Concha M. Reid

Glenn Research Center, Cleveland, Ohio

Advanced Materials and Component Development 

for Lithium-Ion Cells for NASA Missions

NASA/TM—2012-217689

September 2012
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Concha M. Reid

Glenn Research Center, Cleveland, Ohio

Advanced Materials and Component Development 

for Lithium-Ion Cells for NASA Missions

NASA/TM—2012-217689

September 2012

National Aeronautics and

Space Administration

Glenn Research Center

Cleveland, Ohio 44135

Prepared for the

Energy Tech 2012

sponsored by the Institute of Electrical and Electronics Engineers

Cleveland, Ohio, May 29–31, 2012
Acknowledgments

All of the work presented in this paper was funded by the National Aeronautics and Space Administration, Enabling Technology 

Development and Demonstration Program High Effi ciency Space Power Systems Project (formerly the Exploration Technology 

Development Program, Energy Storage Project). Numerous people participated in the synthesis of materials, generation of data, and 

interpretation of results. Contributions from Richard Baldwin, William Bennett and Brianne Scheidegger, NASA Glenn Research 

Center; Judith Jeevarajan, NASA Johnson Space Center; and William West, Marshall Smart, Kumar Bugga, and Jessica Soler, 

NASA Jet Propulsion Lab are gratefully acknowledged. Contributors via efforts funded through NASA Research Announcement 

NNC08ZP022N include the following: Nader Hagh and Ganesh Skandan; NEI Corporation; Arumugam Manthiram, University 

of Texas at Austin; Christopher Lang, Physical Sciences, Inc.; Justin Golightly, Lockheed Martin Space Systems Company; 

Gleb Yushin, Georgia Institute of Technology; Igor Luzinov, Clemson University; Boris Ravdel, Yardney Technical Products; 

Brett Lucht, University of Rhode Island, and support staff at these companies and universities.

Available from

NASA Center for Aerospace Information

7115 Standard Drive

Hanover, MD 21076–1320

National Technical Information Service

5301 Shawnee Road

Alexandria, VA 22312

Available electronically at http://www.sti.nasa.gov

Trade names and trademarks are used in this report for identifi cation 

only. Their usage does not constitute an offi cial endorsement, 

either expressed or implied, by the National Aeronautics and 

Space Administration.

Level of Review: This material has been technically reviewed by technical management. 

This report contains preliminary fi ndings, 

subject to revision as analysis proceeds.
NASA/TM—2012-217689 1 

Advanced Materials and Component Development for Lithium-Ion 

Cells for NASA Missions 

Concha M. Reid 

National Aeronautics and Space Administration 

Glenn Research Center 

Cleveland, Ohio 44135 

Abstract 

Human missions to Near Earth Objects, such as asteroids, planets, moons, liberation points, and 

orbiting structures, will require safe, high specific energy, high energy density batteries to provide new or 

extended capabilities than are possible with today’s state-of-the-art aerospace batteries. The Enabling 

Technology Development and Demonstration Program, High Efficiency Space Power Systems Project 

battery development effort at the National Aeronautics and Space Administration (NASA) is continuing 

advanced lithium-ion cell development efforts begun under the Exploration Technology Development 

Program Energy Storage Project. Advanced, high-performing materials are required to provide improved 

performance at the component-level that contributes to performance at the integrated cell level in order to 

meet the performance goals for NASA’s High Energy and Ultra High Energy cells. NASA’s overall 

approach to advanced cell development and interim progress on materials performance for the High 

Energy and Ultra High Energy cells after approximately 1 year of development has been summarized in a 

previous paper. This paper will provide an update on these materials through the completion of 2 years of 

development. The progress of materials development, remaining challenges, and an outlook for the future 

of these materials in near term cell products will be discussed. 

1.0 Introduction 

NASA is developing High Energy (HE) and Ultra High Energy (UHE) advanced lithium-ion (Li-ion) 

cells with the goals of attaining specific energies of 180 watt-hours per kilogram (Wh/kg) and 260 Wh/kg, 

respectively, when measured at C/10 and 0 °C, in cells that are inherently safe. The HE cell goals are 

being addressed through the development of advanced cathode components, flame retardant electrolytes, 

safety devices, and optimized cell designs. The newly developed components will be combined with a 

commercial graphite anode from Mitsubishi Chemical Corporation (MPG-111) that can achieve a specific 

capacity of 330 milliampere-hours per gram (mAh/g) at C/10 and 0 °C and a commercial battery-grade 

separator to comprise an HE cell design. The UHE cell goals will be achieved through the development of 

advanced anodes and combining them with the cathode, safety device, and separator utilized in the HE 

cell. A flame retardant electrolyte specially formulated to be compatible with the advanced anode will be 

used in the UHE cell design. Background information on the cell chemistries, their components, and cell 

designs are documented in prior papers by Reid and Bennett and by Reid (Refs. 1 and 2). 

A table of Key Performance Parameters (KPPs) is shown in Table 1. These KPPs establish target 

criteria for the performance of cell components and Li-ion cells, and project the expected performance of 

a battery-level system comprised of the cells under development. State-of-the art (SOA) is based on 

aerospace design Li-ion cells and batteries developed by Yardney Technical Products for operation on the 

Mars Exploration Rovers (MER). 
NASA/TM—2012-217689 2 

TABLE 1.—KEY PERFORMANCE PARAMETERS 

Performance 

parameter 

State of the Art Current value Threshold valuea

 Goala

No fire or 

flame 

Instrumentation/controllers 

used to prevent unsafe 

conditions. There is no nonflammable electrolyte in SOA 

Preliminary results indicate 

a small reduction in 

performance using safer 

electrolytes and cathode 

coatings 

Tolerant to electrical and 

thermal abuse such as 

over-temperature, overcharge, reversal, and short 

circuits with no fire or 

thermal runawayc

Tolerant to electrical and 

thermal abuse such as 

over-temperature, overcharge, reversal, and short 

circuits with no fire or 

thermal runawayc

Battery-level 

specific 

energy,b

(Wh/kg) 

90 Wh/kg at C/10 and 30 °C 

83 Wh/kg at C/10 and 0 °C 

(MER rovers) 

160 at C/10 and 30 °C (HE) 

170 at C/10 and 30 °C (UHE) 

80 Wh/kg at C/10 and 0 °C 

(predicted) 

135 Wh/kg at C/10 and 

0 °C “High-Energy” 

150 Wh/kg at C/10 and 

0 °C “Ultra-High Energy” 

150 Wh/kg at C/10 and 

0 °C “High-Energy” 

220 Wh/kg at C/10 and 

0 °C “Ultra-High Energy”

Cell-level 

specific 

energy, 

(Wh/kg) 

130 Wh/kg at C/10 and 30 °C 

118 Wh/kg at C/10 and 0 °C 

199 at C/10 and 23 °C (HE) 

213 at C/10 and 23 °C (UHE) 

100 Wh/kg at C/10 and 0 °C 

(predicted) 

165 Wh/kg at C/10 and 

0 °C “High-Energy” 

180 Wh/kg at C/10 and 

0 °C “Ultra-High Energy” 

180 Wh/kg at C/10 and 

0 °C “High-Energy” 

260 Wh/kg at C/10 and 

0 °C “Ultra-High Energy”

Cathode-level 

specific 

capacity, 

(mAh/g) 

180 mAh/g 252 mAh/g at C/10 and 25 °C 

190 mAh/g at C/10 and 0 °C 

260 mAh/g at C/10 and 

0 °C 

280 mAh/g at C/10 and 

0 °C 

Anode-level 

specific 

capacity, 

(mAh/g) 

280 mAh/g (MCMB) 330 at C/10 and 0 °C (HE) 

1200 mAh/g at C/10 and 0 °C 

for 10 cycles (UHE) 

600 mAh/g at C/10 and 

0 °C 

“Ultra-High Energy” 

1000 mAh/g at C/10 0 °C

“Ultra-High Energy” 

Battery-level 

energy density 

250 Wh/l n/a 270 Wh/l “High-Energy” 

360 Wh/l “Ultra-High” 

320 Wh/l “High-Energy” 

420 Wh/l “Ultra-High” 

Cell-level 

energy density 

320 Wh/l n/a 385 Wh/l “High-Energy” 

460 Wh/l “Ultra-High” 

390 Wh/l “High-Energy” 

530 Wh/l “Ultra-High” 

Operating 

temperature 

–20 to +40 °C 0 to +30 °C 0 to 30 °C 0 to 30 °C 

a

Assumes prismatic cell packaging for threshold values. Goal values include lightweight battery packaging. b

Battery values are assumed at 100% depth-of-discharge (DoD), discharged at C/10 to 3.0 volts/cell, and at 0 °C operating conditions. c

Over-temperature up to 110 °C; reversal 150% excess discharge at 1C; pass external and simulated internal short tests; overcharge 100% at 1C 

for Goal and 80% at C/5 for Threshold Value. 

