Giuseppe L. Di Benedetto, Ph.D. - UMD...Giuseppe L. Di Benedetto, Ph.D. Advanced Materials Technology Branch U.S. Army ARDEC PicatinnyArsenal, NJ, USA, 07806 DISTRIBUTION STATEMENT

Act like someone’s life depends on what we do.

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COMMITMENT

&SOLUTIONS

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U.S. ARMY ARMAMENT

RESEARCH, DEVELOPMENT

& ENGINEERING CENTER

Nanomaterials and Additive Manufacturing for Munitions Power Sources

Giuseppe L. Di Benedetto, Ph.D.Advanced Materials Technology Branch

U.S. Army ARDEC

Picatinny Arsenal, NJ, USA, 07806

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2DISTRIBUTION STATEMENT A: APPROVED FOR PUBLIC RELEASE

DISTRIBUTION IS UNLIMITED

KEY CONTRIBUTORS

R. Carpenter – US Army ARDEC

D. Swanson – EnerSys Advanced Systems

B. Wightman – EnerSys Advanced

Systems

E. Handy – SI2 Technologies, Inc.

K. Maleski – Drexel University

T. Mathis – Drexel University

K. Van Aken – Drexel University

Y. Gogotsi – Drexel University

D. Sabanosh – US Army ARDEC

J. Zunino – US Army ARDEC

D. Schmidt – US Army ARDEC

J. Kraft – US Army ARDEC

L. Zunino – US Army ARDEC

B. Fuchs – US Army ARDEC

L. Holmes – US Army Research Labs

K. Duncan – US Army CERDEC

C. Haines – US Army ARDEC

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Army S&T Performing Organizations

Materiel

AMCArmy Materiel

Command

Personnel

G-1HQDA, G-1

Personnel

Medical

MEDCOMArmy Medical

Command

Infrastructure/Environmental

USACEArmy Corps of

Engineers

Strategic Missile Defense

SMDCArmy Space &

Missile Defense

Command

ATECArmy Test &

Evaluation Command

Test &Evaluation

RDECOMResearch,

Development &

Engineering

Command

AMRDEC

Aviation & Missile

Research,

Development &

Engineering

Command

ARL

Army Research

Laboratory

Armaments

Research,

Development &

Engineering

Command

Communications-

Electronics

Research,

Development &

Engineering

Command

Edgewood

Chemical Biological

Center

Natick Soldier

Research,

Development &

Engineering

Command

Tank-Automotive

Research,

Development &

Engineering

Command

ECBC NSRDECCERDEC TARDECARDEC

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S&T IN RDECOM

XM25

Counter Defilade Target

Engagement System

Discovery Innovation Advanced

Development

Translational

Neuroscience

ARL

RDECs

PMs/PEOS

Engineering &

Production

Support to

Warfighter

Face-Gear

Technology for

Block III Apache

MRAP Armor

MEMS TBI

Sensor

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INTRODUCTION

Why is the Army looking at thermal batteries?:

Thermal batteries remain a key primary power source for critical military

applications, such as precision munitions and missiles.

Competitive technologies have yet to achieve the performance and reliability of

thermal batteries for these applications.

A more compact & powerful thermal battery will lead to increased lethality and

precision.

What does this study aim to accomplish?:

Use a fully scalable high energy milling method to produce kilogram quantities of

nanoscale FeS2, CoS2, NiS2 powders for thermal battery cathodes.

Understand the effect of process parameters on the resulting nanoscale powders.

Theory behind work being done:

Nanomaterials offer an opportunity to produce batteries with improved

performance, such as higher voltages and increased current densities.

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MATERIAL PROCESSING AND MIXING

Micron sized FeS2, CoS2, NiS2 powder are currently used in thermal battery

cathodes.

Through mechanical attrition, powder particle size is reduced to the nanoscale

High energy horizontal attritors used to impart nanostructure.

Provide extremely high amounts of kinetic energy

Processing carried out in inert atmosphere to minimize oxygen pickup.

