High Temperature Primary Batteries for Venus Surface Missions

Dean Glass, John-Paul Jones, Abhijit Shevade and Ratnakumar Bugga

Eric Raub,* and Dharmesh Bhakta*
Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA 91109
*EaglePicher Technologies, Joplin, MO 64802

ECS PRiME Pacific Rim Meeting 2020

Honolulu, Hawaii
October 8, 2020
 Hostile Environment on Venus

• Of all the solar system's planets, Venus is the

closest to a twin of Earth.
• The two bodies are nearly of equal size, and Venus'
composition is largely the same as Earth’s.
• The orbit of Venus is also the closest to Earth's of any
solar system planet.
• Both worlds have relatively young surfaces, and both
have thick atmospheres with clouds (however, Venus'
clouds are mostly made of poisonous sulfuric acid).
• But not enough exploration, because of its hostile
environment
• High Temperature : 25oC at 55 km rapidly increasing to
465oC at the surface
• High pressure: CO2 pressure (90 atm) at the surface
• Corrosive environment: Concentrated H2SO4 droplets
in or above the clouds and sulfur compounds

Fig. 1 Venus temperature/pressure vs. altitude.

Fig.in-situ
Challenging environment for 1 Venusmissions
temperature/pressure vs. altitude

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Pre-Decisional Information – for Planning and Discussion Purposes Only
 Power Generation Challenging on Venus
For 300W at 60km altitude we need: 0.536 m 2 solar cells
Power Density from Solar Array Radioisotope Thermoelectric Generator (RTG)
Power, W/m2 B

Altitude, km

ray as a •function of altitude

Conventional on Venus.
power Fig. B shows
technologies, such the
as solar array or radioisotope power systems are challenging.
ous altitudes.
• Reduced solar flux below the clouds and at the surface: 2600 W/m2 (or roughly twice that of Earth’s solar
flux) at high altitudes and ~2-4 W/m2 at the surface.
• The current Multi-mission Radioisotope Thermoelectric Generator is not capable of operating at 90 bar
pressure and a +465°C heat sink.
• Dynamic RPS is promising but significant development is needed and also requires an energy storage
device for load levelling

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 State of Art Batteries
• There is no battery system that can survive the
Venus surface temperatures
• Li-ion batteries: Not stable above 70oC.
• Previous Venus mission used Li-SO2 batteries (-40
to +120oC). Even with thermal management, the
mission life is limited to a few hours.
• Some of the Li primary systems (Li-SOCl2) may be
modified for warm temperatures, up to 180oC.
• Thermal management system (phase change
materials) would need considerable mass and
volume at the expense of payload.
• There are a few high temperature (rechargeable)
batteries operational over 250-400oC but cannot
survive at >400oC

• There is no battery system currently available (either primary or rechargeable) that can
survive and operate at the Venus surface temperature (465oC)

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 Prior Venus Missions Japan Akatsuki Orbiter

• Orbiters: Russian Venera (4-13) series [4], the US Magellan and the
European Venus Express and Japan Akatsuki (2010)
In-situ Missions
• Balloons: Several missions have been implemented successfully, e. g.,
the Russian "VEGA" missions (1985). VEGA balloon (21 kg)
• Two balloons of 3.5m diameter super-pressure helium balloons with 7-kg
instrumented payload were deployed into the atmosphere, and floated for
48 hours at about 54 km altitude.
• Powered by primary batteries (1 kg of lithium batteries with 250 Wh), the
VEGA balloons operated only in the benign temperature regime.
• Surface missions (Lander/Surface Probes): Probes from the Venera VEGA lander (750 kg)
series, Vega program and Venera-Halley probes.
• Successfully landed on Venus and transmitted images of the Venus surface
but lasted only <2 h due to the failure of batteries and electronics, even
with extensive thermal insulation, phase-change materials and similar heat
sinks.
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 Long-Life In-situ Solar Explorer (LISSE)
• The Venus Lander mission concept project (being developed at
NASA Glenn Research Center) includes the design and
demonstration of a prototype instrument suite and supporting
system to function at the surface conditions of Venus and
communicate periodic measurements of temperature, pressure,
wind velocity and direction, and chemical composition to an
orbiter.
• Periodic (every 8 hr or better) measurements over the duration
of a Venus day-light period including the transitions at either
end, or approximately 60 Earth days, provide a unique and
significant science impact.
• Subsequently, a wind powered version and increasing RF
transmitter carrier frequency with a life expectancy of one Venus
year would be developed.
• High temperature power and electronics technologies are being
developed under NASA HOTTech program