NASA Research Announcement (NRA) contracts that were initiated specifically to develop 

components targeted for the HE and UHE cells have concluded after a two-year period of effort. 

Electroactive materials, electrodes, sample coupons, and electrolytes were delivered to NASA at intervals 

of 6, 11, 18, and 23 months (mo.) into their development and were independently assessed by NASA 

Glenn Research Center (GRC), Johnson Space Center (JSC), and/or Jet Propulsion Laboratory (JPL) 

according to standard procedures established for this development project. These materials will be 

referred to as 6, 11, 18, and 23 mo. deliverables/materials. The progression of the performance of the 

materials over the development timeframe will be discussed in this paper. Comparisons of the materials’ 

performance relative to the goal values will be discussed, parameters that are on target with the goal 

criteria will be highlighted, and areas where technical advancement is still required will be identified. 

Additionally, projected characteristics of cells incorporating these materials will be presented. 
NASA/TM—2012-217689 3 

2.0 High Energy Cell 

2.1 Cathodes

Advanced cathodes are critical to the development of high specific energy HE and UHE cells. 

Layered transition metal oxide materials containing lithium, nickel, manganese, and cobalt 

(Li[LiNMC]O2) are being developed with the goal to attain 280 mAh/g when discharged at C/10 and 0 °C 

to 3.0 volts (V). The cathode materials discussed in this paper were developed at the University of Texas 

at Austin (UTA) and at NEI Corporation (NEI). 

UTA’s focus has been to systematically investigate solid solutions of (1-z)[Li1/3Mn2/3]O2-zLi[Ni1-x-y

MnxCoy]O2 to identify and optimize lithium-rich, layered compositions that can meet the goals stated 

above. The composition Li[Li0.2Mn0.54Ni0.13Co0.13]O2 was targeted as the stoichiometry that could 

potentially offer the desired specific capacity. Improvement in irreversible capacity loss (ICL) (reduction 

of), discharge capacity, and rate capability were achieved through surface modifications (e.g., application 

of coatings) using solution-based processes and blending the base material with lithium-free insertion 

hosts (Ref. 3). NEI’s approach to cathode development has been the design and synthesis of twodimensional layered electrodes based on a composite of Li[Li1/3Mn2/3]O2 and Li[Mn1/3Ni1/3Co1/3]O2

(Ref. 4). 

UTA and NEI materials were independently assessed at NASA JPL using a standard set of test 

conditions in 2032-type coin cell half cells with a Li metal electrode, 1.0 molar (M) lithium 

hexafluorophoshate (LiPF6) in ethylene carbonate:diethyl carbonate:dimethyl carbonate (EC:DEC:DMC) 

electrolyte in a 1:1:1 ratio by volume (baseline electrolyte), and a 20 micron (μm) thick Tonen Setela 

(Toray Tonen) separator, unless otherwise noted. Cathode test procedures are given in Table 2. 

The performance against key metrics that are fundamental to the overall characterization of the 

cathodes has been exhibiting gradual improvement over the course of 2 years. The “best” values 

demonstrated for these parameters are compared to the goal values on the “spider plot” shown in Figure 1. 

Best values are defined as the highest value of the particular parameter achieved over the two-year 

development period. Hence, values are not necessarily for the same material. Table 3 quantitatively lists 

the best and goal values and the materials from which the best values were measured. In addition, it lists 

the values of all the parameters for the most recent deliverables from each developer. Values reported are 

for the average of four cells, with the exception of the UTA 11 mo. material, whose value is the average 

of two cells. The parameters shown include first cycle reversible capacity, specific capacity, temperature 

performance, tap density, rate capability, and cycle life. The following paragraphs describe the data for 

these parameters in more detail. 

TABLE 2.—CATHODE TEST PROCEDURES 

Test stage Test conditions 

Formation At 23 °C, charge at C/20 to 4.8 V, hold voltage, and allow current to taper to C/50. Rest for 

15 min. Discharge at C/20 to 2V. Perform for 5 cycles. 

20 °C Characterization At 20 °C, charge at C/10 to 4.8 V, hold voltage, and allow current to taper to C/50. Rest for 

15 min. Discharge at C/10 to 2V. Perform for 10 cycles. 

0 °C Characterization First charge is performed at 20 °C. All other charges are performed at 0 °C. Charge at C/10 to 

4.8 V, hold voltage, and allow current to taper to C/50. Rest for 15 min. Soak for a minimum 

of 2 hours after a temperature change. At 0 °C, discharge at C/10 to 2V. Perform for 10 cycles. 

30 °C Characterization Soak at 30 °C for a minimum of 2 hours after a temperature change. Charge at C/10 to 4.8 V, 

hold voltage, and allow current to taper to C/50. Rest for 15 min. Discharge at C/10 to 2V. 

Perform for 10 cycles. 
NASA/TM

First cycle 

Specific ca

Specific ca

RT capacit

Tap density

Rate capab

Projected c

initial ca

Projected c

initial ca

2.1.1 R

First-c

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cycled bet

%

The g

ideally be

of lithium

internal N

capacity o

M—2012-21768

TABL

Metric

reversible capac

apacity, RT, C/10

apacity, 0 °C, C/

ty retention at 0 

y (g/cc) 

bility at C/5 as co

cycle life for HE

apacity) 

cycle life for UH

apacity) 

Reversible Ca

cycle reversib

e capacity is e

tween 2.0 V a

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NASA measur

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89 

LE 3.—SUMMA

c

city (%) 

0 to 3V (mAh/g)

10 to 3V (mAh/g

°C (%) 

ompared to C/10

E (cycles to 80% 

HE (cycles to 80%

apacity 

ble capacity i

equivalent to (

and 4.8 V, wh

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 Changes to s

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Goal 

V

81 

) 311 

g) 280 

90 

>1.5 

0 (%) 95 

of 2000 

% of 250 

s measured on

(100 percent m

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ൈ 100, where c

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oxide, a stand

UTA Li[LiNM

synthesis tech

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ODE BEST VAL

Best

Value

87 UTA 18

238 UTA 11

135 UTA 11

72 UTA 23

>2.3 NEI and

uncoat

83 NEI 6 m

81 UTA 

81 UTA 

n the initial fo

minus the per

ICL is given b

charge = charge 

 81 percent, o

is based on ty

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MC]O2 mater

hniques and c

ALUES AND LA

t values 

Material 

8 and 23 mo. coa

 mo. uncoated

 mo. coated

3 mo. coated 

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ted

mo. uncoated

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ATEST VALUES

Values 

UTA 23 

coated

ated 87 

164 

126 

85 

mo. 2.02 

Not meas

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irst-cycle ICL

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the first cycle

 for the first c

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NEI 23

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65

191

130

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 mo. 

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NASA/TM—2012-217689 5 

improving the reversible capacity from the 50 to 75 percent values exhibited in early deliverables to 

NASA. 

2.1.2 Specific Capacity 

Specific capacity at 20 and 0 °C are plotted as a percentage of the specific capacity goals at C/10 and 

3.0 V and the respective temperature. Specific capacity at 20 °C is reported for the first cycle following 

formation. Discharge was continued to 2.0 V and values were measured and reported at 3.0 V. Studies 

performed internally at NASA JPL have shown that there is a slightly higher rate of capacity fade with 

certain Li[LiNMC]O2 materials when they are cycled between 4.7 and 2.0 V as opposed to between 4.7 

and 3.0 V. However, cycling to 2.0 V provides valuable information on the residual capacity remaining 

between 3.0 and 2.0 V. 