RPM, Powder-Ball-Ratio (PBR), Processing time, and Media type all important

variables in tailoring material properties

Multiple experiments were performed with different processing times to achieve

desired powder properties

High Energy Mill Size reduction through particle

collisions with grinding media

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NiS2:

PROCESSED POWDERS

CoS2:

As-Received [Micron FeS2 (right)]

Processed [Nano FeS2 (left)]

FeS2:

As-Received [Micron CoS2 (right)]

Processed [Nano CoS2 (left)]

As-Received

[Micron NiS2 (right)]

Processed [Nano NiS2 (left)]

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CHARACTERIZATION TECHNIQUES

Scanning Electron Microscopy:

Zeiss Supra V40

X-Ray Diffraction

Rigaku Ultima

X-Ray Fluorescence

Rigaku ZSX Primus II

B.E.T.

Quantachrome Nova 4000e

ICP

Perkin Elmer Optima 5300V

LECO Sulfur Analysis

LECO SC632

Single Cell Thermal Battery Testing

from a Proven SANDIA design

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SCANNING ELECTRON MICROSCOPY – FES2


SEM was performed in order to estimate particle size.

Clear size reduction can be seen from top row (as-received) and the lower rows

(processed)

Magnifications (left to right) 500x,

2kx, 15kx, 25kx

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SCANNING ELECTRON MICROSCOPY – COS2



Clear size reduction can be seen from top row (as-received) and the lower row

(processed)

Agglomeration of ultrafine particles was evident at low magnifications of processed

powder.


2kx, 15kx, 30kx

As-Is

10h

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SCANNING ELECTRON MICROSCOPY – NIS2



Clear size reduction can be seen from top row (as-received) and the lower row

(processed).

Agglomeration of ultrafine particles was evident at low magnifications of processed

powder.


2kx, 15kx, 30kx

As-Is

10h

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PARTICLE SIZE & SURFACE AREA

COMPARISON

BET 0h 1h 2h 4h 6h 8h 10h

FeS2 2313 nm - 130 nm - 62 nm - -

CoS2 1165 nm 102 nm 78 nm 86 nm 150 nm 105 nm 124 nm

NiS2 1194 nm 218 nm 266 nm 150 nm 227 nm 123 nm 154 nm

BET 0h 1h 2h 4h 6h 8h 10h

FeS2 0.552 m2/g - 9.814 m2/g - 20.637 m2/g - -

CoS2 0.945 m2/g 10.854 m2/g 14.048 m2/g 12.791 m2/g 7.37 m2/g 10.474 m2/g 8.909 m2/g

NiS2 0.856 m2/g 4.698 m2/g 3.84 m2/g 6.798 m2/g 4.498 m2/g 8.325 m2/g 6.617 m2/g

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Pellet Fabrication:

Electrolyte and binding agent were

added to Nano-sized Iron Disulfide in

an argon atmosphere

Mixture processed , ground, and

sieved

After drying in vacuum, pellets were

pressed at 1000 psi (see photo)

Pellets were uniform and robust

Upon visual inspection, the Nano

Cathode pellets were darker than the

Micron Cathode pellets

PELLET FABRICATION

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SCTB TEST RESULTS

Single Cell Testing:

Comparison of SCTB test results for cells made up with standard Micron Catholyte

and with Nano Catholyte.

Each Nano Catholyte cell showed higher voltage output and longer run time.

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.00

0.50

1.00

1.50

2.00

2.50

0 500 1,000 1,500 2,000

Cu

rre

nt,

Am

ps

Vo

lta

ge

, V

olt

s

Time, Seconds

Cell 1A (Nano)

Cell 1C (Nano)

Cell 1B (Nano)

Cell 1D (Micron)

Current, Amps

G3190B2 sized pellets

Furnace = 500C

C/A = 1.85 - 1.90

Current = 0.35A

(50mA/cm2)Capacity to 1.46 Volt cutoff

Pressure 9.44 PSI

Figure 1: Comparison of SCTB test results

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SCTB TEST RESULTS


The average run time for Nano Catholyte cells were nearly twice that of the Micron

Catholyte cells.