Primary battery for 60 days and rechargeable battery for one year
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 High Temperature Battery Chemistry

• High capacity anode (Li alloys, e.g., Li-Si, Li-Al alloy)

• High energy cathodes
• Metal chalcogenides, Disulfides: FeS, FeS2, CoS2, NiS2, ZrS2, TiS2
• Metal Phosphorous Trisulfides: FePS3, MnPS3, CoPS3 and NiPS3
• Metal Halides (FeCl2 and NiCl2 and CFX)
• Molten salt electrolyte with low vapor pressure (mixed alkali metal
halides)
• Standard LiCl-KCl eutectic (44 wt% LiCl and 56 wt% KCl) (359oC)
• LiBr–KBr–LiF and LiBr–KBr–LiCl eutectics (melt at 324.5 and 321oC)
• LiCl:LiBr:KBr eutectic (12.05 wt% LiCl and 36.54 wt% LiBr and 51.41wt% KBr)
• LiF:NaF:KF eutectic.(29.2 wt% LiF, 11.7 wt% NaF and 59.1 wt% KF)
• Separators that minimize self-discharge.
• MgO, BN, Al2O3, Li2O

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 Cathode Materials for High Temperature Batteries
Electrochemical Characteristics Thermal Stability
Voltage, Sp. Sp. Energy,
Cathode
vs. Li Capacity, Wh/kg
FeS2 1.7 894 1520 FeS
FeS 1.7 610 1036
MoS2
CoS2 1.6 870 1392
Metal
NiS2 1.7 873 1484
Sulfides TiS2
TiS2 2.6 240 624
FeS2
MoS2 1.6 642 1027 CoS2
ZrS2 1.6 690 1104
Metal NiCl2 2.6 413 1074
Chlorides FeCl2 2.3 423 973
Metal FePS3 1.6 1318 2109
Phosphorous CoPS3 1.6 1248 1997
Trisulfides
CFx
NiPS3 1.7 1255 2134

Fluorides CFX 2.5 810 2025

MS < MS2 < MPS3 < CFX

• Thermal stability decreases as FeS >
MoS2 > CFx > CoS2 > FeS2 > TiS2

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 Laboratory High Temperature Cells
• Test conditions:
• Cell operation temperature → 475 OC
• Cell discharge time → 1 month (C/720 rate).
• Also used C/20 discharge rate to screen changes.
• Pellets prepared (13 mm die pressed at 8 metric tons) and
cells assembled in dry room
• Tested in glove box with ultra-low oxygen and moisture
content (<10ppm)

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 Electrochemical Characteristics of Cathodes
150
Norm. Current (A/mol cathode material)

100
FeS 475oC
FeS2

50 MoS2

-50

-100

Scan Rate 0.1 mV/s

-150
0 0.5 1 1.5 2 2.5
Potential (V)

• Original composition from literature:

• FeS2 & MoS2 have two discharge peaks
• Anode: LiAl:LiCl-KCl 65:35; Cathode: MSx:MgO:LiCl-KCl
• 1st Li+ intercalation and Fe/Mo reduction 70:10:20; and Electrolyte: LiCl-KCl:MgO 60:40
• FeS has only one discharge peak • FeS2 and MoS2 display multiple voltage plateaus
• Fe reduction • Li2TMS2 intermediates
• MoS2 peaks downshifted → less discharge potential • FeS displays smooth discharge curve and Higher specific
D. Glass, J. P. Jones, A. Shevade, D. Bhakta, E. Raub, R. Sim, R. V. capacity
Bugga, J. Power Sources 449 (2020) 227492; Fujiwara, S.; Inaba, M.; Tasaka, A. New Molten Salt Systems for High Temperature
Molten Salt Batteries: Ternary and Quaternary Molten Salt Systems Based on LiF-
LiCl, LiF-LiBr, and LiCl-LiBr. J. Power Sources 2011, 196 (8), 4012–4018
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 Optimization of Electrolyte : Binder Ratio
• Used LiCl-KCl eutectic blend 2
Original 20%
• Varied electrolyte concentration for electrodes 1.8
10% 5%
• Electrolyte leakage from cell 1.6
• Soft shorts 1.4