The best specific capacity measured at 20 °C and C/10 from 4.7 to 3.0 V is 238 mAh/g, which is 

77 percent of the goal value of 311 mAh/g. Since project goals were established for 0 °C operation, the 

room temperature (RT) goal was derived from the 0 °C specific capacity goal, based on the desire to 

retain at least 90 percent of RT capacity when operating at 0 °C. In this paper, temperatures between 

20 and 23 °C are considered RT. 

Testing at 0 °C is performed after cycling ten times at 20 °C. Specific capacity at 0 °C is reported for 

the first discharge at 0 °C, after a charge at 20 °C. As with the 20 °C cycling, discharge was continued to 

2.0 V and values were measured and reported at 3.0 V. At 0 °C and C/10 from 4.7 to 3.0 V, 135 mAh/g 

was obtained, only 48 of the goal value of 280 mAh/g. Since capacity at 0 °C is measured on the 11th 

operational cycle (after 20 °C cycling), some capacity fade occurred prior to obtaining the measurement 

at 0 °C. Experimentally, an 18-24 mAh/g decrease was typically observed from the first 20 °C discharge 

to the tenth 20 °C discharge. If the specific capacity delivered at 0 °C is adjusted for the capacity loss due 

to earlier cycling, the value approaches 57 percent of the goal. 

2.1.3 Temperature Performance 

Temperature performance is measured as the percentage of RT capacity retained at 0 °C. Excessive 

capacity loss at lower temperatures can limit the practical design of a battery that must operate at those 

temperatures. In such a case, in order to supply enough operational capacity, a battery may need to be 

oversized to compensate for the decrease in delivered capacity at low temperatures. Alternately, thermal 

management must be designed in as part of the battery system to maintain the operating point at a warmer 

temperature. Either of these options may increase the mass of the battery system unless the battery load 

can be handled as part of a larger, integrated thermal management system, for example, as part of a 

vehicle’s thermal management system. 

Nonetheless, it is desirable to retain as much of the RT capacity when operating at 0 °C as possible. A 

goal of 90 percent was established for temperature performance based on what is reasonably practical 

given current SOA Li-ion cell performance. The specific capacity goals discussed in the previous section 

already take into account a 10 percent difference in temperature performance from 20 to 0 °C. Therefore, 

if 0 °C goals are met yet temperature performance is <90 percent, it is acceptable since in such a case the 

20 °C performance would exceed its goal. 

2.1.4 Tap Density 

Tap density (TD), a measure of how well powders are able to be packed closely together, is a key 

attribute to measure in the determination of a material’s suitability for the fabrication of cathodes from 

raw powders. To determine tap density, powders are placed in a graduated cylinder and taps are applied 

by automated equipment to compress the powder. The mass per unit volume is then measured on the 

compressed sample. The TD of the powders should ideally be > 1.5-1.6 grams per cubic centimeter (g/cc) 

for manufacturability of cathodes of practical thickness on production equipment at Saft America, 

NASA’s industrial partner for building HE and UHE cells. 
NASA/TM—2012-217689 6 

Low tap density also impedes a material’s ability to achieve high energy density, independently of 

production processes (Ref. 13). Materials that do not compress well contain more air between their 

particles, so they have high porosity when packed. These materials are unable to highly loaded (loading = 

capacity per unit area), since not enough material can occupy a unit area, resulting in low energy density. 

2.1.5 Rate Capability 

Rate capability is a measure of a material’s ability to charge and/or discharge at specified currents. 

Rate capability was not routinely measured on cathodes. Studies were performed on early materials (NEI 

6 mo.) to baseline the rate performance of this class of layered Li[LiNMC]O2 materials. There is no 

specific requirement for rate capability at C/5 as compared to C/10 for the HE and UHE cells. However, 

for practical operation in a cell, the cathode should retain a significant portion of the C/10 capacity when 

operating at C/5. A target of 95 percent of the C/10 performance was set for the C/5 performance. 

2.1.6 Cycle Life 

Cycle life is the amount of cycles a cell delivers under specified conditions. Cycle life can vary 

depending upon how an electrode/cell is utilized. For these materials, the cycle life goals specify that the 

cathode should deliver at least 250 cycles until the point that 80 percent of its initial capacity is reached. 

Cycle life assessments are only performed on materials that demonstrate acceptable characteristics in 

other areas, however, NASA has collected limited data on selected deliverables to baseline this 

performance. Eighty-one cycles to 80 percent of initial capacity were projected from 60 cycles of data 

collected on experimental coated materials tested in coin cell half cells at UTA. A constant per cycle 

decrease in ampere-hour capacity was used for this projection. 

Literature reports similar trends in capacity fade for this class of materials. Li et al. report 80 cycles to 

80 percent of first cycle capacity when cycling at C/5 at 20 °C between 4.8 and 2.5 V (Ref. 5). They show 

that a rapid decrease in capacity occurs within the first 30 cycles, then the rate of fade decreases 

substantially for 70 more cycles. This is similar to the effect seen in some UTA coated materials. Li et al. 

also observed that this rapid decrease in capacity during early cycling occurred independently of 

discharge rate. 

NEI also reports rapid fade in their “V2” materials (11 and 18 mo. deliverables) during early cycling 

before cycling stabilizes (Ref. 6). Hagh et al., attribute this phenomenon to an impedance rise rather than 

to intrinsic capacity loss. This suggests that if the impedance rise mechanism that occurs in early cycling 

can be overcome, less fade and better cycling stability can be obtained, which will extend cycle life. 

2.1.7 Discussion 

While NMC materials have potential to offer much higher specific capacity than traditional Li-ion 

cathodes such as lithium cobalt oxide (LiCoO2), the Li[Li1/3Mn2/3]O2 component of the NMC material has 

insulating properties that impacts its electronic conductivity. Additionally, a thick SEI layer is formed at 

the higher operating voltages, leading to slow kinetics and impacting the rate of lithium ion diffusion and 

charge transfer. These factors all lead to lower rate capability in the NMC cathode than is typically seen 

with other Li-ion chemistries (Ref. 14). Temperature performance is also much worse with NMC 

materials than with other lithium-ion chemistries, attributable to slow kinetics at low temperatures. 

Figure 2 and Figure 3 contain spider plots that show the progression of the material properties as 

measured by the parameters discussed above for 6, 11, 18, and 23 mo. materials from UTA and NEI. 

Values plotted in each graph pertain to a single material. Although clear progress in materials 

development has been demonstrated over the past 2 years, component performance has still not achieved 

the goals necessary to enable the performance targets for the HE and UHE cells. For cathodes, most 

notably, specific capacity and cycle life are well below necessary targets. Results for specific capacity 

versus cycle number for representative materials delivered from each company are shown in Figure 4. 

