HIGH VOLTAGE MATERIALS FOR LITHIUM ION · PDF fileHIGH VOLTAGE MATERIALS FOR LITHIUM ION...

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

Public


BL Energy Storage

08.10.2014

Corporate Introduction


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


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


Clariant focuses on creating value

through innovation and sustainability.

6 076

858 EBITDA margin 2013

before exceptionals

323

4

Corporate Center, Pratteln, Switzerland


Four Business Areas* The right portfolio with leading market positions


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

MARGIN** 22.3%

SALES

(CHF m) 1 281


EBITDA

MARGIN** 15.2%

SALES

(CHF m) 2 521


EBITDA

MARGIN** 14.1%

Public


BL Energy Storage

08.10.2014

Business Line Introduction


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


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



Clariant’s roadmap for Energy Storage

10

LiFePO4 LiMnPO4 LiCoPO4 LiNiPO4

5V – High-Voltage Materials

LiMn2O4 LiMn2-xNixO4

Li4Ti5O12


Public


BL Energy Storage

08.10.2014

New Cathode Materials

CLARIANT’S

HIGH-VOLT MATERIALS


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



– 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



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



– 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 -


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


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

– Focus on 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 - Battery tests -


– 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/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




– Rate capability testing had shown very promising results

– Loading about 5 mg/cm2 (thin electrode)

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


High volt spinel - Battery tests / results of customers -


– Full cell test vs. graphite

- 25 °C, cycled with 1 C, 100 % DOD


High volt spinel - dissolution of manganese -


– 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



– 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 -


Summary


– 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

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