J. Barker, R.J. Heap, N. Roche, C. Tan, R. Sayers and Y. Lui
Faradion Limited
Kroto Innovation Centre
University of Sheffield
Sheffield S3 7HQ
United Kingdom
Faradion Limited, 2014
Low Cost Na-ion Battery Technology
Low Cost Na-ion Battery Technology
1
Faradion Limited, 2014
Company Introduction
Faradion Limited is an early stage company (est. 2011) engaged
in the development of low-cost, non-aqueous sodium-ion (Naion) rechargeable batteries for automotive, utility and
consumer sectors.
Low Cost Na-ion Battery Technology
Faradion has also developed low-cost methods for the
synthesis of LiFePO4 and other active materials. These methods
will allow the manufacture of the lowest cost LiFePO4 in the
industry, while still retaining outstanding electrochemical and
safety performance. (Abstract#996 - October 29, 10:40 h)
During its screening of new Na-ion cathode materials, the
companyNon-aqueous
has discoveredNa-ion
a number
of novel
Li-ion cathode
Battery
Technology
phases.
2
2
Oxford, England
.
.
Faradion Limited, 2014
Sheffield, England
Low Cost Na-ion Battery Technology
Company Locations in UK
3
Low Cost Na-ion Battery Technology
Na-ion Batteries: Background
4
Faradion Limited, 2014
Sodium
0.98
23.0
0.3
180
98
<0.005
7000
Tet/Oct
2.6
<200
Oct/Prismatic
Cathode Materials
Layered Oxides,
Spinels, Polyanions,
Halides etc.
Layered Oxides,
Polyanions, Halides
etc.
Anode Materials
Graphite, Hard Carbon,
Oxides, Composites,
Conversion etc.
Hard Carbon, Oxides,
Composites,
Conversion etc.
IP Position (Battery Materials)
Complex
Simpler
E0 vs Li/Li+
o
Melting Point [ C]
Natural Abundance in Earth's Crust [%]
Carbonate Cost [$/tonne]
Ion Co-ordination
Faradion Limited, 2014
Lithium
0.76
6.9
0.0
Property
Ionic Radius [Å]
Atomic Mass [g/mol]
Low Cost Na-ion Battery Technology
Properties: Li vs. Na
5
Faradion Electrolyte + Separator
+
Al (cc)
Faradion Hard Carbon
Al(cc)
Faradion Cathode
4 cm2 or 100 cm2
Typical Faradion Na-ion Pouch Cells
Low Cost Na-ion Battery Technology
-
Faradion Limited, 2014
Na-ion Pouch Cells
Typical cell capacity = 10-12 mAh (4 cm2) and 250-300 mAh (100 cm2)
Typical Bi-cell capacity = 500-600 mAh (100 cm2)
6
S-Y-Hong et al. Energy Environ Sci. 2013
DOI: 10.1039/C3EE40811F
Faradion Limited, 2014
• Anode: Hard Carbons (Commercial and Proprietary)
• Electrolyte: Typically NaClO4-PC or NaPF6 EC/DXC/PC
• Cathode: More than 90 classes of novel active materials screened so far!
1. Polyanions: Phosphates
2. Na3M2XO6 and Na2M2X’O6: O3 and P2 structural types
3. Layered Oxides: O3-structural types
We want to be here!