Table 1: Single Cell Testing Data @ 0.35A @ 500C

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SCTB TEST RESULTS

Figure 2: Correlation of current density with cell capacity


An enhanced cell capacity is seen at all current densities used. At higher current

densities, the difference between Micron and Nano Catholyte cells starts to diminish.

0

50

100

150

200

250

300

0 100 200 300

Sin

gle

Ce

ll C

ap

ac

ity p

er

Gra

m o

fA

cti

ve

C

ath

od

e M

ate

rial, m

Ah

Current Density, mA/cm2

Micron Catholyte

Nano Catholyte

G3190B2 sized Pellets

Temperature: 500C

1.86 < C/A < 2.16

Capacity to 1.46V cutoff

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CONCLUSION

Conclusions:

Nano-sized Iron Disulfide particles were produced by high energy milling of Micron-

sized particles for use in Thermal Batteries.

The processing time and RPM required for the size reduction was determined, and

the particle size and purity were optimized.

Catholyte was produced with Nano-sized Iron Disulfide, and Thermal Battery

electrode pellets from this material were fabricated.

Single cell Thermal Batteries were assembled and tested with these pellets, and

they have been characterized for voltage, capacity, and rate performance.

Single cell Nano Catholyte cells have shown a significant performance

enhancement over single cell Micron Catholyte cell performance.

Future Work:

Build and test full Thermal Batteries using Nano Catholyte cells.

Investigate nanostructuring of alternative thermal battery materials.

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CONCLUSIONS

Nanoscale FeS2, CoS2, and NiS2 particles were produced via high energy milling of

Micron-sized particles for use in Thermal Batteries.

For NiS2, the particle size tended to decrease as a function of milling time up to 10h.

For CoS2, the material tended to reach its smallest size at 2h processing time and

then slightly increase after.

CoS2 tended to have smaller particle sizes as compared to NiS2

Both CoS2 and NiS2 were still larger than previous work done with FeS2

FeS2 [44 mm (325 mesh) 62 nm]

CoS2 [74 mm (200 mesh) 78 nm]

NiS2 [180 mm (80 mesh) 123 nm]

The powders’ tendency for moisture pickup and agglomeration is an issue which

appeared while characterizing the materials.

TGA results displayed a lower onset temperature for nanostructured materials than

their micron counterparts.

More significantly for FeS2 and NiS2 than CoS2.

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FUTURE WORK

Future Work:

Conduct more thorough investigation with new TGA-DSC-Mass Spectrometry

arriving Summer 2016.

Fabricate Thermal Battery electrode pellets from these nanostructured materials.

Validate CoS2 and NiS2 cathode performance through single cell testing, and

characterize them for voltage, capacity, and rate performance.

Build and test full Thermal Batteries using Nanostructured Cathode cells.

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ACKNOWLEDGEMENTS

Lauren Morris and Dr. Rajendra Sadangi

(U.S. Army ARDEC) for help with portions of

characterization and analysis.

Dr. David Swanson and Brian Wightman

(EnerSys Advanced Systems) for providing

Iron Disulfide powder.

This work was partially funded through:

Life Cycle Pilot Process (LCPP) of

Project Director for Joint Services (PD JS).

In-House Laboratory Independent Research (ILIR)

program of U.S. Army ARDEC.

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OPPORTUNITY SPACE

There are opportunities for AM & PE to impact all Army Systems

UAVs, UGVs

Individual Soldier

Protection

Repair Parts

Weapons

Components

Missiles/Munitions:

Warheads, Fuzes

Logistics

Communications

Command & Controls

Vehicles & Sub-

Systems

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Applied

Research

Technology

Development

Demo &

PrototypingTransition to

Production Systems

Surveillance

PolymersMetals Energetics

• Design

• Materials Development

- Inks, Coatings, Substrates

• Process Development

• Characterization

• Flex Hybrid Electronics

• Integration

• Manufacturing Scale-Up

• Testing

• Design

• Formulation

• Materials Development


• Testing

• Qual. & Cert. Support

• Design

• Powder Synthesis

• Metals 3DP

• Machining

• Mechanical Testing


• Post Processing

• Prototyping / Mfg

• Design

• Synthesis

• Formulation


• Pilot Manufacturing

• Munitions Integration

• Qualification Testing

• Integration

• Surveillance

ARDEC AM COMPETENCIES

Demilitarization

Technologies

Printed Electronics

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The M3Platform is a part of the

concepts being developed at ARDEC

looking at new and innovative

production methods to better meet

future Army needs. By combining

multiple manufacturing techniques

with direct write and additive

manufacturing capabilities, ARDEC’s

goal is to have flexible and low cost

capabilities for prototyping and

production. Just-in-Time

Manufacturing and Fab-in-the-Field

concepts are being explored.