 
NASA/TM

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M—2012-21768

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M—2012-21768

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area than thei

hat it provides

ions (Refs. 7 a

ctrochemical 

at UTA and N

m required for

one material

niques, partic

rials exhibited

at NEI on the

ir lower TD c

s a larger elec

and 8). The lo

performance 

NEI to maxim

r manufactura

is critical for

cle morpholog

d lower speci

e higher TD m

counterparts. 

ctrode-electro

ow surface ar

of the materi

mize specific 

ability. The ac

r the success o

gy, and annea

ific capacity t

materials reve

High surface 

olyte interface

rea observed i

ials, resulting

capacity whi

chievement of

of the HE and

aling 

than 

ealed 

area 

e and 

in the 

 in 

le 

f the 

d
NASA/TM

2.2 E

The H

these spec

ionic cond

performan

facilitate t

In a p

electrolyte

concentra

and 20 pe

tests. In th

additives 

This s

Products/U

extensive 

by Smart 

sealed, gla

reference 

otherwise

In a p

DMMP [1

carbonate

5% LiBO

extinguish

TPP-conta

respective

M—2012-21768

Electrolytes 

HE and UHE 

cific cell desig

ductivity betw

nce goals such

the formation

previous paper

e formulation

ations between

ercent were de

his paper, the 

and their com

section report

University of

findings of th

et al. at NAS

ass cells cont

electrodes se

e noted. 

previous paper

1.0M (95% L

e:dimethyl me

B) in EC:EM

hing times (SE

aining carbon

ely, as compa

89 

cells require a

gns. In additi

ween 0 and 30

h as capacity 

n of stable sol

r, the flame-r

ns was present

n 5 and 15 pe

emonstrated t

electrochemi

mpatibility wit

ts on the elect

f Rhode Island

he FY10 Fina

A JPL (Ref. 9

aining spiral 

eparated by tw

r (Ref. 2), it w

iPF6 + 5% lith

ethyl phospho

MC:DMMP in 

ETs) of the el

nate blends. T

ared to an SET

a safe electro

on to its safet

0 °C, provide

and cycling s

id electrolyte

etardant and s

ted (Ref. 2). E

ercent and dim

o self-extingu

ical performa

th the HE and

trolyte develo

d (YTP/URI) 

al Report on e

9). Experimen

rolls of MCM

wo layers of T

was reported t

hium bis(oxa

onate (EC:EM

a 30:50:20 ra

lectrolyte form

The DMMP-co

T of 33.4 sec 

9 

lyte that is co

ty characterist

electrochemi

stability, mus

e interphase (S

self-extinguis

Electrolytes c

methyl methyl

uish faster tha

ance of candid

d UHE chemi

opment efforts

under their c

electrolyte dev

ntal electrolyt

MB-carbon an

Tonen Setela p

that YTP/UR

alato) borate (

MC:DMMP) in

atio] were dem

mulations tes

ontaining blen

for the all-car

ompatible wit

tics, the elect

ical performa

st be stable at 

SEI) layers on

shing properti

containing trip

l phosphonate

an carbonatedate electrolyt

istries are disc

s at NASA JP

contract with N

velopment iss

tes were teste

nodes, LiNiCo

porous polypr

RI electrolytes

(LiBOB)) in e

n a 30:55:15 r

monstrated to

sted, which in

nds exhibited

rbonate electr

th the electrod

trolyte must o

ance that enab

voltages up t

n the electrod

ies of several

phenyl phosp

e (DMMP) co

-based electro

tes with flam

cussed. 

PL and at Yar

NASA. It sum

sued to NASA

ed in three-ele

oO2 cathodes,

ropylene sepa

s containing 1

ethylene carbo

ratio and 1.0M

o have the low

ncluded carbo

d SETs of 1.8

rolyte. 

de couples for

offer excellen

bles project 

to 5.0 V, and 

de surfaces. 

l experimenta

phate (TPP) 

oncentration o

olytes in flame

me-retardant 

rdney Technic

mmarizes the 

A GRC, autho

ectrode, O-rin

, and lithium 

arator, unless 

5 and 20 perc

onate:ethyl m

M (95% LiPF

west selfnate-based an

 and 0.4 sec, 

r

nt 

must 

al 

of 15 

e

cal 

ored 

ng 

cent

methyl 

F6 + 

nd 
NASA/TM

In add

capability

cycle life 

versus Li/

performan

high volta

Despi

DMMP w

beads (MC

YTP/URI

M—2012-21768

dition to their

y over a wide 

performance 

/Li+, these ele

nce observed 

ages is attribu

ite the promis

was quite poor

CMB) and M

I electrolytes w

89 

r superior flam

temperature r

were also ob

ectrolytes we

from the all-c

uted to the add

sing performa

r when cycled

MPG-111. Low

were cycled i

me retardant p

range due to f

served. Addit

re observed to

carbonate ele

dition of LiBO

ance discussed

d in cells cont

w capacity, po

in cells with M

10 

properties, the

favorable cath

tionally, in ha

o offer excell

ctrolyte contr

OB (Ref. 2). 

d above, the p

taining carbon

oor efficiency

MCMB and L

e YTP/URI el

hode kinetics

alf-cells conta

lent performa

rol (Fig. 5). T

performance o

n-based anod

y, and high IC

LiNiCoO2, as 

lectrolytes dis

. Good low-te

aining a high 

ance, compara

This exception

of the electro

des such as me

CL were obser

seen in Figur

splayed good

emperature an

voltage catho

able to the 

nal performan

lytes that con

esocarbon mi

rved when the

re 6. The data

d rate 

nd 

ode 

nce at 

ntain 

croe

a
NASA/TM

shown rep

DMMP on

while cell

capacity o

excessive 

DMMP-c

In alte

promoting

Although 

selected e

which sho

rate from 

Subse

compatibi

TPP into c

Generatio

electrolyte

assessmen

capacity o

The cell w

cell with t

voltage m

Futur

concentra

electrolyte

investigat

M—2012-21768

presents the 5

n average yie

ls with electro

of the cells co

reactivity at 

ontaining ele

ernative elect

g additive, wa

VC was obse

electrolytes ap

ows the disch

4.8 to 2.0 V (

equently, LiB

ility of the TP

carbonate-bas

on #2 electroly

e in an MPGnts of the JPL

or voltage ben

with the basel

the JPL Gene

may also provi

e electrolyte d

ations of TPP 

es, gaining a 

ting other stra

89 

5th formation 

elded 78 perce

olyte containi

ontaining the b

the anode, wh

ctrolytes with

trolyte formul

as included in

erved to bene

ppeared to hav

arge performa

(cells were ch

OB was incor

PP-based form

sed electrolyt

yte that displa

-111-Li[LiNM

L Generation #

nefit when the

ine electrolyt

eration #2 elec

ide better long

development 

and other flam

fundamental 

ategies to imp

cycle, using a

ent of the cap

ng 20 percent

baseline elect

hich led to no

h carbon-base

lations develo

n order to inhi

fit cathode ki

ve a detrimen

ance of sever

harged at room

rporated into 

mulations with

tes and their o

ays comparab

MC]O2 (comm

#2 electrolyte

e system is ch

te delivered ap

ctrolyte delive

g-term cyclin

efforts will b

me-retardant 

understandin

prove electroly

11 

a C/16 rate. C

acity of the c

t DMMP deli

trolyte. The a

on-ideal SEI l

ed anodes prec

oped at NASA

ibit excessive

inetics in low

ntal effect in h

ral electrolyte

m temperature

experimental

h high voltag

optimization r

ble reversible 

mercial Toda 

e at high volta

harged to 4.8 

pproximately

ered 231 mAh

ng stability. 

be focused on 

additives, inc

g of the stabi

yte compatibi

Cells with elec

cells containin

ivered only sl

addition of DM

layer formatio

cludes their u

A JPL, vinyle

e reactivity an

er voltage sys

high voltage s

e formulations

e prior to disc

l electrolytes 

e systems. Th

resulted in the

capacity and 

9100 cathode

ages indicate 

V versus to 4

y 237 mAh wh

h when charg

exploring the

creasing the io

ilizing effect o

ility in high v

ctrolytes cont

ng the baselin

lightly more t

MMP is thoug

on. This incom

use in the HE 

ene carbonate 

nd enhance SE

stems, its inco

systems, as se

s at 0 °C at a 

charge). 

with the goal

he combinatio

e identificatio

d rate capabilit

e) system. Pre

that there is n

4.6 V, as displ

hen charged t

ged to 4.6 V. A

e effects of hi

onic conducti

of LiBOB at h

voltage system

taining 15 per

ne electrolyte,

than half the 

ght to have ca

mpatibility of

cell. 