Low Cost Na-ion Battery Technology
Faradion Cell Chemistry
7
Low Cost Na-ion Battery Technology
Anode Materials
8
Faradion Limited, 2014
1000-1200oC
Nitrogen
250-350oC
Air
Faradion Limited, 2014
Hard Carbon Synthesis
De-water
Foam
Milling
Fine
Powder Pressing
Pellet
Pyrolysis
and
milling
Fine
Powder
[20-100 g scale]
Schematic: Example Preparative Route for Faradion Hard Carbon
Low Cost Na-ion Battery Technology
Carbohydrate
9
Broad reflections indicate the
disordered nature of the HC
Commercial
Faradion Limited, 2014
XRD Profiles
Low Cost Na-ion Battery Technology
Parallel stacks of
graphene sheets,
d002 spacing ~ 3.8 Å
cf Graphite = 3.35 Å
XRD (CuKα) Profiles for Commercial and Faradion Hard Carbons
10
(B) Na
insertion into
nano-pores
1.5
1.0
0.5
300
250
200
150
100
50
0
0
0
50
100
150
200
250
300
350
400
Low Cost Na-ion Battery Technology
(A) Na insertion
2.5
into
graphene
interlayer
space
2.0
Reversible Specific Capacity [ mAh/g]
Electrode Potential [V vs. Na]
Typical particle
sizes = 2-8 μm
Faradion Limited, 2014
Hard Carbon: Faradion
1
2
3
4
5
6
7
8
9
10
Cycle Number
Specific Capacity [mAh/g]
Faradion Hard Carbon vs. Na = 280 mAh/g
FCL = 26%
11
Low Cost Na-ion Battery Technology
Cathode Materials
12
Faradion Limited, 2014
Phosphates
Na7M4(P2O7)4PO4
Na7M3(P2O7)3
Na4M3(PO4)2P2O7
Na3M2XO6
Na2M2X’O6
O3-Na3Ni2SbO6
P2-Na2Ni2TeO6
Layered Oxides
NaNi1-x-y-zM1xM2yM3zO2
Faradion Limited, 2014
Database of Na Cathode Materials > 90 classes in total
Low Cost Na-ion Battery Technology
Na Cathodes
13
Low Cost Na-ion Battery Technology
Phosphates
14
Faradion Limited, 2014
•
•
•
•
Na7M4(P2O7)4PO4; M = V, Fe, Cr, Al etc.
3D framework of MO6 octahedra, P2O7 groups + isolated PO4 tetrahedra
Na+ ions (3 sites) located within cavities in the 3D framework
Tetragonal structure, space group P421c
4000
3000
4
3
2
1
0
20
40
60
80
100
Cathode Specific Capacity [mAh/g]
120
2000
1000
0
-1000
-2000
-3000
-4000
2.5
3.0
3.5
4.0
4.5
Electrode Potential [V vs. Na]
Na7V4(P2O7)4PO4 vs. Na
• Theoretical specific capacity (6 Na per FU; V3+  V5+) = 162 mAh/g
• Achievable reversible specific capacity = 58 mAh/g
Low Cost Na-ion Battery Technology
Electrdeo Potential [V vs Na]
-1
Differential Capacity, dQ/dV [mAh g /V]
5
Faradion Limited, 2014
Na7M4(P2O7)4PO4
15
Na4M3(PO4)2P2O7; M = Fe, Co, Ni, Mn etc.
3D framework of PO4 tetrahedra, MO6 octahedra and P2O7 groups.
Na+ ions (4 sites) located within tunnels in the 3D framework
Orthorhombic structure, space group Pn21a
800
Differential Capacity, dQ/dV [mAh g /V]
4.0
Electrode Potential [V vs. Na]
-1
3.5
3.0
2.5
2.0
1.5
1.0
0
20
40
60
80
100
Cumulative Cathode Specific Capacity [mAh/g]
600
400
200
0
-200
-400
-600
1.0
1.5
2.0
2.5
3.0
3.5
4.0
Electrode Potential [V vs. Na]
Na4Fe3(PO4)2P2O7 vs. Na
• Theoretical specific capacity (3 Na per FU; Fe2+  Fe3+) = 129 mAh/g
• Achievable reversible specific capacity = 86 mAh/g
• Fe phase prepared at around 500oC (single-step, solid-state)
Low Cost Na-ion Battery Technology
•
•
•
•
Faradion Limited, 2014
Na4M3(PO4)2P2O7
16
Low Cost Na-ion Battery Technology
Faradion Limited, 2014
Na3M12-xM2xXO6
and
Na2M12-xM2xX’O6
17
•
•
•
•
•
•
Example phase, Na3Ni2SbO6 – monoclinic structure, C2/m
O3-layered structure, with M/X cation ordering within the slabs
XO6 ocahedron surrounded by 6 MO6 octahedra – honeycomb network
Na ions occupy the interlayer space
Na3Ni2SbO6 – Theoretical specific capacity = 199 mAh/g
Na3Ni1.5Mg0.5SbO6 – Theoretical specific capacity = 208 mAh/g
Faradion Limited, 2014
• Sodium oxo-Metallates = O3-Na3M12-xM2xXO6 or P2-Na2M12-xM2xX’O6
• M1, M2 = Ni, Co, Fe, Cu, Mn, Mg, Ca, Zn etc.
