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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


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


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


A world leader in specialty chemicals


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)


Additives

Seven core Business Units…


Industrial & Consumer Specialties

Functional Materials Catalysts

…and additionally the start-up business line Energy storage

Masterbatches Oil & Mining Services Pigments


Life Power® – Superior Battery Materials


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.


R&D roadmap


LiFePO4 LiMnPO4 LiCoPO4 LiNiPO4

5V - High Volt Materials

LiMn2O4 LiMn2-xNixO4

Life Power ® P2 grades

Life Power® T1 grades

Li4Ti5O12


High volt materials


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


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


– 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 spinels form solid solutions for different ratios of manganese and nickel

– Focus on LiMn1,5Ni0,5O4 and LiMn1,6Ni0,4O4


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


High volt spinel - LiMn2-xNixO4 -


– 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


High volt spinel - Battery tests -


– High voltage may cause problems with cycle life….


– Different electrolytes tested:

- not every electrolyte suitable for high volt compounds:

irreversible capacity, capacity loss


High volt spinel - electrochemical testing conditions -

Electrolyte solution A Electrolyte solution B




– 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




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




– 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




– Rate capability testing had shown very promising results

1/2D 1D 3D 5D 10D


High volt spinel - dissolution of manganese -


– 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


High volt spinel - safety aspects -


– 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


Summary


– 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”

Documents

High volt materials for lithium ion batteries: material ... · PDF fileion batteries: material research and electrochemical testing . ... to sell Textile ... A world leader in specialty