(VC), an SEI

EI formation. 

orporation int

een in Figure

C/10 discharg

l of enhancing

on of LiBOB 

on of a JPL 

ty as the base

eliminary 

no significant

layed in Figu

to 4.8 V and t

A lower char

igher 

ivity of the 

high voltages

ms. 

rcent

,

aused 

f

Ito the 

7, 

ge 

g the 

and 

eline 

t

ure 8. 

the 

ge 

s, and 
NASA/TM

2.3 S

NASA

technolog

reversal, e

tests) with

developed

coating on

LiCoP

shows the

cathode p

two differ

suppresse

uncoated 

eliminate 

Another k

to be effec

of uncoate

cells of a 

Section 2.

cells with

capacity d

Prelim

during lon

cells conta

Li/Li+ wh

lower spe

stability th

M—2012-21768

afety Devic

A’s goals for 

gies that are to

external short

h no fire or th

d an approach

n the cathode 

PO4 coatings 

e results of dif

owders that h

rent concentra

ed the exother

materials. Th

the potential 

key to the suc

ctively incorp

ed and LiCoP

nominal 1 Ah

.1). First cycl

 coated catho

delivered is qu

minary test re

ng term opera

aining an unc

hile cycling at

cific capacity

han the uncoa

89 

es 

inherent safet

olerant to elec

t-circuit, and i

hermal runawa

h to produce s

powders. Th

were applied 

fferential scan

have been coa

ations of the c

rmic peaks su

he use of catho

for thermal ru

cessful imple

porated into th

PO4-coated co

h capacity con

le formation i

odes. Cells we

uite similar fo

sults indicate

ation in cells. 

coated and a L

t C/10 and ro

y through abo

ated cathode. 

ty in the adva

ctrical and the

internal-short

ay. Under con

safer electrode

is is discusse

to commerci

nning calorim

ated. The plot

coating to the

uch that much 

odes that hav

unaway assoc

ementation of

he cell with m

ommercial To

ntaining a car

s shown in Fi

ere charged an

or all the cells

 that the LiCo

Figure 11 sho

LiCoPO4-coat

om temperatu

ut 20 cycles,

12 

anced HE and

ermal abuse s

ts (meaning th

ntract with NA

es by utilizing

d in more det

ial Toda 9100

meter testing o

ts of coated m

e raw powders

less heat flow

e characterist

ciated with th

f a safety com

minimal impac

oda 9100 Li[L

rbonaceous an

igure 10 for tw

nd discharged

s. 

oPO4-coated c

ows the cyclin

ted commerci

ure. After form

however, it e

d UHE cells d

such as over-t

he cell design

ASA, Physica

g a lithium co

tail in Referen

0 Li[LiNMC]O

of the uncoate

materials are th

s. As the figu

w was genera

tically less he

he cathode com

mponent into a

ct on the over

LiNMC]O2 ca

node and the 

wo cells with

d at C/20 betw

cathodes may

ng performan

ial Toda 9100

mation, the co

exhibited less 

dictate a need 

temperature, o

ns pass intern

al Sciences In

obalt phospha

nces 2 and 10

O2 cathode po

ed cathode po

he results of t

ure shows, the

ated as compa

eat flow could

mponent in a 

a cell is measu

rall cell perfo

athodes was p

baseline elect

h uncoated cat

ween 4.6 and 

y offer perform

nce of a differ

0 Li[LiNMC]

oated cathode

fade and bett

for cell-level

overcharge, 

al short circu

ncorporated (P

ate (LiCoPO4)

0. 

owders. Figur

owders and 

the applicatio

e coatings 

ared to the 

d greatly redu

full cell. 

ured by its ab

ormance. Test

performed in p

trolyte (defin

thodes and tw

2.8 V. The 

mance benefi

rent set of pou

O2 cathode v

e initially had

ter cycling 

l

uit 

PSI) 

)

re 9 

on of 

uce or 

bility 

ting 

pouch 

ned in 

wo 

its 

uch 

versus 

d
NASA/TM

Altho

long term

constructe

testing wa

extensive 

not yet be

The e

continue t

powders w

performan

M—2012-21768

ough LiCoPO4

m electrical per

ed in a labora

as performed 

testing that c

een carried ou

extent to whic

to be evaluate

with the PSI L

nce and safety

89 

4-coated catho

rformance, th

atory setting w

to provide an

can provide co

ut. 

ch these comp

ed in a full-ce

LiCoPO4 coat

y of the cells 

odes have bee

he results were

where reprodu

n early indicat

onclusive evid

ponents may i

ell configurati

ting, incorpor

in a more rigo

13 

en evaluated i

e nonconclus

ucibility is cha

tion of the po

dence of the e

impact both sa

ion. Future ef

rating them in

orous set of te

in full pouch 

ive. The cells

allenging. In 

otential benefi

effectiveness 

afety and pra

fforts will focu

nto production

ests. 

cells and test

s had low cap

addition, a lim

its of the coat

of the coatin

actical perform

us on coating

n full cells, an

ted for safety 

pacity and wer

mited set of s

ting, however

g in a full cel

mance will 

g Li[LiNMC]O

nd assessing t

and 

re 

safety 

r, 

ll has 

O2

the 
NASA/TM

3.0 U

3.1 A

Advan

Li[LiNMC

carbonace

C/10 and 

Corporati

GTRC

test condi

EC:DEC:

Formation

anodes co

rigid, and 

were deve

ICL, and m

given in T

Key m

of the pas

values on 

parameter

material. T

were mea

each deve

reversible

efficiency

M—2012-21768

Ultra High

Anodes 

nced anodes a

C]O2 cathode

eous anode op

0 °C. Anode 

on (GTRC) a

C and LMSSC

tions in 2325

DMC electro

n procedures 

ontain very di

may include 

eloped throug

maximizing c

Table 4 and T

metrics that ar

st two years. T

the spider plo

r achieved ov

Table 6 quant

sured. In add

eloper. Values

e capacity, spe

y, and cycle li

89 

h Energy C

are required f

e, approximate

perating at lik

materials disc

and Lockheed

C materials w

-type coin ce

lyte in a 1:1:1

were recomm

fferent silicon

other conduc

gh experiment

capacity and c

Table 5, respec

re fundament

The “best” va

ot shown in F

er the two ye

titatively lists

ition, it lists t

s reported are

ecific capacity

ife. The follow

Cell 

for the succes

ely a three tim

ke conditions.

cussed in this

d Martin Spac

were independ

ll half cells w

1 ratio by vol

mended by the

n:carbon (Si:C

ctive carbon a

tation with th

cycling stabil

ctively. 

al to the over

alues demonst

Figure 12. Bes

ar developme

s the best and 

the values of a

e for the avera

y, temperatur

wing paragrap

14 

ss of the UHE

mes increase i

 The goal for

s paper were d

e Systems Co

dently assesse

with a Li meta

ume, and a 20

e contractors w

C) ratios, bind

additives, uniq

e goals of for

ity. Anode te

rall operation 

trated for thes

st values are d

ent period. He

goal values a

all the param

age of four ce

re performanc

phs describe t

E cell. When c

in specific cap

r advanced an

developed at 

ompany (LMS

ed at NASA G

al counter elec

0 μm thick T

who develope

der types that

que formation

rmation of a g

st procedures

of the anode 

se parameters

defined as the

ence, values a

and the mater

eters for the m

ells. The param

ce, loading, ra

the data for th

coupled with 

pacity is requ

node materials

Georgia Tech

SSC). 

GRC using a s

ctrode, 1.0 M

onen Setela s

ed the materia

t range from e

n procedures 

good SEI laye

s from GTRC

have measur

s are compare

e highest valu

are not necess

rials from whi

most recent d

meters shown

ate capability

hese paramete

a fully succes

uired over a S

s is 1000 mAh

h Research 

standard set o

M LiPF6 in 

separator. 

als. Since the

elastomeric to

for each mate

er, minimizin

C and LMSSC

ed over the co

ed to the goal 

ue of the parti

sarily for the 

ich the best v

deliverables fr

n include 

, coulombic 

ers in more de

ssful 

SOA 

h/g at 

of 

e

o

erial 

g 

C are 

ourse 

icular 

same 

values 

rom 

etail. 
NASA/TM

Test 

23 °C chara

0 °C charact

a

Deliverables

Test 

Formation 

23 °C chara

0 °C charact

a

Deliverable 4

M—2012-21768

stage 

acterization A

C

terization A

ta

P

s 3 and 4 

stage 

P

D

2

V

acterization A

C

terization A

ta

P

4

89 

TABL

At 23 °C, charge 

C/10 to 1.0 V. Pe

All charges are p

aper to C/50. So

Perform for 10 cy

TABL

Perform at 23 °C

De-insert to 0.9 V

2nd cycle: Insert 

V. Rest for 5 min

At 23 °C, charge 

C/10 to 0.9 V. Pe

All charges are p

aper to C/50. So

Perform for 10 cy

LE 4.—GTRC A

at C/10 to 10 m

erform for 10 cyc

erformed at 23 °

ak for 2 hr after 

ycles. 