• X = Sb, Bi, Nb, Ta etc.; X’ = Te, Se etc.
Low Cost Na-ion Battery Technology
Na3M12-xM2xXO6 and
Na2M12-xM2xX’O6
18
500
400
4
3
2
1
0
0
20
40
60
80
100 120 140
Cathode Specific Capacity [mAh/g]
300
200
100
0
-100
-200
-300
-400
1.5
2.0
2.5
3.0
3.5
4.0
4.5
Electrode Potential [V vs. Na]
Na3Ni1.5Zn0.5SbO6 vs. Na
• Ni, Co, Fe, Mn, Cu etc. are all active redox centres
• Charge#2 = 125 mAh/g; Discharge#2 = 115 mAh/g (Cycle#2)
• Average Voltage = 3.34 V vs. Na
Low Cost Na-ion Battery Technology
Electrode Potential [V vs Na]
-1
Differential Capacity, dQ/dV [mAh g /V]
5
Faradion Limited, 2014
Na3Ni1.5Zn0.5SbO6 vs. Na
19
300
Cell Voltage [V]
4
3
2
1
0
0
50
100
Cathode Specific Capacity [mAh/g]
200
100
0
-100
-200
-300
0
1
2
3
Cell Volltage [V]
Hard Carbon//Na3Ni2-xZnxSbO6 (x=0.5)
• Diffuse Differential Capacity Response
• Charge#2 = 135 mAh/g; Discharge#2 = 120 mAh/g
• Average Voltage = 3.26 V
4
5
Low Cost Na-ion Battery Technology
-1
Differential Capacity [mAh g /V]
5
Faradion Limited, 2014
Na-ion: Na3Ni1.5Zn0.5SbO6
20
Low Cost Na-ion Battery Technology
NaNi1-x-y-zM1xM2yM3zO2
21
Faradion Limited, 2014
•
•
•
•
Easy synthesis is air – typically 900oC
For cost reasons we minimize [Ni] but maximize specific capacity
Prepared material is essentially phase pure
No NiO contamination (bad actor electrochemically)
Faradion Limited, 2014
• NaNi1-x-y-zM1xM2yM3zO2: O3-type layered oxide, ABCABC stacking
• Na ions in the interlayer space
Low Cost Na-ion Battery Technology
NaNi1-x-y-zM1xM2yM3zO2
22
1000
4
3
2
1
0
0
50
100
150
Cathode Specific Capacity [mAh/g]
200
800
600
400
200
0
-200
-400
1.5
2.0
2.5
3.0
3.5
4.0
4.5
Electrode Potential [V vs. Na]
NaNi1-x-y-zM1xM2yM3zO2 vs. Na - 2nd Cycle
• Charge Capacity = 185 mAh/g; Discharge Capacity = 165 mAh/g
• Average Discharge Voltage = 3.1 – 3.3 V vs. Na (depends on
composition)
Low Cost Na-ion Battery Technology
Electrode Potential [V vs Na]
-1
Differential Capacity, dQ/dV [mAh g /V]
5
Faradion Limited, 2014
NaNi1-x-y-zM1xM2yM3zO2 vs. Na
23
150
Cell Voltage [V]
4
3
2
1
0
0
50
100
150
Cathode Specific Capacity [mAh/g]
100
50
0
-50
-100
-150
0
1
2
3
4
5
Cell Volltage [V]
Hard Carbon // NaNi1-x-y-zM1xM2yM3zO2 - 2nd Cycle
• Charge Capacity = 165 mAh/g; Discharge Capacity = 165 mAh/g
• Average Discharge Voltage = 3.00 V
Low Cost Na-ion Battery Technology
-1
Differential Capacity [mAh g /V]
5
Faradion Limited, 2014
Na-ion: NaNi1-x-y-zM1xM2yM3zO2
24
Low Cost Na-ion Battery Technology
Na-ion Cells: Performance
25
Faradion Limited, 2014
100
140
120
80
100
60
80
C/20 Charge/Discharge
60
40
40
20
20
0
50
100
150
200
250
300
0
350
Cycle Number
