Centre of Excellence POEMES, IEES (CLEPS), BULGARIAN ACADEMY OF SCIENCES WP 2. Lead-acid batteries for POEMES, LABD Scanning Electron Microscopy (SEM) - construction, components, features and applications

Centre of Excellence POEMES, IEES (CLEPS), BULGARIAN ACADEMY OF SCIENCES WP 2. Lead-acid batteries for POEMES, LABD e-e- Electron gun Vacuum tube - Tungsten filament - Lanthanum hexaboride (LaB6) single crystal - field emission gun Focussed e - beam - accelerating voltage 20 – 200 keV SEM construction, components and features Spot size – nm to m range Magnification: 100 – 200,000 x Resolurion: 0,7 nm to 50 nm Electron optics Objective (final lens) JEOL JSM-890 field emission: Magnification: 900,000 x 35 keV, Resolurion: 0,7 nm Microstructure of the specimen surface

Centre of Excellence POEMES, IEES (CLEPS), BULGARIAN ACADEMY OF SCIENCES WP 2. Lead-acid batteries for POEMES, LABD Sample (one / several) e-e- Condensing magnetic coils SEM construction, components and features Objective (final lens) Electron optics Au: sputter coater

Centre of Excellence POEMES, IEES (CLEPS), BULGARIAN ACADEMY OF SCIENCES WP 2. Lead-acid batteries for POEMES, LABD e-e- Sample Feature: images of morphology or topology - 3-d view Scan coils Scan mode SEM construction, components and features Objective (final lens) Condensing magnetic coils Electron optics

Centre of Excellence POEMES, IEES (CLEPS), BULGARIAN ACADEMY OF SCIENCES WP 2. Lead-acid batteries for POEMES, LABD e-e- Scan coils Objective (final lens) Secondary e - 0,1 - 1 eV Topography Sample Amplifier & detector SEM construction, components and features Condensing magnetic coils B/W photo CCD matrix www video PC control

Centre of Excellence POEMES, IEES (CLEPS), BULGARIAN ACADEMY OF SCIENCES WP 2. Lead-acid batteries for POEMES, LABD e-e- Secondary X rays (element microanalysis, X-ray mapping) Detector Sample SEM construction, components and features Condensing magnetic coils Objective (final lens) Scan coils WD(crystal)S: B – Am, EDS (Si,Ge,Li, Be): B–U(AM), spot 1 m, 0,1% EPMA

Centre of Excellence POEMES, IEES (CLEPS), BULGARIAN ACADEMY OF SCIENCES WP 2. Lead-acid batteries for POEMES, LABD e-e- EBS: crystallography, EBSD: local phase identification and orientation meas., EBS mapping: sp. lattice features, grain boundary misorientation Scan coils Back scattered e keV Atomic Nr, topogr. Sample Amplifier & detector SEM construction, components and features Condensing magnetic coils Objective (final lens)

Centre of Excellence POEMES, IEES (CLEPS), BULGARIAN ACADEMY OF SCIENCES WP 2. Lead-acid batteries for POEMES, LABD e-e- Magnification: up to 50,000 x, resolution 10 nm. Sample E (environmental) SEM Environment: T: -200 to o C Humidity, Atmosphere Real time video VHS recording - Effect of wetting/drying on fibres. - Water reactions with cement to produce bulk properties, -Soil science, catalysis, -Polymers, ceramics, - - Microelectronics.

Centre of Excellence POEMES, IEES (CLEPS), BULGARIAN ACADEMY OF SCIENCES WP 2. Lead-acid batteries for POEMES, LABD PbO 2 crystals morphology vs. electrolyte concentration 6 M, 1.34 s.g.5 M, 1.28 s.g. Source: D. Pavlov, A. Kirchev, M. Stoycheva and B. Monahov, Influence of H2SO4 concentration on the mechanism of the processes and on the electrochemical activity of the Pb/PbO2PbSO4 electrode, accepted for publication in J.Power Sources, 2004

Centre of Excellence POEMES, IEES (CLEPS), BULGARIAN ACADEMY OF SCIENCES WP 2. Lead-acid batteries for POEMES, LABD 2.8 M, 1.17 s.g M, s.g. PbO 2 crystals morphology vs. electrolyte concentration Source: D. Pavlov, A. Kirchev, M. Stoycheva and B. Monahov, Influence of H2SO4 concentration on the mechanism of the processes and on the electrochemical activity of the Pb/PbO2PbSO4 electrode, accepted for publication in J.Power Sources, 2004

