development of microbatteries for implantable...
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March 23 2017 1
Development of Microbatteries for Implantable ApplicationsYUXING WANG, SHURU CHEN, JIE XIAO, ZHIQUN DENG, JIGUANG ZHANGPacific Northwest National Laboratory
Acknowledgment
March 23 2017 2
Jiguang (Jason) Zhang,Laboratory Fellow, PNNL
Zhiqun (Daniel) Deng,Chief Scientist, PNNL
Jie Xiao,Associate Professor, UARK
(Previously, Scientist, PNNL)
Other Contributors:Honghao Chen, Bo Liu, Samuel Cartmell, Qiuyan Li, Shuru Chen, and many others
Funding
• US Army Corps of Engineers• DOE Water Power Technologies
Program• PNNL LDRD Program
Content
March 23 2017 3
Primary batteries and microbatteriesPNNL microbattery project overviewPNNL microbattery design, performance and full tag integrationChallenges in battery miniaturization and our solutionsMicrobatteries of alternative formats and future directions
Primary Batteries
March 24, 2017 4
Battery System
Nominalcell
potential
Gravimetric capacity(mAh/g)
Volumetric capacity
(mAh/cm3)
Specific energy
(mWh/g)
Li/I2 2.8 211 1041 591
Li/MnO2 3.0 308 1540 924
Li/CFx 3.0 865 2335 2595
Li/SVO 3.2 315 1510 1008
Primary batteries make up 37% of battery market value Lithium primary batteries have the highest energy densityAmong lithium primary battery chemistry, Li/CFx has one of the highest gravimetric and volumetric energy densities.
Microbatteries
March 24, 2017 5
Microbatteries find wide application in implantable medical devices, biology studies, miniaturized electronics, military use, etc.
Microbattery
Defibrillators
Fish Tags
Microsensors
Electronic pillsSpy drones
< 1mm3> 100 mm3 100 to 1 mm3
ConventionalThin film
Pin type
3D all solid state
No Moors’ law for batteries
Lack of high energy density microbatteries with size <100 mm3
Lai, W, et al., Adv Mater, 22 (2010) 139
Goal of Fish Tag Project at PNNL
March 24, 2017 6
Hydropower dams adversely affect migratory fishBehaviors and survival rate of fish migration through dams are not well understoodFish size vs. tag size. 2% rule.
Salmon, Lamprey and Eel
Hydropower plants distribution and eel habitat on the east coast
Hydro
Wind
PNNL Microbattery Project
March 24, 2017 7
2012, Beginning of microbattery project at PNNL
2016, lamprey tag design finalized;
Injectable tag technology transfer
2013, Micro V2 (injectable tags) field trial
2014, Micro V3 field trial
2015, Lamprey battery
prototyping
Injectable tags equipped with MB306 greatly improved survival rate
2017, two pilot field trials
PNNL Microbattery Design and Performance
March 24, 2017 8
Design featuresFreestanding cathode film with nanosized CFx
Jelly roll assemblyC-coated Al mesh as current collectorsAl cases, novel sealing method
Size D x L (mm)
Volume (mm3)
Weight (mg)
Capacity (mAh)
Energy density(Wh/L)
Specific energy (Wh/kg)
SR416 4.8 x 1.6 30 130 8.3 420 100
QC0025B 2.8 x 25? 155 ? 25 400 ?
MB306 (PNNL) 3 x 6 42 70 7 420 250
Lamprey (PNNL) 1.8 x 4.2 11 20 1.3 300 160
MB306 Design CG320 (top) vs.Lamprey battery (bottom)
Xiao, J., et al., SPIE, 10.1117/2.1201403.005403
PNNL Microbattery Design and Performance
March 24, 2017 9
0 2 4 6 8
1.61.82.02.22.42.62.83.0
Volta
ge (V
)
Discharge capacity (mAh)
MB306
Voltage drop during a pulse transmission at 0 °C
r.t., C/7
Chen, H., et al., Sci Rep, 4 (2014) 3790
Lamprey batteries at different discharge rate and temperatures
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
1.6
1.8
2.0
2.2
2.4
2.6
2.8
3.0
Vol
tage
(V)
Discharge capacity (mAh)
0.1 mA rt 0.3 mA rt 1 mA rt 0.1 mA 10 C 0.1 mA 0 C
Challenges and Solutions
March 24, 2017 10
Reduce parasitic weight and volume
Reduce voltage drop upon pulse current
Maximize material utilization
Challenges SolutionsLight packaging materials, novel sealing method
Nanosized cathode particle, C-coated current collector
Cathode design, fundamental study
of battery chemistry
A Dual Sealing method
March 24, 2017 11
Dual-sealing designFirst barrier of rubber provide temporary sealing and condition for epoxy curingSecond barrier of epoxies provide hermetic sealing
Sealing procedure of PNNL microbatteries
The length of jelly-roll cell core is 90% of the overall length in MB306
Wang, Y., et al., J Power Sources, 341 (2017) 443
A Dual Sealing method
March 24, 2017 12
Adhesive Name Weight Change (mg/day)
Devcon 10 minute epoxy −0.02
Apiezon wax W −0.1
Loctite 4311 UV-curable −0.08
Masterbond EP51FL −0.02
Loctite E-20HP Severe weight loss starting from day 5
Torr Seal epoxy No measureable weight loss in 8 months
The sealing is stable for at least 10 months at ambient conditionsIntimate bonding between adhesive and Al cases is critical.