Hard Carbon//NaNi1-x-y-zM1xM2yM3zO2 Layered Oxide
• Pouch Cell
• 1.0 – 4.2 V CC/CV @30oC
• C/10 Rate Charge and Discharge
% Discharge Capacity
Cathode Specific Capacity [mAh/g]
160
Faradion Limited, 2014
CELL#306008 FARADION Na-ion CELL
Low Cost Na-ion Battery Technology
Na-ion Cycling: C/10
26
CELL#301056 FARADION Na-ion CELL - STORAGE @C/10 RATE
120
80
6-Months RT
Storage at
Full Charge
60
40
20
0
20
40
60
80
100
120
Cycle Number
Hard Carbon//NaNi1-x-y-zM1xM2yM3zO2 Layered Oxide
• Pouch Cell
• 1.0 – 4.2 V CC/CV @30oC
• C/10 Rate Charge and Discharge
Low Cost Na-ion Battery Technology
% Discharge Capacity
100
Faradion Limited, 2014
Storage Properties:
6 Months @RT
27
o
Na-ion Cell (Cell#302026) Rate Performance @25 C
3
2
1
0
5C
0
20
40
60
4C
80
3C
2C
C C/2 C/5 C/10
100
120
140
Cathode Specific Capacity [mAh/g]
Hard Carbon//NaNi1-x-y-zM1xM2yM3zO2 Layered oxide
• Pouch Cell, ENERGY cell not optimized for POWER
• 1.0 – 4.2 V CC/CV @30oC
• C/10 Rate Charge and Discharge
Low Cost Na-ion Battery Technology
Na-ion Cell Voltage
4
Faradion Limited, 2014
Na-ion: Rate Performance
28
18650 - Energy Cell - Prediction
Cell Chemistry : Graphite // LiFePO4
Cell Chemistry : Hard Carbon // Layered Oxide
Prescription
Activity Material
Residual Carbon
Conductivity Carbon
Binder
Total Long
Foil Thickness(mm) Cu and
Al
1st coat surface long
2nd coat surface long
Coat both single surfaces total
long
Single side thickness not
including foil's thickness
both side including foil
thickness
Width of electrode
single electrode total coat area
Material Coat Wt (g) /cm2
Total Coat Wt (g)/cm2
Theoetical Capacity / g
Reversible Capacity / g
Non reversible Cap.
Capacity / unit area
Press Stretch Rate
Real Unit Area Capacity
Unit Area of C/A Weight
compare
Whole electrode of C/A
Weight Compare
Predicted Capacity
%FCL
Average Discharge Voltage
Cell Energy
Cell Volume
Cell Weight
Predicted Energy Density
Predicted Specific Energy
Cathode
Material / Name
LiFePO4
Residual from synthesis
Anode
Rate / Spec
Material / Name
Rate / Spec
92.00% Graphite
92.75%
2.00% Anode Additive
0.25%
Conductive
Conductive Carbon
2.00% Carbon
3.00%
PVDF/ (High
PVDF/ (High MW)
4.00% MW)
4.00%
664 mm
670 mm
0.02 mm
624 mm
607 mm
0.015 mm
653 mm
603 mm
1231 mm
1256 mm
0.0820 mm
0.0500 mm
0.184 mm
0.115 mm
5.6 cm
5.75 cm
689.36 cm^2
722.2 cm^2
0.016192 g/cm^2
0.0072 g/cm^2
0.0176 g/cm^2
0.00780 g/cm^2
140 mAh/g
360 mAh/g
125 mAh/g
300 mAh/g
10
20 mAh/g
2.02 mAh/cm^2
2.06 mAh/cm2
100.3 %
100.1 %
2.02 mAh/cm^2
2.06 mAh/cm2
Unit Area of A/C
Capacity
2.234 Compare
1.021
Whole Electrode
A/C Capacity
2.132 Compare
1.069
1395 mAh
First Charge Cap.
