Advanced Energy Storage Materials for Battery Applications. Advanced Materials December 12 th, Peter H.L. Notten

Transcription

1 Advanced Energy Storage Materials for Battery Applications Advanced Materials December 12 th, 2012 Peter H.L. Notten Eindhoven University of Technology >> Focus on sustainability, innovation and international

2 Diversification Automotive : The dream Automotive System Batteries Supercaps Fuel Cells µ-power Batteries Fuel Cells Portable Batteries Mini-FC Autonomous devices Integrated Batteries Supercaps Energy density mwh Wh kwh

3 Diversification Automotive : The dream Automotive System Batteries Supercaps Fuel Cells µ-power Batteries Fuel Cells Portable Batteries Mini-FC Autonomous devices Integrated Batteries Supercaps Energy density mwh Wh kwh

4 Ambient Intelligence In-Home Autonomous devices optical Server 1Gb/s Residential Ambient Intelligence Server 100bit/s 5Mb/s µwatt node mwatt node 10Gb/s Router ~ 10 other homes 100Mb/s Watt node

5 Autonomous device Light Temperature Speed Vibrations Magnetic Acoustics Moisture Air pressure Sensor(s) Communication Microcontroller Energy scavenging Power Supply Energy storage Optical RF Acoustics Light Temperature Vibrations Acoustic waves

6 Thin Film Micro-batteries

7 Li-ion battery concept lithium electrode cobaltoxide electrode storage capacity LiC ch Li + e - Li + - CoO 2 charge C Li + e - d LiCoO 2 discharge

8 Planar All-Solid-State batteries Drawbacks: Low storage capacity: only 45 µah/cm 2. µm Low power capability Metallic Lithium moving interface low melting point

9 Phase diagram LiSi Li 21 Si 5

10 Morphology after Li-(de)intercalation in single-crystal Si-wafer 2 µm Philips 50 µm

11 Li-storage in Si-nanowires B. Laic, Electrochim. Acta, 53 (2008) L. Baggetto, Thesis Eindhoven University (2010).

12 Li-storage in Si-nanowires L. Baggetto, Thesis Eindhoven University (2010).

13 Li-storage in honeycomb-structured Si before Lithiation L. Baggetto et al., Adv. Mater. 23 (2011) 1563.

14 Li-storage in honeycomb-structured Si before Lithiation L. Baggetto et al., Adv. Mater. 23 (2011) 1563.

15 Li-storage in honeycomb-structured Si before Lithiation after Lithiation L. Baggetto et al., Adv. Mater. 23 (2011) 1563.

16 Li-storage in honeycomb-structured Si before Lithiation after Lithiation L. Baggetto et al., Adv. Mater. 23 (2011) 1563.

17 Li-storage in honeycomb-structured Si before Lithiation after Lithiation L. Baggetto et al., Adv. Mater. 23 (2011) 1563.

18 Li-storage in honeycomb-structured Si 0 % 15 % 40 % 70 % 100 % L. Baggetto et al., Adv. Mater. 23 (2011) 1563.

19 LPCVD p-si thin film electrodes φ=15 mm Ti N p-si O-ring Patterning provides an accurate amount of active material p-si Ti N

20 Thin film Si-electrode Silicon: >3500 >3000 mah/g Graphite: 375 mah/g!

21 Rate capability Si-electrode C, 0.2 min 0.75 E(V) C, 10 hours Baggetto et al., Adv. Funct. Mat. 18 (2008) 1. Capacity (mah/g)

22 Cycle-life of 50nm-thick PECVD a-si 3500 Capacity (mah/g) Liquid electrolyte Cycle Notten et al., Adv. Mat., 19 (2007) 4564.

23 Cycle-life of 50nm-thick PECVD a-si 3500 Capacity (mah/g) Solid-state electrolyte 500 Liquid electrolyte Cycle Notten et al., Adv. Mat., 19 (2007) 4564.