LE 5.—LMSSC 

. 1st cycle: Inser

V. 

at C/8 to 150 m

n after each comp

at C/10 to 150 m

erform for 10 cyc

erformed at 23 °

ak for 2 hr after 

ycles. 

15 

ANODE TEST P

Test c

mV, hold voltage,

cles. Rest for 5 m

°C. Charge at C/

all temperature 

ANODE TEST 

Test c

rt at C/20 to 25 m

V, hold voltage 

plete insertion an

mV, hold voltage

cles. Rest for 5 

°C. Charge at C/

all temperature 

PROCEDURESa

conditions 

, and allow curre

min after each ch

/10 to 10 mV, ho

changes. At 0 °C

PROCEDURES

conditions 

mV, hold voltag

and allow curren

and de-insertion.

e, and allow cur

min after each c

/10 to 150 mV, h

changes. At 0 °C

a

ent to taper to C/

harge and discha

old voltage, and 

C, discharge at C

Sa

ge and allow curr

nt to taper to C/5

rrent to taper to C

charge and disch

hold voltage, and

C, discharge at C

/50. Discharge a

arge. 

allow current to

C/10 to 1.0 V. 

rent to taper to C

50. De-insert to 

C/50. Discharge 

harge. 

d allow current t

C/10 to 0.9 V. 

at 

o

C/50. 

0.9 

at 

to 
NASA/TM—2012-217689 16 

TABLE 6.—SUMMARY OF ANODE BEST VALUES AND LATEST VALUES 

Metric Goal Best values Values for latest materials 

 Value Material GTRC 23 mo. LMSSC 23 mo. 

Total reversible capacity 

(after 2-3 cycles) (%) 

89 70 GTRC 23 mo. 70 4 

Specific capacity, RT, C/10 

(mAh/g) 

1110 1660 LMSSC 6 mo. 1598 1209 

Specific capacity, 0 °C, C/10 

(mAh/g) 

1000 1528 GTRC 23 mo. 1528 1186 

RT capacity retention at 0 °C (%) 90 107 GTRC 18 mo. 96 98 

Loading (mAh/cm2) 3.7 3.0 GTRC 11 mo. 0.9 2.7 

Rate Capability at C/2 as 

compared to C/10 (%) 

93 103 GTRC 18 mo. 94 81 

Coulombic Efficiency (%) 99.5 98.8 GTRC 23 mo. 98.8 97.9 

Projected Cycle Life (cycles to 

80% of initial capacity) 

250 ~365 at C/2. 96% of 

initial capacity has 

been demonstrated 

through 130 cycles. 

GTRC 23 mo. ~365 at C/2. 96% of 

initial capacity has 

been demonstrated 

through 130 cycles. 

~23 at C/10 

3.1.1 Reversible Capacity 

Reversible capacity for anodes is measured after the second or third formation cycle (after the second 

cycle for the 23 mo. materials). The percentage of reversible capacity is equivalent to (100 percent minus 

the percentage of the cumulative ICL). The cumulative percent ICL is calculated by the formulas: 

ሻ௜݃݁ݎ݄ܿܽݏ݀݅ െ௜ ݃݁ݎ݄ܿܽሺ ෍ൌ ܮܥܫ	݁ݒ݅ݐ݈ܽݑ݉ݑܥ

௡

௜ୀଵ

ൌ ܮܥܫ	%	݁ݒ݅ݐ݈ܽݑ݉ݑܥ

ܮܥܫ	݁ݒ݅ݐ݈ܽݑ݉ݑܿ

௡݃݁ݎ݄ܿܽݏ݀݅

ൈ 100

where n = number of cycles (n = 2 or 3), chargei = ith cycle insertion capacity, and dischargei = ith cycle 

deinsertion capacity. 

The goal for cumulative reversible capacity of the anode is 89 percent, or inversely, the cumulative 

ICL should ideally be no greater than 11 percent. This value is based on the irreversible capacity of MPG111 as measured by Saft America and independently confirmed by GRC. The results of NASA internal 

measurements show that the GTRC 23 mo. material exhibited a cumulative reversible capacity of 

70 percent after the second formation cycle as compared to only 4 percent for the LMSSC 23 mo. 

material. 

GTRC’s initial average charge capacity (first formation cycle) was 2184 and 1739 mAh/g was 

delivered on discharge. On the second formation cycle 1827 mAh/g was inserted, and 1733 mAh/g was 

deinserted. As seen, the average percentage ICL on the second formation cycle improved to ~5 percent as 

compared to ~26 percent on the first cycle, resulting in a 30 percent cumulative percent ICL. 

The LMSSC material attained a much higher specific insertion capacity on the first formation charge 

than the GTRC material, demonstrating an average of 3762 mAh/g. However, an average 35 percent ICL 

was measured for this cycle in which full insertion and de-insertion of Li was performed, almost 

10 percent higher than the GTRC material. In subsequent cycles, LMSSC procedures called for voltage 

limits that allowed only partial insertion of Li. On the next cycle, an average of 1508 mAh/g was inserted, 

but only 1266 mAh/g was reversible, resulting in a 19 percent ICL on the second cycle and a cumulative 

ICL of 96 percent after the first two cycles. 

 
NASA/TM

The e

capacity l

of the amo

crystalline

cycling be

to higher 

within the

This cycli

capacity o

cathode ca

of the cath

3.1.2 S

Speci

measured 

respective

formation

characteri

at 0 °C is 

LMSS

Specific c

goal value

M—2012-21768

extremely high

oss, but rathe

orphous rang

e phase. LMS

etween the tw

fade, as was i

e specified vo

ing method pr

of the Si anod

apacity must 

hode in the ce

pecific Capa

fic capacity a

between the 

e temperature

n. For anodes,

ization is perf

reported for d

SC 6 mo. mat

capacity meas

e of 1110 mA

89 

h irreversible

er is induced b

e of Si (below

SSC’s internal

wo phases (am

initially repor

oltage limits a

recludes the m

de must still b

be matched t

ell as well, ev

acity 

at 23 and 0 °C

voltage limit

. Specific cap

 characterizat

formed on to 

discharge at 0

terial demons

sured at 23 °C

Ah/g. Howeve

 capacity of t

by the cycling

w 50 mV) and

l studies show

morphous and 

rted by Obrov

as given in Ta

materials’ pra

be carried and

o the initial S

ven after the I

C are plotted a

s specified fo

pacity at both 

tion at 0 °C is

avoid any cap

0 °C after a 23

strated the bes

C and C/10 on

er, the materia

17 

the LMSSC an

g procedures a

d into the rang

wed that for th

crystalline) a

vac and Kraus

able 5 is still p

actical applica

contributes t

Si capacity, w

CL of the cat

as a percentag

or each materi

23 and 0 °C

s performed o

pacity fade in

3 °C charge. 

st specific cap

n this material

al had high IC

node beyond 

adopted by L

ge in which S

heir material 

adversely imp

se (Ref. 11). H

poor on these 

ation in a ligh

to the mass of

which thereby 

thode is accou

ge of the spec

ial (see Table

is reported fo

on a different 

ntroduced by p

pacity of all o

l is 1660 mAh

CL and poor r

the first cycl

LMSSC to avo

Si is converted

composition,

pacted cycling

However, cyc

materials, as

htweight cell, 

f the cell. In a

increases the

unted for. 

cific capacity 

e 4 and Table 

or the first cyc

set of cells th

prior cycling.

of the develop

h/g, which far

rate capability

e is not a true

oid cycling ou

d into its 

, continuous 

g stability and

cling stability

 seen in Figur

since the unu

addition, the 

e mass contrib

goals at C/10

5) and at the 

cle following 

han the 23 °C

. Specific cap

pmental mater

r exceeded th

y. The GTRC 

e

utside 

d led 

y

re 13. 

usable 

bution 

0 as 

C

pacity 

rials. 

he 
NASA/TM—2012-217689 18 

23 mo. material was a close second, achieving 1598 mAh/g. At 0 °C and C/10, 1528 mAh/g was obtained 

on the same material, which also far exceeded the 1000 mAh/g goal value. While this material exhibited 

excellent capacity retention at 0 °C, rate capability, and cycling stability, coulombic efficiency, ICL, and 

loading still need improvement. Project goals were established for 0 °C operation. Room temperature 

(RT) goals were calculated as the expected minimum specific capacity, based on the desire to retain at 

least 90 percent of RT capacity when operating at 0 °C. 

