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Lithium Ion Battery Accelerated Life Testing Report

November 3, 2011
This document was prepared by Advanced Energy. Primary Investigator / Author Shawn Fitzpatrick, P.E. Staci Haggis Contributors Matt Murray Cal Foshee Organizations Progress Energy Duke Energy NCEMC

North Carolina Advanced Energy Corporation is a registered engineering firm with the North Carolina Board of Examiners for Engineers and Surveyors. This report was prepared under the responsible charge of the Professional Engineer whose seal appears below.

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Table of Contents
Executive Summary .............................................................................................................................3 Acronyms and Abbreviations ................................................................................................................4 Introduction ..........................................................................................................................................5 Battery Pretesting .................................................................................................................................6 Accelerating Factors.............................................................................................................................7 ALT Test Procedures ...........................................................................................................................7 End of Test Criteria ..............................................................................................................................9 Post Test Care .....................................................................................................................................9 Additional Battery Characteristic Tests.................................................................................................9 Potential Issues with ALT ................................................................................................................... 10 Conclusions........................................................................................................................................ 11

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Executive Summary
Many organizations, such as electric utilities and national laboratories, are looking for a method of obtaining used lithium-ion batteries for testing with secondary life applications. One method is to accelerate the aging process of the batteries through accelerated life testing. This process aims to age new lithium-ion batteries to a used state in order to make secondary life application experiments as reliable as possible. Based on research conducted for this report, Advanced Energy has found the industry standard for accelerated life testing seems to be trending toward performing a series of dynamic stress tests on the batteries at elevated temperatures. This test method will degrade the batteries in a similar fashion to normal battery use, but at a faster-than-normal rate. Periodic reference performance tests should also be performed on the test batteries in order to keep an accurate account of the state of health of the batteries. Once the batteries have been degraded to 70 to 80 percent of their original power or capacity, end of test conditions have been reached and the batteries are at the appropriate state of health for secondary life application testing.

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Acronyms and Abbreviations

ALT: Accelerated Life Testing BOL: Beginning of Life DST: Dynamic Stress Test EOT: End of Test FreedomCAR: Freedom Cooperative Automotive Research INL: Idaho National Laboratory Li-ion: Lithium-Ion NREL: National Renewable Energy Laboratory RPT: Reference Performance Testing SOC: State of Charge USABC: United States Advanced Battery Consortium

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Introduction
With the coming widespread arrival of plug-in electric vehicles, many organizations, such as electric utilities and national laboratories, are considering how electric vehicle batteries may be used in secondary life applications. The lithium-ion (Li-ion) batteries widely used in electric vehicles are insufficient for vehicle use after they have degraded to 70 to 80 percent of their original capacity1; however, the remaining storage capacity could still be useful in other applications. Such applications include using the batteries as backup power supplies for data centers or for communities prone to power outages. They could also be used to help stabilize the electric grid by tempering fluctuations in supply and demand, and as storage for electricity generated from renewable energy sources, such as solar panels and wind farms2. The United States government has even shown interest in exploring secondary life applications for batteries by awarding a $1.3 million Department of Energy grant in April 2011 to the National Renewable Energy Laboratory (NREL) to study the feasibility, durability and value of Li-ion batteries for secondary life applications3. In addition, organizations such as the Electric Power Research Institute, University of California Davis, University of California Berkeley, Rochester Institute of Technology and more are all working on secondary battery life activities. One challenge associated with secondary battery life applications is how to accurately test those applications. Mass-market electric vehicles are just now entering the marketplace and with expected electric vehicle battery lifetimes of eight to 10 years, organizations performing secondary life studies cannot wait for these batteries to age naturally. To address this problem, these organizations are looking to accelerate battery aging through a process called accelerated life testing (ALT). The purpose of this report is to define a method for accelerating the life of a Li-ion battery to the point where it is no longer fit for vehicular use but still has second-life utility, emulating the battery state at the end of an electric vehicle battery life. The batteries can then be used to conduct research into their secondary life applications. In ALT, it is important that batteries be aged in a way that minimizes time and monetary resources without causing damage or degradation to the battery that would not naturally occur during normal battery life.

