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Public
C. Brünig / G. Nuspl
BL Energy Storage
08.10.2014
Striving for energy density
HIGH VOLTAGE MATERIALS
FOR LITHIUM ION BATTERIES
C. Brünig / G. Nuspl, BL Energy Storage, 08.10.2014
Table of contents
Public, Striving for energy density 2
Corporate introduction 3
Business line Energy Storage 7
Clariant high volt materials 11
Lithium cobalt phosphate LiCoPO4 13
High volt spinel LiMn1,6Ni0,4O4 15
Summary 24
C. Brünig / G. Nuspl, BL Energy Storage, 08.10.2014
Historical milestones
Public, Corporate Introduction 4
Clariant has come a long way – now we are going beyond what has already been
achieved
2013 2011
2009/2010
2000
1997
1995
Acquisition of Süd-Chemie Divestment of 5 Businesses
Clariant Spin-Off and IPO
Acquisition of Hoechst Specialty Chemicals
Acquisition of BTP
Restructuring
2000 – 2009
2009 – 2010 ff.
1995 – 2000
C. Brünig / G. Nuspl, BL Energy Storage, 08.10.2014
Employees 2013
18 099
Business Areas
EBITDA 2013 (CHF m)
before exceptionals
14.1%
Net result 2013 (CHF m)
from continuing operations
Sales 2013 (CHF m)
from continuing operations
A globally leading company in specialty chemicals
Public, Corporate Introduction 5
Clariant focuses on creating value
through innovation and sustainability.
6 076
858 EBITDA margin 2013
before exceptionals
323
4
Corporate Center, Pratteln, Switzerland
C. Brünig / G. Nuspl, BL Energy Storage, 08.10.2014
Four Business Areas* The right portfolio with leading market positions
Public, Corporate Introduction 6
Care
Chemicals
Catalysis
& Energy
Natural
Resources
Plastics
& Coatings
SALES
(CHF m) 1 561
EBITDA** (CHF m) 263
EBITDA
MARGIN** 16.8%
*Results full year 2013
**Before exceptional items, as reported
SALES
(CHF m) 713
EBITDA** (CHF m) 159
EBITDA
MARGIN** 22.3%
SALES
(CHF m) 1 281
EBITDA** (CHF m) 195
EBITDA
MARGIN** 15.2%
SALES
(CHF m) 2 521
EBITDA** (CHF m) 356
EBITDA
MARGIN** 14.1%
C. Brünig / G. Nuspl, BL Energy Storage, 08.10.2014
8
Global HQ for Business Line Energy Storage relocate from Munich
to Singapore as of 1st January 2013
R&D/pilot facilities Production facilities
• R&D facility and pilot plants
• LFP (P2S), LTO
• LMFP, LMNO
• Opened in 20081
Moosburg, Germany
• LFP plant (P2, P2E)
• Opened in 2012
• Sales Office
• Capacity expansion
Candiac, Canada
1 Start of regular production
Switzerland, Pratteln
• LiFePO4 + C Licensing AG
Legal Entity Headquarter
Singapore
• Headquarter
Sales Office
Tokyo, Japan
• Sales Office
South Korea
• Sales Office
Munich, Germany
• Sales Office
Shanghai, China
• Sales Office
Wisconsin, USA
• Sales Office
Public, Business Line Introduction
C. Brünig / G. Nuspl, BL Energy Storage, 08.10.2014
9
• Powder
• Life Power ® P2 very high rate capability due to
small primary particles
• Life Power ® P2E reduced BET surface area and
increased D50 versus P2 for
reduced solvent demand and
easier dispersion
• Spherical agglomerates
• Life Power ® P2S spherical agglomerates for easier
product handling and electrode coating
Group of materials
Physical
characteristics
Grades
LFP - Clariant’s main cathode material
P2 & P2E P2S
Public, Business Line Introduction
C. Brünig / G. Nuspl, BL Energy Storage, 08.10.2014
Clariant’s roadmap for Energy Storage
10
LiFePO4 LiMnPO4 LiCoPO4 LiNiPO4
5V – High-Voltage Materials
LiMn2O4 LiMn2-xNixO4
Li4Ti5O12
Public, Business Line Introduction
Public
C. Brünig / G. Nuspl
BL Energy Storage
08.10.2014
New Cathode Materials
CLARIANT’S
HIGH-VOLT MATERIALS
C. Brünig / G. Nuspl, BL Energy Storage, 08.10.2014
High volt materials
Public, New Cathode Materials 12
3 possible candidates (and derivatives of these)
Nickel manganese spinel
LiMn2-xNixO4
Lithium cobalt phosphate
LiCoPO4
Lithium nickel phosphate
LiNiPO4
Promising results in
battery test, good cycle
life, good rate capability,
positive safety test
Synthesis of fine
particulate and phase
pure samples possible,
till now no battery tests
with an acceptable cycle
life, problems during
safety tests
Synthesis phase pure
samples possible, till
now impossible to
charge/discharge the
material in half cells,
also no positive results
in literature
C. Brünig / G. Nuspl, BL Energy Storage, 08.10.2014
Public, New Cathode Materials 13
– Synthesis of phase pure and fine particulate
powders possible with Clariant synthesis
routes
– Till now the tested materials show strong
capacity loss after a few cycles
Lithium cobalt phosphate - LiCoPO4
C. Brünig / G. Nuspl, BL Energy Storage, 08.10.2014
Public, New Cathode Materials 14
Lithium Cobalt Phosphate - LiCoPO4
– Thermal behavior of LCP is different from LFP and LMP
– Thermal behavior of LCP is depending on the state of charge
Experimental investigation on the electrochemical and thermal behavior of LiCoPO4-based cathode
Journal of Power Sources, Volume 222, 15 January 2013, Pages 72-78
Simon Theil, Meike Fleischhammer, Peter Axmann, Margret Wohlfahrt-Mehrens
Fully charged Fully charged
C. Brünig / G. Nuspl, BL Energy Storage, 08.10.2014
Public, New Cathode Materials 15
– Voltage vs. Li°/Li+: 4.75V
– Voltage vs. C-anode (graphite) 4.5 V
– Theoretical spec. capacity: 147 mAh/g
– Spec. Energy (powder, theo.) 655 Wh/kg
– Energy Density 2670 Wh/l
– Rechargeable spec. Capacity: ≈135 mAh/g
Practical reality of a high volt Li-Ion Battery is still an open question!