24 Planar all-solid-state battery Current collector LiCoO 2 Solid-state electrolyte Metallic Li Philips Storage capacity: 45 µah/cm 2. µm

25 Integrated All-Solid-State battery. Si-substrate Notten et al., Adv. Mat., 19 (2007) 4564.

26 Integrated All-Solid-State battery - Current collector. Si-substrate Notten et al., Adv. Mat., 19 (2007) 4564.

27 Integrated All-Solid-State battery - Current collector. Si-substrate Notten et al., Adv. Mat., 19 (2007) 4564.

28 Integrated All-Solid-State battery - Current collector.. Si-substrate Barrier layer Notten et al., Adv. Mat., 19 (2007) 4564.

29 Integrated All-Solid-State battery - Current collector... Si-substrate Si Barrier layer Notten et al., Adv. Mat., 19 (2007) 4564.

30 Integrated All-Solid-State battery - Current collector Solid electrolyte.... Si-substrate Si Barrier layer Notten et al., Adv. Mat., 19 (2007) 4564.

31 Integrated All-Solid-State battery -. Current collector LiCoO 2 Solid electrolyte.... Si-substrate Si Barrier layer Notten et al., Adv. Mat., 19 (2007) 4564.

32 Current collector, e.g. Pt + Integrated All-Solid-State battery - Current collector LiCoO 2. Solid electrolyte.... Si-substrate Si Barrier layer Notten et al., Adv. Mat., 19 (2007) 4564.

33 Surface area calculation A = 2 ll + 2hl ( L ( w + s) s) L L = 1 cm l = 1 cm s = 2 µm w = 2 µm h = 50 µm s w h l A = 50 cm 2 /cm 2 Notten et al., Adv. Mat., 19 (2007) 4564.

34 Autonomous integrated energy system Integrated solar cell Integrated battery

35 In vivo Integrated Energy system Integrated fuel cell Integrated battery

36 RIE-etching of slits in crystalline-si Surface 10 µm Notten et al., Adv. Mat., 19 (2007) µm

37 RIE-etching of pores in crystalline-si Cross-section Surface 5 µm 5 µm Notten et al., Adv. Mat., 19 (2007) 4564.

38 LPCVD reactor

39 Plasma-assisted ALD Home-built ALD-I system (remote plasma, 4 wafers, open-load) Oxford Instruments FlexAL system (remote plasma, 8 wafers, loadlock)

40 ALD-deposited 3D-TiN Top Aspect ratio=21; T dep =90 o C; plasma exposure=20 s Bottom

41 LPCVD 3D-Si anode Top TiN Middle Bottom Si Si-substrate Si TiN Si-substrate

42 LPCVD 3D-LiCoO 2 cathode 500 nm 10 µm 400 nm

43 Q Battery = Notten et al., Adv. Mat., 19 (2007) * Q Integrated capacitors! Roozeboom, et al., Thin Solid Films 504 (2006) 391.

44 All-solid-state batteries a challenging route towards 3D-integration facilitating future Autonomous devices Medical implants

45 Targeted specifications All-solid-state micro-batteries 40-60x surface enlargement increasing Energy and Power density Capacity density: 2 mah / µm.cm 2 (double-sided) Voltage: 3.8 V Energy density: 10 mwh / µm.cm 2 ( 1 $) Power density: 1 mw / µm.cm 2 at 0.1 C-rate 100 mw / µm.cm 2 at 10 C-rate Notten et al., Adv. Mat., 19 (2007) 4564.

46 LPCVD deposition of LiTaO 3 electrolyte -20 T (K) Ln Rdep(mole cm -2 s -1 ) Diffusion controlled Kinetically controlled Inverse of the Susceptor Temperature ( 10-3 K -1 )

47 LPCVD deposition of LiTaO 3 electrolyte -20 T (K) Ln Rdep(mole cm -2 s -1 ) Diffusion controlled Kinetically controlled 10 µm 3 µm Diffusion controlled Kinetically controlled 873 K, 5 h 773 K, 5 h 673 K, 20 h Inverse of the Susceptor Temperature ( 10-3 K -1 ) 1 µm

48 Pinholes creating art.!

49 Pinholes creating art.!

50 Q Battery = Notten et al., Adv. Mat., 19 (2007) * Q Integrated capacitors! Roozeboom, et al., Thin Solid Films 504 (2006) 391.