Potential (V)
1.2
• Lower concentrations → not enough
1
conductivity
0.8
• 20% electrolyte→ 95.6% discharge capacity 0.6
0.4 C/20 at 475oC
60% Electrolyte 20% Electrolyte 10% Electrolyte 5% Electrolyte
Electrode 0.2
(wt-%) (wt-%) (wt-%) (wt-%)
LiAl:LiCl-KCleu LiAl:LiCl-KCleu LiAl:LiCl-KCleu LiAl:LiCl-KCleu 0
Anode
(65:35) (80:20) (90:10) (95:5) 0 100 200 300 400 500 600 700
LiCl-KCleu:MgO LiCl-KCleu:MgO LiCl-KCleu:MgO LiCl-KCleu:MgO
Specific Capacity (mAh/g)
Electrolyte /
Separator (60:40) (20:80) (10:90) (5:95)

Cathode MS x :MgO:LiCl-KCleu :: 70:10:20 (M = Mo or Fe and x = 1 or 2)

D. Glass, J. P. Jones, A. Shevade, D. Bhakta, E. Raub, R. Sim, R. V. Bugga, J. Power Sources 449 (2020) 227492;

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 Stability of Cathode in the Electrolyte melt
• 20% electrolyte blend tested for stability over a range 2
of discharge rates C/20 C/170
475oC
• Cathode capacity decrease with increase discharge 1.5 C/720 C/7200

Potential (V)
duration
1
• Trend follows logarithmic decay
• Stability is an issue at longer discharge rates 0.5

2.0 0
C/20 C/170
475oC 0 10 20 30
1.6 C/720 C/7200 Discharge Time (days)
Potential (V)

1.2
120
0.8 475oC

Discharge Time/Discharge Rate

100

0.4 80

60
0.0
40
0 200 400 600 800 y = -15.5ln(x) + 146.41
20
Spec. Capacity (mAh/g)
0
D. Glass, J. P. Jones, A. Shevade, D. Bhakta, E. 0 2000 4000 6000 8000
Raub, R. Sim, R. V. Bugga, J. Power Sources 449 1/Discharge Rate (1/C)
(2020) 227492; Batteries for Venus Surface Missions
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 Cell Design Modifications
3-Pellet Stack 4-Pellet Stack
• 4 Pellet design:
Composite Cathode
• Press anode and electrolyte together Composite Cathode
Electrolyte Pellet
} Two pellets
• Press cathode and electrolyte together Electrolyte Pellet
Electrolyte Pellet
• ~13% enhancement discharge capacity vs. 3 pellet design Composite Anode Composite Anode } Two pellets

Li-FeS cell (with 4 Pellets) at C/2400

4 Pellet

D. Glass, J. P. Jones, A. Shevade, D. Bhakta, E. Raub, R. Sim, R. V. 26 days of operation on the Venus Surface!
Bugga, J. Power Sources 449 (2020) 227492;
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 Transition to Industry- Prototype Venus Lander Cells
(Cells fabricated by EaglePicher with the electrode and electrolyte powders provided by JPL)

Prototype Cells Tested in air at 455C Tested in Ar at 475C

• Prototype Cells manufactured b

Technologies with JPL materials
• Stainless steel can and
proprietary Seal
• Capacity: 1.58 Ah (Anode limited
• Prototype cells manufactured by • Discharged at C/1540 with C/10 • Discharged at C/1440 with C/10
EaglePicher Technologies with JPL pulses for 1 second after each 8h pulses for 2 min after each 8h
materials and recipe
• 26 days of operation and 52% of • 19 days of operation and 53% of
• Stainless steel can and header and
cathode utilization cathode utilization
proprietary seal
• Capacity: 1.58 Ah (anode limited)
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 Prototype Venus Lander Rechargeable Cell
(Cells fabricated by EaglePicher with the electrode and electrolyte powders provided by JPL)