Neubauer, Jeremy and Ahmad Pesaran. PHEV/EV Li-Ion Battery Second-Use Project [PowerPoint slides]. April 2010. Retrieved from National Renewable Energy Laboratory website: <http://www.nrel.gov/vehiclesandfuels/energystorage/pdfs/48018.pdf> 2 Bullis, Kevin. A Second Life for Old Vehicle Batteries. Technology Review (published by MIT). September 23, 2010. Retrieved from: <http://www.technologyreview.com/energy/26331/page1/> 3 NREL Newsroom. NREL Team Investigates Secondary Uses for Electric Drive Vehicle Batteries. NREL News Release NR-1411. April 5, 2011. Retrieved from: <http://www.nrel.gov/news/press/2011/959.html> Lithium Ion Battery Accelerated Life Testing Report | 5

Battery Pretesting
Pretesting of batteries prior to ALT is an important step. Pretesting allows testers to gauge the current condition of the battery and allows them to determine appropriate test conditions so the data gathered will be accurate and reliable. Batteries should first be inspected for signs of damage. Early detection of faulty batteries or cells will save time and resources over the duration of the ALT process that would otherwise be wasted if failure conditions are not identified prior to the start of aging. It is important to characterize the starting condition of the battery that will undergo ALT prior to testing. The starting condition is the power or capacity of the battery before any testing is performed. The primary method to initially characterize Li-ion batteries is beginning of life (BOL) performance testing. The results from the BOL test will not only give an indication of the current state of the battery being tested, but will also be used to compare later performance test results to track the progress of the ALT and to ensure that the testing is not harming the battery. The main objectives of BOL performance testing are to: 1. 2. Verify the initial capabilities of the Li-ion battery being tested. Determine appropriate test parameters based on the battery under test and the application for which it is being tested. Idaho National Laboratory (INL) has developed a test manual for BOL testing entitled Battery Technology Life Verification Test Manual4. The test manual outlines procedures for two characterization tests that should be performed on each battery cell that will undergo ALT. Procedures for the characterization tests are in Section 3.1 of the manual, and are: 1. 2. Verification of the rated capacity. This test characterizes the discharge capacity of the battery. Pulse power verification. This test verifies pulse power capabilities at the minimum and maximum state of charge (SOC). The initial verification of the pulse power capabilities of all the battery cells should be done using the Minimum Pulse Power Characterization test procedure.

4 Haskins, Harold, et al. Battery Technology Life Verification Test Manual. Idaho National Laboratory Report No. INEEL/EXT-04-01986. February 2005.

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Accelerating Factors
Accelerating factors are the stress factors used to artificially age a Li-ion battery. These factors will preferably be easy to control and will not degrade the battery in an unnatural way. INL, along with Freedom Cooperative Automotive Research (FreedomCAR), named four accelerating factors in their report on ALT of Li-ion batteries. These are: Temperature; SOC; Rate of discharge energy throughput ; and Discharge and regenerative pulse power levels5 .

INL and FreedomCAR suggest elevating temperature as the best method for artificially accelerating Li-ion battery aging because it is a relatively cheap and controllable mechanism5. However, there are potential issues with performing ALT via elevating temperature, which are discussed further in the Potential Issues with ALT section of this report. Note there are some groups who have performed ALT on Li-ion batteries using SOC as the primary accelerator. Although SOC can work as an accelerator, it is the most stressful acceleration factor for Li-ion batteries, and therefore the likelihood of unnaturally degrading the batteries is higher6.