1563
10.7 %
3.20 V
4.46 Wh
16.5 cm^3
45.0 g
270 Wh/l
99 Wh/kg
Graphite//LiFePO4
Li-ion Industry Standard
99 Wh/kg
Prescription
Activity Material
Residual Carbon
Cathode
Material / Name
Layered Oxide
Residual from synthesis
Conductivity Carbon
Conductive Carbon
Anode
Rate / Spec
Material / Name
Rate / Spec
94.00% Hard Carbon
92.75%
0.00% Anode Additive
0.25%
2.00% Conductive Carbon
PVDF/ (High
4.00% MW)
478 mm
3.00%
Binder
PVDF/ (High MW)
4.00%
Total Long
472 mm
Foil Thickness(mm) Al both
sides
0.02 mm
0.02 mm
1st coat surface long
432 mm
461 mm
2nd coat surface long
415 mm
421 mm
Coat both single surfaces total
long
847 mm
882 mm
Single side thickness not
including foil's thickness
0.0820 mm
0.0500 mm
both side including foil
thickness
0.184 mm
0.120 mm
Width of electrode
5.6 cm
5.75 cm
single electrode total coat area
474.32 cm^2
507.15 cm^2
Material Coat Wt (g) /cm2
0.02491 g/cm^2
0.0164 g/cm^2
Total Coat Wt (g)/cm2
0.0265 g/cm^2
0.01770 g/cm^2
Theoetical Capacity / g
200 mAh/g
360 mAh/g
Reversible Capacity / g
150 mAh/g
240 mAh/g
Non reversible Cap.
20
120 mAh/g
Capacity / unit area
3.74 mAh/cm^2
3.74 mAh/cm2
Press Stretch Rate
100.3 %
100.1 %
Real Unit Area Capacity
3.73 mAh/cm^2
3.74 mAh/cm2
Unit Area of A/C
Unit Area of C/A Weight
Capacity
compare
1.514 Compare
1.004
Whole Electrode
Whole electrode of C/A
A/C Capacity
Weight Compare
1.416 Compare
1.073
Predicted Capacity
1772 mAh
First Charge Cap.
2363
%FCL
25.0 %
Average Discharge Voltage
3.20 V
Cell Energy
5.67 Wh
Cell Volume
16.5 cm^3
Cell Weight
45.0 g
Predicted Energy Density
343 Wh/l
Predicted Specific Energy
126 Wh/kg
Hard Carbon//Layered Oxide
Faradion Na-ion
126 Wh/kg
Faradion Limited, 2014
18650 - Energy Cell - Prediction
Low Cost Na-ion Battery Technology
Na-ion: 18650 Comparison
29
• Demonstrated state-of-the-art Na-ion battery performance >300 cycles
• Screened a large range of novel Cathode Materials (>90 classes)
Faradion Limited, 2014
Faradion Na-ion: Summary
• Hard Carbon Anode gives comparable performance to commercial grade
• Preliminary safety data (not shown here) looks encouraging (at a
material level)
• Cycle life and energy density, rate similar to commercial Li-ion cells
Low Cost Na-ion Battery Technology
• Selected best Cathode iterations for (i) energy; (ii) power; (iii) cost
• Cost Analysis (not shown here) looks encouraging……suggesting
significantly cheaper than equivalent Li-ion
30
Dr. Richard Heap
Noel Roche
Dr. Chaou Tan Dr. Ruth Sayers
Dr. Yang Lui
For more information:
jerry.barker@faradion.co.uk
www.faradion.co.uk
Faradion Limited, 2014
Low Cost Na-ion Battery Technology
Acknowledgements
31