UN38.3 test report
Wang, Y., et al., J Power Sources, 341 (2017) 443
0 100 200 300-0.20-0.15-0.10-0.050.000.050.100.150.20
Wei
ght c
hang
e (m
g)
Storage time (days)
MB306 Lamprey #1 Lamprey #2 Lamprey #3
A Dual Sealing method
March 24, 2017 13
0 4 8 12 16 20 24 28 323.25
3.30
3.35
OC
V (V
)
Time (day)
MB3 MB4
0 100 200 300 4000
50
100
150
200
Z'' (Ω
)
Z' (Ω)
MB3 1d MB3 30d MB4 1d MB4 30d
EVE MB306 cells sealed with the novel sealing method showed stable electrochemical performance for at least 30 days.
0 1 2 3 4 5 6 7 8
1.6
2.0
2.4
2.8
Volta
ge (V
)
Discharge capacity (mAh)
MB3 day30 MB4 day30 MB1 day1 MB2 day1
Wang, Y., et al., J Power Sources, 341 (2017) 443
The Challenge of High Cell Impedance (Lamprey)
March 24, 2017 14
0 50 100
20
40
60
80
100
Rs
(Ω)
Depth of Discharge (%)
Rs
0
500
1000
1500
2000
2500
Rct
Rct
(Ω)
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
1.61.82.02.22.42.62.83.0
Volta
ge (V
)
Discharge capacity (mAh)
Lamprey battery
0 1 2 3 4 5 6 7 8
1.8
2.0
2.2
2.4
2.6
2.8
3.0
3.2 Initialization
Cut-off: 2.13 V
Vol
tage
(V)
Time (s)
L130 46/900 L141 56/2800 L127 30/4000 L164 61/4300 L168 69/6200
Rs/Rct
Simulation of initialization process in real tags
If the cell impedance is too high, tags fail at initialization step
Large pulse current
Typical behavior of Li/CFx cell impedance as a function of DOD Activation (initial
discharge 1%) is requiredHigh voltage drop only occurs in lamprey cellsOnly a problem at the initialization stage of tag operation
The Challenge of High Cell Impedance (Lamprey)
March 24, 2017 15
0 20 400
5000
10000
15000
20000
Discharge 10%
Rct
(Ω)
Days
L124 L153
Discharge 1%
Typical impedance evolution of lamprey cells with/without C coating
Case study of high impedance cells
0.000 0.002 0.004 0.006 0.008 0.010 0.0122.0
2.2
2.4
2.6
2.8
3.0
Vol
tage
(V)
Capacity (mAh)
Bare Al mesh C-coated Al mesh
Voltage curve during activation
High and unstable impedance is likely due to contact resistanceC-coated Al mesh helps lower the impedance greatly
5 10 15 200
2000
4000
6000
8000
10000
No C coating With C coating
Rct
Days
Microbatteries of alternative formats and future directions
March 24, 2017 16
Future directionsCan we further improve energy and power densities?What is the size limit?Rechargeable?
Sturgeon tags Radio frequency tags
Tube batteriesEnergy harvesting tags
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
1.6
1.8
2.0
2.2
2.4
2.6
2.8
Volta
ge (V
)
Discharge capacity (mAh)
Lamprey battery1.9 mAh430 Wh/L240 Wh/kg
Summary
Non-rechargeable microbatteries of volume 42 mm3 and 11 mm3 with high energy density (400 Wh/L) have been developed at PNNLAcoustic and radio frequency microtransmitters powered by PNNL microbatteries extend the size limit of biology study subjects and potentially make great contribution to the conservation efforts of precious animal speciesDesign of microbatteries needs to be tailored to specific applicationsA novel sealing method was developed which greatly reduce parasitic weight and volume
March 24, 2017 17
Advanced Battery Facility
March 24, 2017 18
Dry room and pouch cell lineGroup research interest: high voltage cathode, Li metal, Li sulfur, silicon anode, Na battery, etc.
