Overview of biochar for electrochemistry applications

Transcription

1 Engineering Conferences International ECI Digital Archives Biochar: Production, Characterization and Applications Proceedings Overview of biochar for electrochemistry applications Capucine Dupont CEA Grenoble, France Follow this and additional works at: Part of the Engineering Commons Recommended Citation Capucine Dupont, "Overview of biochar for electrochemistry applications" in "Biochar: Production, Characterization and Applications", Franco Berruti, Western University, London, Ontario, Canada Raffaella Ocone, Heriot-Watt University, Edinburgh, UK Ondrej Masek, University of Edinburgh, Edinburgh, UK Eds, ECI Symposium Series, (2017). This Abstract and Presentation is brought to you for free and open access by the Proceedings at ECI Digital Archives. It has been accepted for inclusion in Biochar: Production, Characterization and Applications by an authorized administrator of ECI Digital Archives. For more information, please contact

2 Overview of biochars for energy storage Capucine DUPONT

3 Biochar applications? Volatile matter Gas (CO, CO 2, CH 4 ) Condensates (water, tars) Products Biomass C 6 H 9 O 4 Pyrolysis Biochar upgrading Solid fuel Amendment Biochar C 6 H x<9 O y<4 Activated carbon (water/gas filtration) Catalyst Electrode for energy storage Temperature ( C) 2

4 Why these applications? Huge increase of energy storage needs! X 10 3

5 Energy storage: main performance criteria Specific energy Wh.kg 1 V I t m Long runtime Specific power W.kg 1 V I m High current load

6 Ragone plot for energy storage devices Specific power at cell level (W.kg 1 ) Specific energy at cell level (Wh.kg 1 ) 5

7 Supercapacitors 6

8 Use of supercapacitors Very high charge and discharge rates Very little degradation over cycles Low energy density On the market Opening of emergency exit doors in aircrafts Memory back up in data centers Regenerative braking, peak power delivery in cars, buses, trains, cranes and elevators Stability in blade pitch systems 7

9 Supercapacitor principle Energy stored through electrostatic phenomenon Two types: Electrochemical Double Layer Capacitor (EDLC) Pseudocapacitor 8

10 Supercapacitor principle Energy stored through electrostatic phenomenon Two types: Electrochemical Double Layer Capacitor (EDLC) Medium dielectric constant Electrode surface area Electrode Collector Electric double layer Electrode Collector Electric double layer S Capacitance d Distance between layers Electrolyte Separator 9

11 Electrode material: specifications High surface area Optimal pores distribution Micropores: same size as ions in electrolyte for higher energy density Macropores/mesopores: fast electrolyte diffusion for higher power density High electric conductivity High cristallinity Low surface area Wettability Surface functionalities 10

12 Electrode material: current situation High surface area Optimal pores distribution Micropores: same size as ions in electrolyte for higher energy density Macropores/mesopores: fast electrolyte diffusion for higher power density High electric conductivity High cristallinity Low surface area Wettability Surface functionalities Activated carbons Usually based on fossil sources Expensive

13 Electrode material: current situation High surface area Optimal pores distribution Micropores: same size as ions in electrolyte for higher energy density Macropores/mesopores: fast electrolyte diffusion for higher power density High electric conductivity High cristallinity Low surface area Wettability Surface functionalities Activated carbons Usually based on fossil sources Expensive Biochar

14 Biochar for supercapacitors today Severaldozensof articles since 2004 Good performances of biochar Various biomass types Mainly agricultural waste Selection criteria: Cost and availability Nanostructure First stage: Biomass to biochar Slow pyrolysis HydroThermal Carbonization 13

15 Biochar for supercapacitors today Severaldozensof articles since 2004 Good performances of biochar Various biomass types Mainly agricultural waste Selection criteria: Cost and availability Nanostructure First stage: Biomass to biochar Slow pyrolysis HydroThermal Carbonization Second stage: Biochar upgrading Activation: mainly chemical Surface functionalization Sulfonation Heteroatom doping Pyrolysis under NH 3 From in situ elements Use of inorganic nanotemplates Si spheres 14

