scheme was used, together with tapered current charging, to overcome deleterious effects associated with end-of-charge and end-of-discharge voltages. The study indicates that Li-TiS2 cells hold promise for eventual synchronous satellite-type applications. Problem areas associated with performance degradation and reconditioning effects are identified.

Otzinger, B.↗

NASA NTRS1985

Geosynchronous Performance of a Lithium-titanium Disulfide Battery

An ambient temperature rechargeable Lithium-Titanium disulfide (Li-TiS2) five cell battery has completed the first orbital year of accelerated synchronous orbit testing. A novel charge/discharge, state of charge (SOC) control scheme is utilized, together with taper current charge backup to overcome deleterious effects associated with high end of charge and low end of discharge voltages. It is indicated that 10 orbital years of simulated synchronous operation may be achieved. Preliminary findings associated with cell matching and battery performance are identified.

Otzinger, B.↗

NASA NTRS1987

Earth Radiation Budget Satellite (ERBS) orbiting profiles and Ni-Cd use

The Earth Radiation Budget Satellite (ERBS) is one of the more recently launched satellites of the Goddard Space Flight Center. The flight data of the two 50 Ah NASA standard batteries that are being flown on the ERBS are presented. Trend characteristics of the batteries were collected over a period of two years. The parameters that were trended are: the battery end-of-discharge voltage, time in peak power track, and time in constant current mode. All were plotted versus mission elapsed time. The slopes exhibited by the trended parameters indicate no adverse trends that would signify any appreciable degradation in the batteries.

Enciso, Marlon L.↗

NASA NTRS1991

Raman spectral observation of a new phase observed in nickel electrodes cycled to failure

A ‘new phase’ is reported in nickel electrodes from Ni/H2 boilerplate cells which were cycled to failure in electrolyte of variable KOH concentration (21–36%). Raman spectra clearly show the presence of this phase, and these spectra have been used to estimate the amounts present on these electrodes. Ten of twelve electrodes examined contain this new phase. The cycle life at higher KOH concentrations (31 and 36%) was greatly reduced, and nickel electrodes from these cells exhibited extensive amounts of this new phase. The presence of this ‘new phase’ correlates with cell failure defined by low end of discharge voltages. It is proposed that the lowered capacity and failure of these electrodes was caused by loss of active mass and formation of a phase with reduced electrochemical activity. These results indicate that formation of this new phase is accelerated at higher KOH concentrations.

Patricia L Loyselle↗

NASA NTRS1994

Space Station Freedom NiH2 cell testing program

Testing for the Space Station Freedom Nickel Hydrogen Cell Test Program began in 1990 at Crave Division, Naval Surface Warfare Center. The program has included receipt inspection, random vibration, acceptance, characterization, and life cycle testing of Ni-H2 cells in accordance with the NASA LeRC Interagency Order C-31001-J. A total of 400 Ni-H2 cells have been received at NAVSURFWARCENDIV Crane from three separate manufacturers; Yardney Technical Products (Yardney), Eagle Picher Industries (Eagle Picher), and Gates Energy Products (Gates). Of those, 308 cells distributed among 39 packs have undergone life cycle testing under a test regime simulating low earth orbit conditions. As of 30 September 1993, there are 252 cells assembled into 32 packs still on life cycle test. Since the beginning of the program, failed cells have been detected in all phases of testing. The failures include the following; seven 65 AmpHr and 81 AmpHr Yardney cells were found to be leaking KOH on receipt, one 65 AmpHr Eagle Picher cell failed the acceptance test, one 65 AmpHr Gates cell failed during the characterization test, and six 65 AmpHr Gates cells failed the random vibration test. Of the 39 life cycle packs, testing on seven packs, 56 cells, has been suspended because of low end of discharge voltages. All of the failed life cycle packs were cycled at 60% depth of discharge.

Moore, Bruce↗

NASA NTRS1995

Preventing Overcharge And Overdischarge Of Lithium Cells

Secondary lithium cells operating at ambient temperature protected against overcharge and overdischarge by use of cathode additives acting as sources and sinks of electroactive chemical species, which is lithium. Additive in cathode limits excursion of voltage of cell during both overcharge and overdischarge. In addition to protecting cell, also serves as part of state-of-charge indicator: attainment of greater or lesser limiting voltage indicates end of charge or end of discharge, respectively. Concept applied to Li/TiS2 system, and also applicable to such other lithium systems as Li/MoS2, Li/NbSe3, and Li/V2O5.

Huang, Chen-Kuo↗

NASA NTRS1999

Status of SPV/CPV Testing

This presentation reviews the status test of Single Pressure Vessel (SPV)/Common Pressure Vessel (CPV) being conducted by the Navy. Slides review the design and tests by NASA, and the Airforce of CPV's. There are 5 different CPV models of CPV's which have been tested or are currently being tested for NASA and the Air Force. The batteries, tests, and results are presented. Graphs show the life cycle voltage, the pressure trend, the discharge/charge profile and the pressure profile for the batteries tested. Descriptions of those CPV batteries are given for those batteries which have been received but have not been tested. The development of the SPV is briefly described, followed by design specification for two packs from NASA and the Air Force. The acceptance test criteria are reviewed, followed by a review of the life cycle test conditions. The trend plots of voltage vs. cycle is given for the two packs. The end of charge, and the end of discharge voltages plots are shown. Plots showing the pressure and recharge vs. cycle are shown. Plots also show the voltage profiles. These plots are shown for both batteries using the SPV design submitted by NASA and the Air Force.

