This white paper describes the program vision, objectives, and R&D targets in 5 to 10 years for the Department of Energy (DOE) Office of Electricity (OE) Microgrid R&D Program. The vision is to facilitate the nation’s transitions to (1) a more resilient and reliable, (2) more decarbonized electricity infrastructure, in which (3) microgrids have a reduced cost to implement. This strategy is developed in the context that the United States’ electricity delivery system is becoming more distributed in nature. The electricity generation capacity in 10 years may be 30-50% distributed energy assets.
Energy storage systems with Li-ion batteries are increasingly deployed to maintain a robust and resilient grid and facilitate the integration of renewable energy resources. However, appropriate selection of cells for different applications is difficult due to limited public data comparing the most commonly used off-the-shelf Li-ion chemistries under the same operating conditions. This article details a multi-year cycling study of commercial LiFePO4 (LFP), LiNixCoyAl1-x-yO2 (NCA), and LiNixMnyCo1-x-yO2 (NMC) cells, varying the discharge rate, depth of discharge (DOD), and environment temperature. The capacity and discharge energy retention, as well as the round-trip efficiency, were compared. Even when operated within manufacturer specifications, the range of cycling conditions had a profound effect on cell degradation, with time to reach 80% capacity varying by thousands of hours and cycle counts among cells of each chemistry. The degradation of cells in this study was compared to that of similar cells in previous studies to identify universal trends and to provide a standard deviation for performance. All cycling files have been made publicly available at batteryarchive.org, a recently developed repository for visualization and comparison of battery data, to facilitate future experimental and modeling efforts.
This paper takes a critical look at the materials aspects of thermal runaway of lithium-ion batteries and correlates contributions from individual cell components to thermal runaway trends. An accelerating rate calorimeter (ARC) was used to evaluate commercial lithium-ion cells based on LiCoO2 (LCO), LiFePO4 (LFP), and LiNixCoyAl1-x-yO2 (NCA) at various states of charge (SOC). Cells were disassembled and the component properties were evaluated by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and temperature-resolved X-ray diffraction (TR-XRD). The whole cell thermal runaway onset temperature decreases and peak heating rate increases with SOC due to cathode destabilization. LCO and NCA cathodes are metastable, with NCA cells exhibiting the highest thermal runaway rates. By contrast, the LFP cathode is stable to >500 °C, even when charged. For anodes, the decomposition and whole cell self-heating onset temperature is generally independent of SOC. DSC exotherm onset temperatures of the anodes were generally within 10 °C of the onset of self-heating in whole cell ARC. However, onset temperatures of the cathodes were typically observed above the ARC onset of whole cell runaway. This systematic evaluation of component to whole cell degradation provides a scientific basis for future thermal modeling and design of safer cells.
Lithium-ion battery safety is prerequisite for applications from consumer electronics to grid energy storage. Cell and component-level calorimetry studies are central to safety evaluations. Qualitative empirical comparisons have been indispensable in understanding decomposition behavior. More systematic calorimetry studies along with more comprehensive measurements and reporting can lead to more quantitative mechanistic understanding. This mechanistic understanding can facilitate improved designs and predictions for scenarios that are difficult to access experimentally, such as system-level failures. Recommendations are made to improve usability of calorimetry results in mechanistic understanding. From our perspective, this path leads to a more mature science of battery safety.
Lithium ion batteries have a well documented tendency to fail energetically under various abuse conditions. These conditions frequently result in decomposition of the electrochemical components within the battery resulting in gas generation and increased internal pressure which can lead to an explosive case rupture. The 18650 format cell incorporates a vent mechanism located within a crimped cap to relieve pressure and mitigate the risk of case rupture. Cell venting, however, introduces additional safety concerns associated with the flow of flammable gases and liquid electrolyte into the environment. Experiments to quantify key parameters are performed to elucidate the external dynamics of battery venting. A first experiment measures the vent burst pressure. Burst vent caps are then tested with a second experimental fixture to measure vent opening area and discharge coefficient during choked-flow venting, which occurs during battery failure. Vent opening area and discharge coefficient are calculated from stagnation temperature, stagnation pressure, and static pressure measurements along with compressible-isentropic flow equations and conservation of mass. Commercially-sourced vent caps are used with repeated tests run to quantify repeatability and variability. Validation experiments confirmed accuracy of opening area and discharge coefficient measurement. Moreover, trials conducted on vent caps from two sources demonstrate the potential for variation between manufacturers.
Here, this Review Article focuses on the highly versatile and effective method of radiolysis for the synthesis of nanoparticles (NPs). In particular, the formation of bimetallic and alloyed nanoparticles (or nanoalloys), including both known super alloys and novel alloy NP compositions, is described. This Review Article discloses the synthesis techniques that rely on ionizing radiation sources to create metallic NPs. Then, alloy NPs formed from combinations of transition metals and noble metals with varied structures are described. Some of the advantages of radiolysis including exquisite control over the size, monodispersity, and alloying structure of NPs are discussed. Additionally, methodologies that facilitate the synthesis or deposition of NPs onto a range of supports under inert environments are described. Finally, applications of metallic NPs formed by radiolysis are summarized.
Battery energy storage systems (BESS) are a critical technology for integrating high penetration renewable power on an intelligent electrical grid. As limited energy restricts the steady-state operational state-of-charge (SoC) of storage systems, SoC forecasting models are used to determine feasible charge and discharge schedules that supply grid services. Smart grid controllers use SoC forecasts to optimize BESS schedules to make grid operation more efficient and resilient. This study presents three advances in BESS state-of-charge forecasting. First, two forecasting models are reformulated to be conducive to parameter optimization. Second, a new method for selecting optimal parameter values based on operational data is presented. Last, a new framework for quantifying model accuracy is developed that enables a comparison between models, systems, and parameter selection methods. The accuracies achieved by both models, on two example battery systems, with each method of parameter selection are then compared in detail. The results of this analysis suggest variation in the suitability of these models for different battery types and applications. Finally, the proposed model formulations, optimization methods, and accuracy assessment framework can be used to improve the accuracy of SoC forecasts enabling better control over BESS charge/discharge schedules.
The goal of the DOE OE ESS Safety Roadmap1 is to foster confidence in the safety and reliability of energy storage systems. There are three interrelated objectives to support the realization of that goal: research, codes and standards and communication/coordination. The objective focused on codes and standards is To apply research and development to support efforts that are focused on ensuring that codes and standards are available to enable the safe implementation of energy storage systems in a comprehensive, non-discriminatory and science-based manner. The following activities are intended to support that objective and realization of the goal: a. Review and assess codes and standards which affect the design, installation, and operation of ESS systems. b. Identify gaps in knowledge that require research and analysis that can serve as a basis for criteria in those codes and standards. c. Identify areas in codes and standards that are potentially in need of revision or enhancement and can benefit from activities conducted under research and development. d. Develop input for new or revisions to existing codes and standards through individual stakeholders, facilitated task forces, or through laboratory staff supporting these efforts. The purpose of this document is to support the above activities by providing information on current and upcoming efforts being conducted by U.S. standards developing organizations (SDOs) and other entities that are focused on energy storage system safety.