16 Biochar for supercapacitors today Severaldozensof articles since 2004 Good performances of biochar Various biomass types Mainly agricultural waste Selection criteria: Cost and availability Nanostructure First stage: Biomass to biochar Second stage: Biochar upgrading Slow pyrolysis HydroThermal Carbonization Sophisticated upgrading processes Attractive Tailored materials Cheap? In line with biochar goal? Ecofriendly? Activation: mainly chemical Surface functionalization Sulfonation Heteroatom doping Pyrolysis under NH 3 From in situ elements Use of inorganic nanotemplates Si spheres 15

17 Biochar for supercapacitors today Severaldozensof articles since 2004 Good performances of biochar Various biomass types Mainly agricultural waste Selection criteria: Cost and availability Nanostructure First stage: Biomass to biochar Slow pyrolysis HydroThermal Carbonization Few parametric studies on biochar production Pyrolysis temperature No systematic study feedstock/process/product Mainly from electrochemists viewpoint! Second stage: Biochar upgrading Activation: mainly chemical Surface functionalization Sulfonation Heteroatom doping Pyrolysis under NH 3 From in situ elements Use of inorganic nanotemplates Si spheres 16

18 Biochar for supercapacitors in the future? Severaldozensof articles since 2004 Good performances of biochar Various biomass types Mainly agricultural waste Selection criteria: Cost and availability Nanostructure First stage: Biomass to biochar Slow pyrolysis HydroThermal Carbonization Systematic study feedstock/process/product Biomass characterization Biochar process optimization Application to hybrid supercapacitors Carbon based composites Second stage: Biochar upgrading Activation: mainly chemical Surface functionalization Oxidation, sulfonation Heteroatom doping Pyrolysis under NH 3 From in situ elements Use of inorganic nanotemplates Si spheres 17

19 Li ion batteries Specific power at cell level (W.kg 1 ) Specific energy at cell level (Wh.kg 1 ) 18

20 Li ion batteries 19

21 Use of Li ion batteries High energy density Reduced weight Low self discharge Medium power density On the market Computers Phones Solar power storage Electric vehicles 20

22 Li ion battery: principle Energy stored through chemical red/ox reactions Cathode Separator Anode Collector Collector Elemental Li Electrolyte 21

23 Li ion battery: principle Cathode Li ion Separator Anode Collector Collector Elemental Li... e e e Electrolyte Power supply Charging 22

24 Li ion battery: principle Cathode Li ion Separator Anode Collector Collector Elemental Li.. e e Electrolyte Power supply Charging... e e e 23

25 Li ion battery: principle Cathode Separator Anode Collector Li ion Collector Electrolyte.. e e Power supply Charging Elemental Li.. e e 24

26 Li ion battery: principle Cathode Separator Anode Collector Li ion Collector Electrolyte Power supply Charging Elemental Li... e e e 25

27 Li ion battery: principle Cathode Discharging Power load Separator Li ion... e e e Anode Collector Collector Electrolyte Elemental Li 26

28 Li ion battery: principle.. e e Cathode Discharging. Power.. e load e Separator Anode Li ion e Collector Collector Electrolyte Elemental Li 27

29 Li ion battery: principle.. e e Cathode Discharging. Power.... e load e e Separator e e Anode Li ion Collector Collector Elemental Li Electrolyte Elemental Li 28

30 Li ion battery: principle... e e e Cathode. e Discharging Power load Separator Anode Li ion Collector Collector Elemental Li Electrolyte 29

31 Li ion battery: principle Anode 30

32 Anode material: specifications Optimal pores distribution Subnanometric pores favour ion diffusion High N content Neighbouring C more electronegative prone to intercalate Li All key influential properties not well known Lackof systematic study with mechanisms understanding Different experimental devices 31

33 Anode material: current situation Optimal pores distribution Subnanometric pores favour ion diffusion High N content Neighbouring C more electronegative prone to intercalate Li All key influential properties not well known Lackof systematic study with mechanisms understanding Different experimental devices Graphitic carbon Based on fossil sources Expensive 32

34 Anode material: current situation Optimal pores distribution Subnanometric pores favour ion diffusion High N content Neighbouring C more electronegative prone to intercalate Li All key influential properties not well known Lackof systematic study with mechanisms understanding Different experimental devices Graphitic carbon Based on fossil sources Expensive Biochar 33

35 Biochar for Li ion batteries today Few dozens of articles since 1996 Biochar is not graphitizable not suitable a priori Feasibility proven Various biomass types Agricultural waste Selection criterion: cost and availability First stage: Biomass to biochar Slow pyrolysis HydroThermal Carbonization No upgrading = better! Sophisticated processes Tailored materials In line with biochar goals? Second stage: Biochar upgrading None Heteroatom doping Pyrolysis under NH 3 From in situ elements Use of inorganic nanotemplates 34