suitable electrolyte with stability between -0.5 to 5.5V for the 4.5 V
Li-Ion Battery required
High volt spinel - Basic information -
C. Brünig / G. Nuspl, BL Energy Storage, 08.10.2014
High volt spinel Energy Density on cell level
16
Projected energy density of a 18650 cell with graphite anode compared to other
cathode materials and assuming equal electrode loadings and porosities
5V-Spinel offers the
opportunity of raising energy
density on cell level vs. NMC
by roundabout 20%.
The higher cell voltage of 5V-
spinel offers an additional
benefit on pack level by a
reduced number of cells in
series.
Public, New Cathode Materials
C. Brünig / G. Nuspl, BL Energy Storage, 08.10.2014
– High volt spinels form solid solutions for different ratios of manganese and nickel
– Focus on LiMn1,6Ni0,4O4
Public, New Cathode Materials 17
High volt spinel - LiMn2-xNixO4 -
– phase pure samples
– Particle size distribution: D(0,50) ≈ 7-8 µm
– BET-surface: ≈ 1 qm/g
– Press density: ≈ 2.3 g/cm3
C. Brünig / G. Nuspl, BL Energy Storage, 08.10.2014
High volt spinel - Battery tests -
Public, New Cathode Materials 18
– Battery test results:
- Capacity values ≈ 135 mAh/g @ C/2, close to theoretic capacity of 147 mAh/g
- Electrolyte FEC:DMC 1:4, half cell testing
- Good cycle life for 200 cycles in half cells
C. Brünig / G. Nuspl, BL Energy Storage, 08.10.2014
High volt spinel - Battery tests -
Public, New Cathode Materials 19
C/5 / D/5, 25 °C
100 cycles
– Tests at CEA institute show that the results are reproducible
– Also good results at higher temperature
C/5 / D/5, 55 °C
100 cycles
C. Brünig / G. Nuspl, BL Energy Storage, 08.10.2014
High volt spinel - Battery tests -
Public, New Cathode Materials 20
– Rate capability testing had shown very promising results
– Loading about 5 mg/cm2 (thin electrode)
1/2D 1D 3D 5D 10D
C. Brünig / G. Nuspl, BL Energy Storage, 08.10.2014
High volt spinel - Battery tests / results of customers -
Public, New Cathode Materials 21
– Full cell test vs. graphite
- 25 °C, cycled with 1 C, 100 % DOD
C. Brünig / G. Nuspl, BL Energy Storage, 08.10.2014
High volt spinel - dissolution of manganese -
Public, New Cathode Materials 22
– Manganese dissolution is a key factor in limiting cycle and calendar life of
manganese spinel (LMO) cells
– Soaking test of a 4 V spinel sample compared with a high volt spinel
– Electrode films prepared from both samples
– Stored in EC:DMC 1:1, LiPF6 at 60 °C for 2 weeks
– Dissolution of manganese in the high volt spinel samples clearly lower
C. Brünig / G. Nuspl, BL Energy Storage, 08.10.2014
Public, New Cathode Materials 23
– Only small exothermal behaviour when charged material is heated in the presence
of electrolyte
– The nickel doped spinel is a safe cathode material
[W/g]
[W/g]
Temperature °C Temperature °C
LiMn1.6Ni0.4O4
High volt spinel - safety aspects, DSC analysis -
C. Brünig / G. Nuspl, BL Energy Storage, 08.10.2014
Summary
Public, New Cathode Materials 24
– Till now the nickel doped manganese spinel is the most promising high volt
material
– Status: batch size: 2,5 kg, up-scaling in progress
– Synthesis route yields phase pure samples of the nickel doped manganese spinel
– Nickel doped spinel shows no critical exothermal reaction during heating
– Only small dissolution of manganese in the electrolyte
– Promising results in the battery tests:
Capacity values ≈ 135 mAh/g (LiMn1,6Ni0,4O4) close to theoretic capacity
of 147 mAh/g
First rate capability tests show a good behaviour at high rates
Full cell tests of customers are very promising, over 500 cycles vs. graphite