ALT Test Procedures

Although ALT for the purposes of evaluating secondary battery life uses is a relatively new field, there are a number of organizations that have attempted to perform ALT on Li-ion batteries. At the time of publication, an official standard for ALT on Li-ion batteries does not exist; therefore, it is up to each of these individual testing agencies to determine their test methods. Many of the studies and experiments that have been performed using ALT on Liion batteries have been performed in order to gauge the full life of the batteries and to help battery manufacturers learn where potential flaws exist in an attempt to improve the batteries and extend life. This testing can be quite extensive and tests are often performed that are not necessary for the scope of this report.

Christophersen, Jon P. et al. Advanced Technology Development Program for Lithium-Ion Batteries: Gen 2 Performance Evaluation Final Report. Idaho National Laboratory Report No. INL/EXT-05-00913. July 2006. 6 Christophersen, Jon P. et al. Advanced Technology Development Program for Lithium-Ion Batteries: Gen 2 Performance Evaluation Report Revision 4. Idaho National Laboratory Report No. INL/EXT-06-11488. July 2006. Lithium Ion Battery Accelerated Life Testing Report | 7

NREL senior engineers, Jeremy Neubauer and Ahmad Pesaran, have initiated research on secondary life applications of Li-ion batteries. In order to obtain aged batteries for their experiments, they typically perform ALT on new batteries. When interviewed by Advanced Energy about their test procedure, Neubauer and Pesaran suggested the United States Advanced Battery Consortium (USABC) Electric Vehicle Battery Test Procedures Manual7. This manual is not battery chemistry-specific and can be used for most types of batteries. Advanced Energy determined this is likely the most appropriate test procedure for the goal of this report. The objective of the USABCs ALT procedure is to accelerate failure modes and degradation within the battery. The test procedures focus on what is termed overstress testing. Overstress testing involves determining the forms of normal stress a Li-ion battery will be exposed to during typical deployment as a vehicle battery. These stresses are then applied at an elevated level to degrade the battery at a faster rate. The goal of each individual test should be to simulate actual battery use, with the exception of the accelerating stress factor. It is important that the batteries subjected to this testing are monitored to ensure they do not degrade in an atypical manner. Continuous electrical cycling, also referred to as time compression, is a required component of the USABCs ALT procedures. Another key component of the test procedure is dynamic stress testing (DST). The purpose of DST is to simulate the cycles batteries will experience in an electric vehicle. INL also recommends conducting reference performance testing (RPT) at regularly set intervals during ALT8. The purpose of RPT is to monitor the cumulative battery deterioration in order to keep an accurate account of the batterys aging. Each RPT should be performed with the procedures discussed in the Battery Pretesting section of this report. For more detailed information on accelerated battery aging, the USABC also recommends consulting the reference book Accelerated Testing9.

Hunt, Gary et al. Electric Vehicle Battery Test Procedures Manual, Revision 2. United States Advanced Battery Consortium. January 1996. 8 Haskins, Harold, et al. Battery Technology Life Verification Test Manual. Idaho National Laboratory Report No. INEEL/EXT-0401986. February 2005. 9 Nelson, Wayne. Accelerated Testing. John Wiley and Sons, 1990.
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End of Test Criteria

End of Test (EOT) criteria signal the termination of the ALT sequence. EOT criteria can be based on many monitored test parameters and are generally selected based on the goals of the test. For the purpose of this report, EOT criteria are defined as parameters that signify the Li-ion batteries under test have been aged and conditioned for second life application testing. An NREL engineer interviewed by Advanced Energy suggested that setting an EOT criterion for the battery to be at 70 to 80 percent of its original power or capacity is reasonable, as this is the condition the majority of used electric vehicle batteries are expected to be in when they are acquired for second use applications.

Post Test Care

An important step using Li-ion batteries in secondary life application testing is post test care. Post test care consists of storing and monitoring the batteries for later use. For example, if there will be a lag period of more than two to three days between the conclusion of ALT and the start of secondary life application testing, it is important to ensure that additional unnatural battery degradation does not occur. If the batteries will be stored for several months before beginning secondary life application testing, it is possible they will not be in the same condition as when ALT concluded. Therefore, it is recommended that additional RPT be conducted before beginning secondary life application testing.