3.1.3 Temperature Performance 

Temperature performance is measured as the percentage of RT capacity retained at 0 °C. A goal of 

90 percent was established for temperature performance based on what is reasonably practical given 

current SOA Li-ion cell performance. With the exception of the first set of deliverables from both 

contracts, all subsequent materials have demonstrated excellent temperature performance. The best values 

column in Table 6 indicates a value of 107 percent for the percentage of RT capacity retained at 0 °C 

since the capacity of the GTRC 23 mo. material tends to improve with cycling. 

3.1.4 Loading 

Loading is a measure of capacity per unit area. The target loading for the NASA anodes is 

~3.7 mAh/cm2

. Currently the LMSSC and GTRC anodes have very low loading as compared to that 

found in practical cells that are designed to offer high capacity at moderate discharge rates. Low loading 

will necessitate larger electrode area to provide the equivalent capacity as electrodes with higher loading, 

which adversely impacts energy density. Specific energy will also suffer, as larger areas of current 

collector and possibly larger cell housings (i.e., inactive components) will be needed to accommodate 

impractically sized electrodes. Through our studies, trends showed that higher loaded anodes tended to 

have lower coulombic efficiency and cycle life. This is an area for further study and optimization. 

3.1.5 Rate Capability 

Rate capability testing is performed at C/5 and C/2 and compared to specific capacity achieved at 

C/10. A target of 93 percent of the C/10 performance was established for C/2 performance. The Si:Cbased anodes have demonstrated excellent rate capability. The rate capability for recent deliverables has 

consistently measured between 94 and >100 percent (the specific capacity of the GTRC 23 mo. material 

improved with cycling). 

3.1.6 Cycle Life 

Cycle life assessments are performed at 23 °C in half-cells vs. Li/Li+. The goal for the UHE cell is 

200 cycles at 100 percent DoD to 80 percent of initial capacity when cycled at C/2. To attain 200 cycles 

on the cell level, 250 cycles is desired from the components. Cycle life of the LMSSC material is assessed 

at C/10 due to the high fade observed in early cycling. Figure 13 shows results of cycle life testing for 

GTRC and LMSSC 23 mo. materials. Here, initial capacity is defined as the capacity delivered on the first 

discharge of continuous cycling (cycle 10 for the LMSSC material and cycle 16 for the GTRC material). 

The LMSSC material displays poor cycling stability, achieving only 23 cycles to our defined point of 

failure. Further, it only achieves 37 cycles prior to its specific capacity falling below the anode threshold 

value of 600 mAh/g, the minimum success criteria. The GTRC material demonstrated >45 cycles with 

virtually no fade, and as previously discussed, the specific capacity tended to improve with cycling. 

Ninety-six percent of the initial capacity is measured after 130 cycles. Cycling on this material is still in 

progress. Using a linear extrapolation based on the rate of fade, approximately 365 cycles are projected to 

80 percent of the initial capacity. 

In order to improve cycling stability of the Si-based anodes, <10 percent by weight of VC was added 

to the baseline electrolyte in both GTRC and LMSSC cells. While a beneficial effect on cycling stability 

was seen in the GTRC material, the performance of the LMSSC material did not improve with the 

addition of VC. 
NASA/TM

3.1.7 D

Figur

above for 

to a single

anode ma

performan

coulombic

M—2012-21768

Discussion 

e 14 and Figu

6, 11, 18, and

e material. NA

aterials when p

nce, rate capa

c efficiency, a

89 

ure 15 contain

d 23 mo. mat

ASA has dem

performance 

ability and cyc

and loading r

n spider plots 

terials from G

monstrated exc

is measured b

cling stability

emain as chal

19 

that show the

GTRC and LM

cellent perform

based on spec

y metrics. For

llenges to be 

e progression

MSSC. Values

mance with th

cific capacity

r the GTRC m

addressed fur

n of the param

s plotted in ea

hese NRA-de

at 23 and 0 °

materials, imp

rther. 

meters discuss

ach graph per

eveloped Si-b

°C, temperatu

provements to

ed 

rtain 

based 

ure 

o IC, 
NASA/TM

As dis

would req

large mas

anode wa

4.0 C

Cell-l

materials 

Projected 

the most p

the projec

Rover bat

project us

M—2012-21768

scussed in the

quire the use o

s penalties. U

s eliminated f

Cell Projec

level specific 

that provide t

values for ce

promising ma

cted values ar

tteries is also 

ses as a baseli

89 

e section on r

of cycling reg

Upon modelin

from further c

ctions 

energy and e

the best comb

ell level specif

aterials’ perfo

e shown in Fi

included for 

ine to measure

eversible cap

gimes that lim

ng its practical

consideration

energy density

bination of hig

fic energy and

ormance at C/

igure 16. Perf

comparison. T

e progress. 

20 

acity, the inco

mit the useable

l application i

 in the UHE c

y values are p

gh specific ca

d energy dens

10 to 3.0 V an

formance of L

These cells co

orporation of

e capacity in t

in an integrat

cell. 

predicted usin

apacity and h

sity are based

nd 0 °C (Ref.

Li-ion cells fr

ontain the che

f the LMSSC 

the cell, there

ted cell design

ng the cathode

igh capacity r

d on projectio

f. 12). The goa

rom the 2003 

emistry that th

anode in a ce

eby resulting 

n, the LMSSC

e and anode 

retention to d

ons using data

al values vers

Mars Explor

his developm

ell 

in 

C

date. 

a for 

sus 

ation 

ment 
NASA/TM

When

considere

performan

lower and

below 3.0

the capaci

some of th

performan

moves tow

performan

fundamen

5.0 S

Stead

and UHE 

discussed 

achieve fu

Additiona

singular c

their suita

Electr

containing

properties

with Si-ba

investigat

LiCoP

powders o

materials 

M—2012-21768

n projecting p

d. Poor perfo

nce penalties 

d more sloping

0 V. Ultimatel

ity of the elec

he developme

nce. These an

ward building

nce modeling

ntal research e

Summary

dy progress in 

Li-ion cells f

in this paper

ull success wi

ally, the comb

cathode and a 

ability for inco

rolytes that ar

g a combinati

s, high voltag

ased electrode

tion. 