MULTI-AXIS MULTIFUNCTIONAL MANUFACTURING

PLATFORM M3P

FDM extruder tool module Router tool moduleSyringe deposition

tool module

Camera/inspection

tool module4-point robe/inspection

tool module

Spray/encapsulant

tool module

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UNIQUE AM TECHNOLOGY

SuperScrypt

With Scan-to-print capability, the SuperScrypt can deposit on complex curves,

or build 3D shapes from scan data.

Inverse kinematics enabled 6-axis motion control allows for true 3D printing

instead of stacking 2D layers. Robust hardware allows for +/- 200nm precision.

Dubbed the SuperScrypt, this multi-technology printing

system is the only one of its kind. The systems is

based on nScrypt processing controls and software,

which are fully open for manipulation (variation of

processing parameters). This system includes:

•Line Scanning

•Thermoplastic Extrusion (up to 400)

•Thermoset Deposition

•Ink Deposition

•6-Axis Motion Control

•Tool Switching

•Pick-n-Place

To be added:

•Micro-Sprayer

•Micro-Milling

•Laser Sintering

•Aerosol Jet Deposition

•Micro Cold Spray Deposition

•Materials Hopper

•Auger

Tools can be

added as needed

Conformal

Printing

Fabricate a

functioning

device

(0 to 2,000,000cP,

with pico-liter control)

Scan-to-Print

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HYBRIDIZATION

Dissimilar materials

Conventional AMDirect WriteConformal Printing

Part Scanning

Pick and Place

Print what you can, place what you can’t !!!

Source: Zunino, Holmes, Church

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Conventional PCB - RBIS Flex Hybrid Integration ~ 60% COTS Components

Hybrid Printed Iteration – Direct

Write & Inkjet Components

Integrated with COTS

RESERVE BATTERY INITIATION SYSTEM (RBIS)

Hybrid Printed Flex RBIS < 30% COTS

Integrated Thermal Reserve

Battery with RBIS Hybrid Circuitry

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RESERVE BATTERY INITIATION SYSTEM (RBIS)

• Initial Conversion from PCB to Flex

Hybrid Designs (80mm x 80mm)

• 4 Layer Design

– 80mm x 80mm

– 1st: Silver Traces/Contact Pads

(Drop-on-Demand; Dimatix)

– 2nd: Silver Resistors (Direct Write,

nScrypt)

– 3rd: Pyralin Dielectric for Capacitor

(Direct Write, nScrypt)

– 4th: Silver Conductive Paste (Direct

Write, nScrypt)

• Interconnects to Interface with

Standard Components

• 4-Layer approach

• Minimizes traces to decrease

chance of trace impedance to

Ground.

• Smaller Form Factor

(60mm x 70mm)

• Common Interconnects to

interface with standard

Components.

• Hybrid Circuit

• Smaller Form Factor < 40mm

• Including Printed Passives

with COTS Active

Components

• Utilizes an automated Pick-n-

Place system to adhere Active

Components to Substrate.

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Giuseppe L. Di Benedetto, Ph.D.Armaments Engineering Analysis & Manufacturing Directorate

US Army ▪ ARDEC ▪ RDAR-MEA-P

[email protected]

973-724-1977

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Giuseppe L. Di Benedetto, Ph.D. - UMD...Giuseppe L. Di Benedetto, Ph.D. Advanced Materials Technology Branch U.S. Army ARDEC PicatinnyArsenal, NJ, USA, 07806 DISTRIBUTION STATEMENT