High volt materials for lithium ion batteries: material ... · PDF fileion batteries: material...
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Public
Christian Brünig
Business Line
Energy storage
29.05.2013
High volt materials for lithium ion batteries: material research and electrochemical testing
Christian Brünig, Business Line, Energy storage, 29.05.2013
Table of contents
Public, Clariant high volt spinel 2
03 The Clariant Story
04 Clariant company, Business & Products
06 Life Power® - Clariant lithium iron phosphate
07 R&D roadmap business line “Energy storage”
08 High volt materials
10 Clariant high volt spinel: product and electrochemical testing
20 Summary
Christian Brünig, Business Line, Energy storage, 29.05.2013
Acquisition of
Hoechst Specialty
Chemicals
Acquisition
of BTP
Divestment of
Cellulose Ethers
Divestment
of Electronic
Materials
Divestment of
Acetyl Building
Blocks
Acquisition of CIBA
Masterbatches
Divestment of
Custom
Manufacturing
Acquisition of
Rite Systems
and Ricon Colors
Acquisition of Prairie
Petro-Chem
Takeover of
Süd-Chemie AG
Acquisition of Italtinto S.r.l.
Takeover of all minority
shares in Colex Spolka
Purchase of Oberhausen
Technology Center
Acquisition of Octagon
Process LLC
Divestment of
European Emulsion
Business and
Hydrosulfite North
America
Divestment of
Pharmaceutical Fine
Chemicals
ACQUISITIONS
DIVESTMENTS
CLARIANT
SPIN-OFF
FROM
SANDOZ
AND IPO
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1997 2000 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 1995 > 2012
Signed agreement
to sell Textile
Chemicals, Paper
Specialties and
Emulsions to SK
Capital
The Clariant story
Christian Brünig, Business Line, Energy storage, 29.05.2013
A world leader in specialty chemicals
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Clariant focuses on creating value
by investing in future profitable and
sustainable growth.
KEY FACTS
Sales 2012 (CHF m)
6 038
More than
100 Group companies worldwide
EBITDA 2012 (CHF m)
before exceptionals
802
End 2012
~21 202 employees
Represented in
76 countries worldwide
7 Business Units
(incl. discontinued operations)
Christian Brünig, Business Line, Energy storage, 29.05.2013
Additives
Seven core Business Units…
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Industrial & Consumer Specialties
Functional Materials Catalysts
…and additionally the start-up business line Energy storage
Masterbatches Oil & Mining Services Pigments
Christian Brünig, Business Line, Energy storage, 29.05.2013
Life Power® – Superior Battery Materials
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Life Power®
A pioneering, high-performance cathode
material based on lithium iron phosphate,
made by a proprietary process for use in
lithium-ion batteries.
Compared with other cathode materials,
lithium iron phosphate is noted for its high-
power density; superior material safety;
outstanding durability; favorable material
cost; and excellent cycle stability.
Christian Brünig, Business Line, Energy storage, 29.05.2013
R&D roadmap
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LiFePO4 LiMnPO4 LiCoPO4 LiNiPO4
5V - High Volt Materials
LiMn2O4 LiMn2-xNixO4
Life Power ® P2 grades
Life Power® T1 grades
Li4Ti5O12
Christian Brünig, Business Line, Energy storage, 29.05.2013
High volt materials
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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
Christian Brünig, Business Line, Energy storage, 29.05.2013
High volt materials
– Compounds with an operating voltage around 5 V
– Higher voltage results in higher energy density of the battery (greater range of EV)
E = Q x U
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– 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
Christian Brünig, Business Line, Energy storage, 29.05.2013
– High volt spinels form solid solutions for different ratios of manganese and nickel
– Focus on LiMn1,5Ni0,5O4 and LiMn1,6Ni0,4O4
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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
Christian Brünig, Business Line, Energy storage, 29.05.2013
High volt spinel - LiMn2-xNixO4 -
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– Electrochemical tests show higher capacity values for LiMn1,6Ni0,4O4
– LiMn1,6Ni0,4O4 crystallizes in the disordered spinel phase (Fd-3m) resulting in a better
electrochemical performance
LiMn1,5Ni0,5O 4 LiMn1,6Ni0,4O 4
Christian Brünig, Business Line, Energy storage, 29.05.2013
High volt spinel - Battery tests -
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– High voltage may cause problems with cycle life….
Christian Brünig, Business Line, Energy storage, 29.05.2013
– Different electrolytes tested:
- not every electrolyte suitable for high volt compounds:
irreversible capacity, capacity loss
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High volt spinel - electrochemical testing conditions -
Electrolyte solution A Electrolyte solution B
Christian Brünig, Business Line, Energy storage, 29.05.2013
High volt spinel - Battery tests -
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– Capacity values ≈ 135 mAh/g, close to theoretic capacity of 147 mAh/g
– Only small capacity loss after 50 cycles
– Charge and discharge rate of 1/2 C (no CV charging)
– “Electrolyte C”
– Intensive drying, optimization of electrode film preparation
Christian Brünig, Business Line, Energy storage, 29.05.2013
High volt spinel - Battery tests -
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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
Christian Brünig, Business Line, Energy storage, 29.05.2013
High volt spinel - Battery tests -
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– Tests at CEA institute had shown that several hundred cycles are possible, even at
elevated temperature
3C / 3D, 25 °C
700 cycles
3C / 3D, 55 °C
300 cycles
Christian Brünig, Business Line, Energy storage, 29.05.2013
High volt spinel - Battery tests -
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– Rate capability testing had shown very promising results
1/2D 1D 3D 5D 10D
Christian Brünig, Business Line, Energy storage, 29.05.2013
High volt spinel - dissolution of manganese -
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– 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
Christian Brünig, Business Line, Energy storage, 29.05.2013
High volt spinel - safety aspects -
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– DSC analysis carried out at the ZSW test institute in Ulm
– Only small exothermal behaviour when charged material is heated
– The nickel doped spinel is a safe cathode material
Christian Brünig, Business Line, Energy storage, 29.05.2013
Summary
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– Synthesis route yields phase pure samples of the nickel doped manganese spinel
– Status: lab scale, up-scaling in progress, first tests of larger batches (around 3 kg)
– 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 and 120 mAh/g for LiMn1,5Ni0,5O4
First rate capability tests show a good behaviour at high rates
Good cycle life at high charge / discharge rates (also at high temperature)
Different electrolytes: best results with “electrolyte C”