2.0
EP Cell Discharged at ~C/2880 8hrs with ~C/20 pulses 2min
1.8

1.6

1.4

1.2

Potential (V)
1.0

0.8
3-4 weeks of
0.6
interruption
0.4 due to COVID
0.2

0.0
0 10 20 30 40 50 60 70 80 90
Discharge Time (days)

• Discharged at C/1440 with C/10 pulses for 2 min after • Discharged at C/2480 with C/20 pulses for 2 min after
each 8h and charged at C/20 in the first three cycles. each 8h and charged at C/20 in the first three cycles.
• Subsequently, the cell was recharged after 10 pulses. • There was about 3-4 weeks of interruption which had
no impact on the performance.
• In the last charge the cell was charged at CC-CV, i.e.,
with tapered current • Rechargeable battery can be tested during spacecraft
• Operated over 120 days at 475oC integration
• Higher capacity observed for the 2nd cycle
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 Prototype Venus Probe/Lander Rechargeable Cell
DAVINCI+
(Deep Atmosphere Venus Investigation of
Noble gases, Chemistry, and Imaging)
Probe life: 8h after
deployment from the orbiter

• Discharge at successively decreasing rates (C/20, C/50, C/100 and C/500)

• High efficiency, i.e., 71% of theoretical cathode capacity at C/20
• No change in the capacity at C/50 vs C/20 (with an improvement the
voltage), while at C/100, there is a slight reduction in the capacity.

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 MPS3 Cathode Materials
• Transition metal phosphorous trisulfides have higher specific capacity than mono or disulfides
• Capacity of 1250-1318 mAh/g (vs 610 mAh/g for FeS) at the same voltage of 1.6-1.7 V
• Synthesized by mixing stoichiometric amounts of highly pure metal powder (Fe or Ni), red
phosphorous and sulfur and placed in quartz tube, which was then evacuated and heated to 970-
1070K for one week
TGA of Cathode Materials at 10 OC/min XRD of Cathode Materials at 10 OC/min

FePS3 NiPS3

Dean Glass, John-Paul Jones, Abhijit Shevade, and Ratnakumar Bugga, J. Electrochem. Soc., 2020 167 110512

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 FePS3 and NiPS3 Cathode Materials – Cyclic Voltammetry
1) FePS3 + 1.5Li+ + 1.5e- ↔ Li1.5FePS3
2) Li1.5FePS3 + 4.5Li+ + 4.5e- → 3Li2S + Fe + P CV scan at 0.1 mV/s
3) P + 3Li+ + 3e- → Li3P

0.08 DG-07a-FePS3 CV scan at 0.1 mV/s DG09a-NiPS3 Cell CV Scan at 0.1 mV/s
0.1
2nd Scan
0.06 0.08 3rd Scan
475oC 2nd Scan
0.06 4th Scan
0.04 3rd Scan 5th Scan
4th Scan 0.04
Current (A)

0.02 5th Scan 0.02

Current (A)
0 0
-0.02
-0.02
-0.04
-0.04 -0.06

-0.06 -0.08
0 0.5 1 1.5 2 2.5 0 0.5 1 1.5 2 2.5
Potential (V) Potential (V)
• Multiple lithium ions intercalated/reduced
Dean Glass, John-Paul Jones, Abhijit Shevade, and Ratnakumar Bugga, J. Electrochem. Soc., 2020 167 110512

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 Preliminary Discharge Curves of TMPS3 Materials
2.5
475oC
2 FeS FePS3 NiPS3

Potential (V)
1.5

0.5

0
0 200 400 600 800
Spec. Discharge Capacity (mAh/g)