Additional Battery Characteristic Tests

Additional battery tests that are not part of ALT procedures, but may be of interest to a testing agency, are thermal performance testing and stand testing. A thermal performance test will demonstrate how a batterys performance will vary in excessively high or low temperatures. A stand test will demonstrate how much of the batterys charge and capacity will be lost over time if it is not used. These test procedures are outlined in the USABC Electric Vehicle Battery Test Procedures Manual10.

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Hunt, Gary et al. Electric Vehicle Battery Test Procedures Manual, Revision 2. United States Advanced Battery Consortium. January 1996. Lithium Ion Battery Accelerated Life Testing Report | 9

Potential Issues with ALT

In Advanced Energys interviews with subject matter experts in the field of ALT, some potential issues with Li-ion battery ALT were raised. In 2010, NASA researched Li-ion battery ALT using elevated temperatures to accelerate battery aging. They found that Li-ion batteries experience higher capacity and power fades at elevated temperatures and that the relationships are non-linear. NASAs Jet Propulsion Laboratory experts concluded that ALT for Li-ion batteries using elevated temperature aging is unreliable and unusable because of the complexity of the battery and the many different factors that affect battery age. They also concluded that real time performance testing is the most valid test method11. Potential problems NASA identified with using a temperature above 50C as an accelerator include: Increased capacity fade rates with cycling Irreversible capacity loss associated with high temperature storage Increased cell self-discharge rates Poor low temperature performance capabilities Increased cell impedance Increased gas generation and pressure build-up within the cell High voltage operation and storage resulting from increased cell degradation and performance loss Advanced Energy also contacted Progressive Technologies Inc., a Li-ion battery manufacturer, and was advised that because Li-ion batteries are complicated in their design, it would be difficult to assume the condition of a used battery from an electric vehicle, and that to execute a performance test on the battery would be prohibitively expensive.

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Christo, Jim. Problems with the Interim Li Ion Rechargeable Batteries Type Approval Procedure [PowerPoint slides]. NASA Search and Rescue Mission Office, May 20, 2010. Retrieved from: <http://www.sarsat.noaa.gov/BMW%202010_files/Proposed%20changes%20to%20the%20Interim%20Li%20Ion%20rechargeable%20 rev%201_JC.pdf> Lithium Ion Battery Accelerated Life Testing Report | 10

Conclusions
As electric vehicles become more prevalent, many organizations are looking at how electric vehicle batteries can be used in secondary life applications. In order to test the viability of these applications, it is necessary to have batteries at the end of their electric vehicle lifespan on which to experiment. However, with an expected life of eight to 10 years, these organizations cannot wait for used electric vehicle batteries and are instead looking to ALT to artificially age Li-ion batteries. This report aimed to define a method for ALT of Li-ion batteries for secondary life application testing. Upon researching Li-ion battery ALT, it is recommended to use the USABCs test procedures for ALT with elevated temperature as the accelerating factor, and to use a DST profile to mimic actual battery cycling conditions. Using elevated temperature as the accelerating factor is beneficial because it is both relatively inexpensive and controllable. If monitored correctly, it should not degrade the battery in an unnatural manner. However, there are some issues to consider when using elevated temperatures as an accelerating factor: If not monitored correctly, the batteries subjected to this acceleration can become damaged and unusable in further testing. NASAs Jet Propulsion Laboratory does not believe it is an accurate way to accelerate battery life. If the elevated temperature used in testing is too high (above 65C) there could be an increased chance of battery thermal runaway. Despite these potential issues, ALT using elevated temperature is the test method currently in use by NREL, who is also looking into second use applications of Li-ion batteries. While performing ALT at elevated temperatures, it is important to regularly conduct RPT to accurately gauge the condition of the batteries being accelerated. Regular performance checks can help testing agencies manage potential issues by having an accurate account of the battery state throughout the ALT process.

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