Striving for energy density

Transcription

1 Striving for energy density HIGH VOLTAGE MATERIALS FOR LITHIUM ION BATTERIES Public C. Brünig / G. Nuspl BL Energy Storage

2 2 Public, Striving for energy density Table of contents Corporate introduction 3 Business line Energy Storage 7 Clariant high volt materials 11 Lithium cobalt phosphate LiCoPO 4 13 High volt spinel LiMn 1,6 Ni 0,4 O 4 15 Summary 24

3 Corporate Introduction Public C. Brünig / G. Nuspl BL Energy Storage

4 4 Public, Corporate Introduction Historical milestones Clariant has come a long way now we are going beyond what has already been achieved Clariant Spin-Off and IPO Acquisition of Hoechst Specialty Chemicals Acquisition of BTP /2010 Restructuring ff Acquisition of Süd-Chemie 2013 Divestment of 5 Businesses

5 5 Public, Corporate Introduction A globally leading company in specialty chemicals Clariant focuses on creating value through innovation and sustainability Sales 2013 (CHF m) from continuing operations 858 EBITDA 2013 (CHF m) before exceptionals 4 Business Areas 323 Net result 2013 (CHF m) from continuing operations 14.1% EBITDA margin 2013 before exceptionals Employees 2013 Corporate Center, Pratteln, Switzerland

6 6 Public, Corporate Introduction Four Business Areas* The right portfolio with leading market positions Care Chemicals Catalysis & Energy Natural Resources Plastics & Coatings SALES (CHF m) SALES (CHF m) 713 SALES (CHF m) SALES (CHF m) EBITDA** (CHF m) 263 EBITDA** (CHF m) 159 EBITDA** (CHF m) 195 EBITDA** (CHF m) 356 EBITDA MARGIN** 16.8% EBITDA MARGIN** 22.3% EBITDA MARGIN** 15.2% EBITDA MARGIN** 14.1% *Results full year 2013 **Before exceptional items, as reported

7 Business Line Introduction Public C. Brünig / G. Nuspl BL Energy Storage

8 8 Public, Business Line Introduction Global HQ for Business Line Energy Storage relocate from Munich to Singapore as of 1 st January 2013 Sales Office Headquarter Legal Entity R&D/pilot facilities Production facilities Candiac, Canada LFP plant (P2, P2E) Opened in 2012 Sales Office Capacity expansion Munich, Germany Sales Office Moosburg, Germany R&D facility and pilot plants LFP (P2S), LTO LMFP, LMNO Opened in Shanghai, China Sales Office South Korea Sales Office Wisconsin, USA Sales Office Tokyo, Japan Sales Office Switzerland, Pratteln LiFePO 4 + C Licensing AG Singapore Headquarter 1 Start of regular production

9 9 Public, Business Line Introduction LFP - Clariant s main cathode material Group of materials Physical characteristics Powder P2 & P2E P2S Spherical agglomerates Grades 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 Life Power P2S spherical agglomerates for easier product handling and electrode coating

10 10 Public, Business Line Introduction Clariant s roadmap for Energy Storage LiFePO 4 LiMnPO 4 LiCoPO 4 LiNiPO 4 5V High-Voltage Materials LiMn 2 O 4 LiMn 2-x Ni x O 4 Li 4 Ti 5 O 12

11 New Cathode Materials CLARIANT S HIGH-VOLT MATERIALS Public C. Brünig / G. Nuspl BL Energy Storage

12 12 High volt materials 3 possible candidates (and derivatives of these) Nickel manganese spinel LiMn 2-x Ni x O 4 Lithium cobalt phosphate LiCoPO 4 Lithium nickel phosphate LiNiPO 4 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

13 13 Lithium cobalt phosphate - LiCoPO 4 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

14 14 Lithium Cobalt Phosphate - LiCoPO 4 Thermal behavior of LCP is different from LFP and LMP Thermal behavior of LCP is depending on the state of charge Fully charged Fully charged Experimental investigation on the electrochemical and thermal behavior of LiCoPO 4 -based cathode Journal of Power Sources, Volume 222, 15 January 2013, Pages Simon Theil, Meike Fleischhammer, Peter Axmann, Margret Wohlfahrt-Mehrens

15 15 High volt spinel - Basic information - 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

16 16 High volt spinel Energy Density on cell level Projected energy density of a 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 5Vspinel offers an additional benefit on pack level by a reduced number of cells in series.

17 17 High volt spinel - LiMn 2-x Ni x O 4 - High volt spinels form solid solutions for different ratios of manganese and nickel Focus on LiMn 1,6 Ni 0,4 O 4 phase pure samples Particle size distribution: D(0,50) 7-8 µm BET-surface: 1 qm/g Press density: 2.3 g/cm 3

18 18 High volt spinel - Battery tests - Battery test results: - Capacity values 135 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

19 19 High volt spinel - Battery tests - Tests at CEA institute show that the results are reproducible Also good results at higher temperature C/5 / D/5, 25 C 100 cycles C/5 / D/5, 55 C 100 cycles

20 20 High volt spinel - Battery tests - Rate capability testing had shown very promising results Loading about 5 mg/cm 2 (thin electrode) 1/2D 1D 3D 5D 10D

21 21 High volt spinel - Battery tests / results of customers - Full cell test vs. graphite - 25 C, cycled with 1 C, 100 % DOD

22 22 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, LiPF 6 at 60 C for 2 weeks Dissolution of manganese in the high volt spinel samples clearly lower

23 23 High volt spinel - safety aspects, DSC analysis - 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] LiMn 1.6 Ni 0.4 O 4 [W/g] Temperature C Temperature C

24 24 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 (LiMn 1,6 Ni 0,4 O 4 ) 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