• FeS: ~95% discharge capacity at C/20 rate

• NiPS3: ~50% discharge capacity at C/20 rate. Higher voltage
• Equivalent to spec. discharge capacity (in mAh/g) of FeS
• FePS3: ~35% discharge capacity at C/20 rate
• Different plateaus could signify different phases of TMPS3 during discharge
Dean Glass, John-Paul Jones, Abhijit Shevade, and Ratnakumar Bugga, J. Electrochem. Soc., 2020 167 110512

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 Cathode coatings to improve stability

2.4
• Reduce cathode dissolution with surface 2.2
coatings 2.0
• ALD coating of Al2O3 (NREL) 1.8
FeS AlPO4 AlBO3 Al2O3
NREL-BENEQ
Al2O3

• Coating of AlPO4 and AlBO3 by wet chemical 1.6

method 1.4

• There is an improvement in the cathode

Potential (V)
1.2
efficiency and capacity with surface coating 1.0

• 50% improvement observed with AlBO3 coating 0.8

in laboratory cells compared to pristine FeS 0.6

cathode 0.4

• Prototype cell demonstration with the AlBO3- 0.2

coated FeS cathode underway 0.0

0 4 8 12 16 20
Discharge Time (days)

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 Solid Electrolytes for Cathode and Separator
• Motivation: Use a solid electrolyte DG12a-FeS Cell with LLZTO Separator Discharge at ~C/720 rate
as a separator in place of 2.5

electrolyte-binder pellet to 475oC

minimize sulfide solubility 4 days offline at
2
RT
• Solid electrolytes:

Potential (V)
• Oxide based solid electrolytes 1.5

(Garnets)
• LLZO (Li7La3Zr2O12) 1

• Lithium-Lanthanum-
Zirconium-Tantalum-Oxide 0.5
from Toshima, Japan
• Sulfide glasses 0
0 1 2 3 4 5 6 7 8 9
• LGPS (Li10GeP2S12) Discharge Time (days)
• Phosphate based LiSICONs
• Lithium Aluminum Titanium
Phosphate (Ohara)
• LLZTO intact and easily separated from pellets

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 Path Towards Technology Validation for the Venus Probe
• Develop a prototype cell with high strength and high- 2-Cell stack (Laboratory)
temperature tolerant alloy (cell case and header)
FeS Two-cell series discharged at ~C/720
4.0
• Develop a pressure-tolerant (92bar) cell design
3.5
• Demonstration of cell performance in simulated Venus 3.0
environment, i.e., in the Glenn Extreme Environments FeS Two-cell series discharg
2.5
Research (GEER) chamber at NASA-GRC 4.0

Potential (V)
3.5
2.0 Cathode

• Develop bipolar cell design for multi-cell batteries Electrolyte

Anode
3.0
1.5
Stainless Steel

• Optimize cell design for improving specific energy (goal of Spacer 2.5

Potential (V)
1.0
50-100 Wh/kg) 2.0

0.5 Heating Strips 1.5

• Develop prototype multi-cell Venus probe battery with the 0.0 1.0

desired voltage and capacity (not form and fit) 0 1 2 3 4

0.5
Time (days)
5 6 7 8

• Demonstrate battery performance in GEER 0.0

0 1 2 3 4
Time (days)
• Test prototype Venus Probe Battery for the flight
environments

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Venus Lander Batteries
Pre-Decisional Information – for Planning and Discussion Purposes Only
 Summary and Conclusions

• Molten salt based batteries with Li alloys and metal sulfide cathode with
optimized cell design have lifetimes of ~30 days at Venus surface
temperatures.
• These systems have shown good rechargeability and may be coupled with an
energy generation source (e.g., wind power, solar, RTG) for extended surface
studies on Venus
• Strategies to improve operational life and specific energy include:
• Surface coatings on FeS
• New cathodes
• New electrolyte with reduced cathode dissolution, may be solid electrolytes
• New cell and (multi-cell) battery designs
• These batteries enable new missions with extended scientific studies on the
surface of Venus.

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Pre-Decisional Information – for Planning and Discussion Purposes Only
 The work described herein was carried out at the Jet Propulsion Laboratory, California
Institute of Technology, under contract with National Aeronautics and Space
Administration (NASA), and supported by NASA HOTTech Program.

10/13/2019