36 Biochar for Li ion batteries today Few dozens of articles since 1996 Biochar is not graphitizable not suitable a priori Feasibility proven Various biomass types Agricultural waste Selection criterion: cost and availability First stage: Biomass to biochar Slow pyrolysis HydroThermal Carbonization Few parametric studies on biochar production Pyrolysis temperature No systematic study feedstock/process/product Mainly from electrochemists viewpoint! Second stage: Biochar upgrading None Heteroatom doping Pyrolysis under NH 3 From in situ elements Use of inorganic nanotemplates 35

37 Biochar for Li ion batteries in the future? Few tens of articles since 1996 Biochar is not graphitizable not suitable a priori Feasibility proven Various biomass types Agricultural waste Selection criterion: cost and availability First stage: Biomass to biochar Slow pyrolysis HydroThermal Carbonization Systematic study feedstock/process/product Biomass characterization Biochar process optimization Application to alternative Li based batteries Carbon composite as cathode in batteries Li S, Li Se Second stage: Biochar upgrading None Heteroatom doping Pyrolysis under NH 3 From in situ elements Use of inorganic nanotemplates 36

38 Conclusion Biochars as electrodes for energy storage? Active field of research with significant number of publications On the main commercial devices: supercapacitors, Li ion batteries Whatever the device: Feasibility proven with various Biomass types Pyrolysis/Upgrading processes Lack of systematic pluridisciplinary study biomass/process/product 1. Mechanism understanding 2. Process optimization and upscaling 37

39 Future research options? Systematic pluridisciplinary study on the whole value chain Biomass properties Carbon properties Electrochemical performances Process conditions Application in other advanced technologies of energy storage 38

40 Biochars as source of anodes for sodium ion batteries: Feasibility study based on various biomass types Carolina DEL MAR SAAVEDRA RIOS, Virginie SIMONE, Loïc SIMONIN, Sébatien MARTINET, Capucine DUPONT

41 2. Feedstock 3. Biochar preparation 4. Biochar characterization 5. Electrochemical performances 6. Conclusion Why Na ion battery? Available in very few regions on Earth Polluting extraction fromdriedsaltlakes Development of Na ion battery Abundant

42 2. Feedstock 3. Biochar preparation 4. Biochar characterization 5. Electrochemical performances 6. Conclusion Why Na ion battery? Available in very few regions on Earth Polluting extraction fromdriedsaltlakes Development of Na ion battery Abundant and cheap Excellent electrochemical performances High energy density High power density Long life duration

43 2. Feedstock 3. Biochar preparation 4. Biochar characterization 5. Electrochemical performances 6. Conclusion Na ion battery: principle Energy stored through chemical red/ox reactions Cathode Separator Anode Collector Collector Elemental Na Electrolyte 42

44 2. Feedstock 3. Biochar preparation 4. Biochar characterization 5. Electrochemical performances 6. Conclusion Na ion battery: principle Cathode Na ion Separator Anode Collector Collector Elemental Na... e e e Electrolyte Power supply Charging 43

45 2. Feedstock 3. Biochar preparation 4. Biochar characterization 5. Electrochemical performances 6. Conclusion Na ion battery: anode Na ion Anode 44

46 2. Feedstock 3. Biochar preparation 4. Biochar characterization 5. Electrochemical performances 6. Conclusion Na ion battery: anode Na ion Graphitic carbon 45

47 2. Feedstock 3. Biochar preparation 4. Biochar characterization 5. Electrochemical performances 6. Conclusion Na ion battery: anode Na ion Hard carbon Na ion Graphitic carbon 46

48 2. Feedstock 3. Biochar preparation 4. Biochar characterization 5. Electrochemical performances 6. Conclusion Na ion battery: anode Hard carbon Na ion Graphitic carbon Elemental Na 47

49 2. Feedstock 3. Biochar preparation 4. Biochar characterization 5. Electrochemical performances 6. Conclusion Na ion battery: anode Based on fossil polymers Expensive Hard carbon Na ion Graphitic carbon Elemental Na 48

50 2. Feedstock 3. Biochar preparation 4. Biochar characterization 5. Electrochemical performances 6. Conclusion Na ion battery: anode Based on fossil polymers Expensive Hard carbon Elemental Na 49