Centre of Excellence POEMES, IEES (CLEPS), BULGARIAN ACADEMY OF SCIENCES WP 2. Lead-acid batteries for POEMES, LABD 0.18 M, s.g. 0.5 M, s.g. PbO 2 crystals morphology vs. electrolyte concentration Source: D. Pavlov, A. Kirchev, M. Stoycheva and B. Monahov, Influence of H2SO4 concentration on the mechanism of the processes and on the electrochemical activity of the Pb/PbO2PbSO4 electrode, accepted for publication in J.Power Sources, 2004

Centre of Excellence POEMES, IEES (CLEPS), BULGARIAN ACADEMY OF SCIENCES WP 2. Lead-acid batteries for POEMES, LABD Our secret goal: green battery, 100% natural products Nephrolepis (fern) Polypodium (fern)

Centre of Excellence POEMES, IEES (CLEPS), BULGARIAN ACADEMY OF SCIENCES WP 2. Lead-acid batteries for POEMES, LABD PAM, charged, after thermal rise 1 m Source: D. Pavlov, B. Monahov, and A. Kirchev, to be published

Centre of Excellence POEMES, IEES (CLEPS), BULGARIAN ACADEMY OF SCIENCES WP 2. Lead-acid batteries for POEMES, LABD NAM, formed, before thermal rise 1 m3.3 m Source: D. Pavlov, B. Monahov, and A. Kirchev, to be published

Centre of Excellence POEMES, IEES (CLEPS), BULGARIAN ACADEMY OF SCIENCES WP 2. Lead-acid batteries for POEMES, LABD NAM, charged, after thermal rise 1 m Source: D. Pavlov, B. Monahov, and A. Kirchev, to be published

Centre of Excellence POEMES, IEES (CLEPS), BULGARIAN ACADEMY OF SCIENCES WP 2. Lead-acid batteries for POEMES, LABD Determinations in PAM/AMCL/CL 1.XRD: - phase composition, - average crystallite size; 2.SEM: - crystal morphology, - structure SGT positive plate structure studies setup Sample collecting points Pb CL AMCLPAM Pb strap grid interface - sample collecting point

Centre of Excellence POEMES, IEES (CLEPS), BULGARIAN ACADEMY OF SCIENCES WP 2. Lead-acid batteries for POEMES, LABD Morphology of PbO 2 in the corrosion layer dense aggregates on the metal surface fine, globular, hydrated PbO 2 particles, almost no pores

Centre of Excellence POEMES, IEES (CLEPS), BULGARIAN ACADEMY OF SCIENCES WP 2. Lead-acid batteries for POEMES, LABD dense structure porous structure Morphology of PbO 2 in the AMCL

Centre of Excellence POEMES, IEES (CLEPS), BULGARIAN ACADEMY OF SCIENCES WP 2. Lead-acid batteries for POEMES, LABD e-e- TEM construction, components and features The internal structure of the specimen (2-d imaging) Electron gun U acc - up to 1000 keV Sample: 0,2 m Magnification: ,000 x Resolurion: down to 0,2 nm JEOL JEM atoms Magnification: 2,000,000x keV, Resolurion: 0,15 nm Mesh, goniometer specimen stages Secondary X rays (element microanalysis) TEM microprobe TEM nanoprobe STEM EDS CCD camera Cryogenic facility

Centre of Excellence POEMES, IEES (CLEPS), BULGARIAN ACADEMY OF SCIENCES WP 2. Lead-acid batteries for POEMES, LABD Source: D. Pavlov, I. Balkanov, and P. Rachev, J. Electrochem. Soc., 134 (1987) a: TEM micrograph of an active mass agglomerate after discharge; b: electronogram of the crystals in the defined area with interpretation of its interplanar spacings TEM micrograph and electron diffractogram of a PbO 2 particle

Centre of Excellence POEMES, IEES (CLEPS), BULGARIAN ACADEMY OF SCIENCES WP 2. Lead-acid batteries for POEMES, LABD 1.Structure of the Pb/PbSO 4 electrode system. Membrane model of PbSO 4. 2.Structure of the Pb/PbO/PbSO 4 electrode system. Semiconductor model of PbO n. 3.Structure of PAM. PbO 2 agglomerates, aggregates and particles. Hydrated structures in PAM and in the corrosion layer. Gel-crystal model of PbO 2. Influence of the electrolyte concentration on the crystal morphology of PbO 2. 4.Structure of NAM. Skeleton and energetic structures. 5.Structure of the CL. CL/AMCL/PAM model. 6.Mapping of PAM and the corrosion layer. Battery knowledge developed using SEM/TEM microscopy