Brown, Harry↗

NASA NTRS2006

An Update on the Performance of Li-Ion Rechargeable Batteries on Mars Rovers

NASA's Mars Rovers, Spirit and Opportunity have been exploring the surface of Mars for the last thirty months, far exceeding the primary mission life of three months, performing astounding geological studies to examine the habitability of Mars. Such an extended mission life may be attributed to impressive performances of several subsystems, including power subsystem components, i.e., solar array and batteries. The novelty and challenge for this mission in terms of energy storage is the use of lithium-ion batteries, for the first time in a major NASA mission, for keeping the rover electronics warm, and supporting nighttime experimentation and communications. The use of Li-ion batteries has considerably enhanced or even enabled these rovers, by providing greater mass and volume allocations for the payload and wider range of operating temperatures for the power subsystem and thus reduced thermal management. After about 800 days of exploration, there is only marginal change in the end-of discharge (EOD) voltages of the batteries or in their capacities, as estimated from in-flight voltage data and corroborated by ground testing of prototype batteries. Enabled by such impressive durability from the Li-ion batteries, both from a cycling and calendar life stand point, these rovers are poised to extend their exploration well beyond 1000 sols, though other components have started showing signs of decay. In this paper, we will update the performance characteristics of these batteries on both Spirit and Opportunity.

low temperatures↗

NASA NTRS2013

Advanced Methods for Determining Prediction Uncertainty in Model-Based Prognostics with Application to Planetary Rovers

Prognostics is centered on predicting the time of and time until adverse events in components, subsystems, and systems. It typically involves both a state estimation phase, in which the current health state of a system is identified, and a prediction phase, in which the state is projected forward in time. Since prognostics is mainly a prediction problem, prognostic approaches cannot avoid uncertainty, which arises due to several sources. Prognostics algorithms must both characterize this uncertainty and incorporate it into the predictions so that informed decisions can be made about the system. In this paper, we describe three methods to solve these problems, including Monte Carlo-, unscented transform-, and first-order reliability-based methods. Using a planetary rover as a case study, we demonstrate and compare the different methods in simulation for battery end-of-discharge prediction.

prognosis↗

NASA NTRS2015

Towards Characterizing the Variability in the Loading Demands of an Unmanned Aerial Vehicle

This paper presents a computational methodology to characterize and quantify the variability in the power demands during the take-off of an unmanned aerial vehicle (UAV). A lithium-ion battery-based power system is used to power the unmanned aerial vehicle, and the capabilities of the unmanned aerial vehicle are driven by the amount of charge in this battery. In order to design the power system, it is necessary to analyze the power and charge requirements of the UAV. This paper focuses on the take-off segment, and aims to quantify the amount of charge that is required for this particular segment. Sparse data is available through different flight tests and this data is used to analyze the flight profile and the charge requirement during take-off. The amount of charge required for take-off depends on several factors that are not only variable but cannot be controlled in reality, and hence, the entire flight profile and the corresponding charge requirement are variable in nature. The information available through flight tests is converted into multi-dimensional sparse data and a new method is developed in this paper for variability characterization using multi-dimensional sparse data. This analysis is useful for prognostics and health management where it is necessary to anticipate future charge requirements in order to compute the end-of-discharge of the battery, and hence, the remaining useful life of the power system.

unmanned aerial vehicle↗

NASA NTRS2019

String Midpoint Monitoring for Li-Ion Batteries

The paper introduces the midpoint monitoring method for detecting cell voltage imbalance in a series string of 8 electrochemical cells. Monte Carlo analysis is performed for normal cell End of Discharge open and closed circuit voltage behavior to assess the extent to which derived guard band voltage limits will detect over discharged cells, provide false positive indication, or fail to detect over discharged cells. Forward work is proposed to refine the battery monitoring method for operational use in 28V lithium ion batteries.

Russell, S.↗

NASA NTRS2020

Prognostics for Systems Health Management - Model and Hybrid Based Approaches. Where are We Heading?

To facilitate and solve the prediction problem, awareness of the current state and health of the system is key, since it is necessary to perform condition-based system health predictions. To accurately predict the future state of any system, it is required to possess knowledge of its current health state and future operational conditional. In case of next generation electric aircrafts, computing remaining flying time is safety-critical, since an aircraft that runs out of power (battery charge) while in the air will eventually lose control leading to catastrophe. In order to tackle and solve the prediction problem, it is essential to have awareness of the current health state of the system, especially since it is necessary to perform condition-based predictions. To be able to predict the future state of the system, it is also required to possess knowledge of the current and future operational conditions and flight profiles for accurate estimation of end-of-discharge (EOD) for the batteries. Similar framework can be implemented to other complex systems and subsystems. Our research approach is to develop a system level health monitoring safety indicator which runs estimation and prediction algorithms to estimate remaining useful life predictions at system, subsystem swell as component levels. Given models of the current and future system behavior, a general approach of model-based prognostics is discussed as a solution to the prediction problem and further for decision making. Data driven prognostics approaches have been equally used with good results in the past, where respective approaches have their own challenges to tackle. This limits their applicability to complex real-world domains: (a) high complexity or incompleteness of physics-based models and (b) limited representativeness of the training dataset for data-driven models. With the advent of internet of things for data collection and increased use of ML algorithms, hybrid approaches are the next avenue to reduce the challenges and achieve better results. An hybrid framework for fusing information from physics-based performance models along with deep learning algorithms for prognostics of complex safety critical systems is presented. In this framework, we use physics-based performance models to infer unobservable model parameters related to the system's components health solving a calibration problem.

Prognostics↗