PO4 coatings 

on the compo

is required in

89 

erformance o

rmance of the

at 0 °C. Addi

g discharge p

ly, the develo

ctrode it is bei

ental material

nd other integr

g cells. They a

, electrolyte o

efforts that tar

the developm

for NASA’s E

, in each of th

ith the materi

bination of the

singular anod

orporation int

re compatible

ion of LiBOB

e stability, an

es and that fa

have been sh

nent level. Sa

n order to asse

on a cell level

e NMC catho

itionally, as d

profile in a cel

opmental anod

ing paired wi

ls, and may be

ration issues a

are currently b

optimization, 

rget specific c

ment of advan

Exploration ap

he component

als and bring 

e parameters 

de system is n

to practical ce

e with the com

B and TPP hav

nd reversible c

cilitate stable

hown to impro

afety testing o

ess their safet

21 

, integration i

odes at 0 °C al

discussed in R

ll than graphi

de or cathode 

th. Attaining 

e detrimental 

are among ch

being address

component c

characteristic

nced compone

pplications ha

t areas, additi

them to matu

described abo

necessary for 

ells. 

mponents are a

ve demonstrat

capacity. For 

e SEI layer for

ove the therm

of higher capa

ty benefits in 

issues betwee

lso translates 

Reference 12, 

ite anodes, res

 must also be

higher loadin

to other aspe

hallenges to b

sed through c

compatibility 

s of material

ents for safe, 

as been achie

ional develop

urity for use i

ove that meet

full success o

also required

ated an ideal c

UHE cells, e

rmation on th

mal properties 

acity, represen

an integrated

en the anode a

into significa

Si-based ano

sulting in sign

e loaded such 

ngs has been c

ects of the ma

be addressed a

cell design mo

trials, and ad

improvement

lightweight, a

ved over the 

pment work is

in production 

ts or exceeds 

of the electro

d. For HE cell

combination o

electrolytes th

hese novel ma

of Li[LiNMC

ntative cells c

d Li-ion system

and cathode w

ant cell-level 

odes produce a

nificant capac

that it can ma

challenging w

aterials’ 

as the project 

odeling, 

dditional 

t and optimiz

and compact 

past 2 years. 

s still required

cells. 

our goals in a

de materials a

s, electrolytes

of flame-retar

hat are compat

aterials are un

C]O2 cathode

containing the

m. 

were 

a

city 

atch 

with 

zation. 

HE 

As 

d to 

a

and 

s

rdant 

tible 

nder 

ese 

NASA/TM—2012-217689 23 

Appendix—Nomenclature 

°C degrees Celsius 

C carbon 

DEC diethyl carbonate 

DMC dimethyl carbonate 

DMMP dimethyl methyl phosphonate 

DoD depth-of-discharge 

EC ethylene carbonate 

EMC ethyl methyl carbonate 

g/cc grams per cubic centimeter 

GRC Glenn Research Center 

GTRC Georgia Tech Research Corporation 

HE High Energy 

ICL irreversible capacity loss 

JPL Jet Propulsion Laboratory 

JSC Johnson Space Center 

KPP key performance parameters 

LiBOB lithium bis(oxalato) borate 

LiCoPO4 lithium cobalt phosphate 

Li-ion lithium-ion 

LiPF6 lithium hexafluorophosphate 

LMSSC Lockheed Martin Space Systems Company 

Li[LiNMC]O2 lithium nickel manganese cobalt oxide 

M molar 

mAh/g milliampere-hours per gram 

MCMB mesocarbon microbeads 

MER Mars Exploration Rovers 

mo. month(s) 

mV millivolts 

NASA National Aeronautics and Space Administration 

NEI NEI Corporation 

PSI Physical Sciences, Incorporated 

RT room temperature 

SEI solid electrolyte interface 

SET self-extinguishing time 

Si silicon 

Si:C silicon:carbon 

SOA state-of-the-art 

TD tap density 
NASA/TM—2012-217689 24 

TPP triphenyl phosphate 

UHE Ultra High Energy 

μm micrometer 

UTA University of Texas at Austin 

V volts 

VC vinylene carbonate 

Wh/kg watt-hours per kilogram 

Wh/L watt-hours per liter 

YTP/URI Yardney Technical Products/University of Rhode Island 
NASA/TM—2012-217689 25 

References 

1. C.M. Reid and W.R. Bennett, “A Study on Advanced Lithium-Based Battery Cell Chemistries to 

Enhance Lunar Exploration Missions,” National Aeronautics and Space Administration Glenn 

Research Center, Cleveland, OH, NASA/TM—2010-216791, September 2010. 

2. C.M. Reid, “Progress in Materials and Component Development for Advanced Lithium-ion Cells for 

NASA’s Exploration Missions,” National Aeronautics and Space Administration Glenn Research 

Center, Cleveland, OH, NASA/TM—2011-217209, September 2011. 

3. A. Manthiram, High-energy density cathodes for next generation lithium-ion batteries, Final Report to 

NASA Glenn Research Center from The University of Texas at Austin for contract NNC09CA08C, 

March 2011. 

4. N.M. Hagh, F. Badway, M. Moorthi, G. Skandan, W. West, R. Bugga, C. Reid, Improvements in 

Energy Density and Stability of Advanced Cathode Materials for NASA’s Applications, NASA 

Aerospace Battery Workshop, November 16-18, 2010. 

5. J. Li, R. Klopsch, M.C. Stan, S. Nowak, M. Kunze, M. Winter, and S. Passerini, Synthesis and 

electrochemical performance of the high voltage cathode material Li[Li0.2Mn0.56Ni0.16Co0.08]O2 with 

improved rate capability, J. Power Sources, 196 (2011) 4821-4825. 

6. N.M. Hagh, F. Badway, K. Martin, M. Moorthi, and G. Skandan, High Energy Density Cathode 

Materials for Li-Ion Battery Applications, 44th Power Sources Conference, Las Vegas, NV, June 14-

17, 2010. 

7. N.M. Hagh, G.G. Amatucci, A new solid-state process for synthesis of LiMn1.5Ni0.5O4−δ spinel, J. 

Power Sources, 195 (2010) 5005-5012. 

8. J.M. Zheng, X.B. Wu, and Y. Yang, A comparison of preparation method on the electrochemical 

performance of cathode material Li[Li0.2Mn0.54Ni0.13Co0.13]O2 for lithium ion battery, Electrochimica 

Acta 56 (2011) 3071-3078. 

9. M.C. Smart, F.C. Krause, W.C. West, J. Soler, L. Whitcanack, and R.V. Bugga, “Development of 

Electrolytes With Improved Safety Characteristics,” Final FY10 Report for the NASA Exploration 

Technology Development Program Energy Storage Project, September, 2010. 

10. C.M. Lang, A. Newman, K. Constantine, and J. Ma, Improved Cathode Material Safety via a Metal 

Phosphate Coating, NASA Aerospace Battery Workshop, Huntsville, AL, November, 2009. 

11. M.N. Obrovac and L.J. Krause, Reversible Cycling of Crystalline Silicon Powder, J. Electrochem. 

Soc. 154 (2007) A103-A108. 

12. W.R. Bennett, “Forecasts for Hypothetical Li-Ion Cells Using FY2010 Data for ETDP Electrodes,” 

National Aeronautics and Space Administration Glenn Research Center, Cleveland, OH, 

NASA/TM—2011-TBD, 2011 (to be published). 

13. R. Staniewicz, personal communication, September 2011. 

14. J. Liu, Q. Wang, B. Reeja-Jayan, and A. Manthiram, Carbon-coated high capacity layered 

Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathodes, Electrochemistry Communications, 12 (2010) 750-753. 
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Advanced Materials and Component Development for Lithium-Ion Cells for NASA Missions 

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13. SUPPLEMENTARY NOTES

14. ABSTRACT

Human missions to Near Earth Objects, such as asteroids, planets, moons, liberation points, and orbiting structures, will require safe, high 

specific energy, high energy density batteries to provide new or extended capabilities than are possible with today’s state-of-the-art 

aerospace batteries. The Enabling Technology Development and Demonstration Program, High Efficiency Space Power Systems Project

battery development effort at the National Aeronautics and Space Administration (NASA) is continuing advanced lithium-ion cell 

development efforts begun under the Exploration Technology Development Program Energy Storage Project. Advanced, high-performing 

materials are required to provide improved performance at the component-level that contributes to performance at the integrated cell level in 

order to meet the performance goals for NASA’s High Energy and Ultra High Energy cells. NASA’s overall approach to advanced cell 

development and interim progress on materials performance for the High Energy and Ultra High Energy cells after approximately 1 year of 

development has been summarized in a previous paper. This paper will provide an update on these materials through the completion of 2 

years of development. The progress of materials development, remaining challenges, and an outlook for the future of these materials in near 

term cell products will be discussed. 

15. SUBJECT TERMS

Lithium batteries; Storage batteries; Electric batteries; Electrochemical cells; Energy storage; Space missions; Spacecraft power 

supplies; Electric power supplies 

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