51 2. Feedstock 3. Biochar preparation 4. Biochar characterization 5. Electrochemical performances 6. Conclusion Na ion battery: anode Based on fossil polymers Expensive Hard carbon Biochar Renewable Cheap Non graphitizable Until now? Very few electrochemical tests On some non characterized biomass samples Only electrochemists involved Elemental Na 50

52 2. Feedstock 3. Biochar preparation 4. Biochar characterization 5. Electrochemical performances 6. Conclusion Objective and working plan Objective: Evaluate quality of biochars from various biomass types as source of anode material for Na ion battery Working plan: Char preparation from selected biomass samples Char characterization Electrochemical performances Influence of biomass composition 51

53 2. Feedstock 3. Biochar preparation 4. Biochar characterization 5. Electrochemical performances 6. Conclusion Feedstock Sampling Drying Resinous wood Pine Deciduous wood Ash wood Perennial crop Miscanthus Agricultural co product Wheat straw Different macromolecular composition

54 2. Feedstock 3. Biochar preparation 4. Biochar characterization 5. Electrochemical performances 6. Conclusion Feedstock Sampling Drying Resinous wood Pine Deciduous wood Ash wood Perennial crop Miscanthus Agricultural co product Wheat straw Different macromolecular composition Different ash amount

55 2. Feedstock 3. Biochar preparation 4. Biochar characterization 5. Electrochemical performances 6. Conclusion Feedstock Sampling Drying Resinous wood Pine Deciduous wood Ash wood Perennial crop Miscanthus Agricultural co product Wheat straw Different macromolecular composition Different ash amount and inorganic elements amounts

56 2. Feedstock 3. Biochar preparation 4. Biochar characterization 5. Electrochemical performances 6. Conclusion Biochar preparation procedure Gas exit Inert gas Pressure: atmospheric Inert gas flow: 1.6 NL.min 1 Sample mass: 30 g Particle size: <300 µm Second stage: upgrading of biochar structure First stage: biomass pyrolysis to biochar 55

57 2. Feedstock 3. Biochar preparation 4. Biochar characterization 5. Electrochemical performances 6. Conclusion Biochar characterization XRay Diffraction Carbon interplanar distance d 002 0,375 nm 0,371 nm Bragg' s 2dsin law Carbon interplanar distance large enough for Na ion insertion/disinsertion Presence of Si in miscanthus/wheat straw Confirmation of biomass chemical characterization 56

58 2. Feedstock 3. Biochar preparation 4. Biochar characterization 5. Electrochemical performances 6. Conclusion Coin cell production from biochar Little cap Metallic resort Electrode support stainless steel Metallic Na electrode Separator CELGARD Separator VILEDON Electrolyte: 1M NaPF 6 EC:DMC (1:1) Carbon electrode Biochar 100 µm thick Slurry coating Formulation 80 / 10 / 10 Carbon black (Timcal ) Plastic gasket Large case Polyvinylidene fluoride in N methylpyrolidone 57

59 2. Feedstock 3. Biochar preparation 4. Biochar characterization 5. Electrochemical performances 6. Conclusion Coin cell production from biochar Little cap Metallic resort Electrode support stainless steel Metallic Na electrode Separator CELGARD Separator VILEDON Electrolyte: 1M NaPF 6 EC:DMC (1:1) 100 µm thick Slurry coating Formulation 80 / 10 / 10 Carbon electrode Plastic gasket Large case Coin cell Biochar Carbon black (Timcal ) Polyvinylidene fluoride in N methylpyrolidone 58

60 2. Feedstock 3. Biochar preparation 4. Biochar characterization 5. Electrochemical performances 6. Conclusion Biochar electrochemical performances Regime: C/10 (with C=372 ma.g 1 ) Cycling limits: 3V 10mV (+one step at constant voltage) Galvanostatic test First cycle Irreversibility Coulombic efficiency Na ion disinsertion capacity Na ion insertion capacity 59

61 2. Feedstock 3. Biochar preparation 4. Biochar characterization 5. Electrochemical performances 6. Conclusion Coulombic efficiency = All except wheat straw: satisfactory performances 60

62 2. Feedstock 3. Biochar preparation 4. Biochar characterization 5. Electrochemical performances 6. Conclusion Coulombic efficiency = All except wheat straw: satisfactory performances Correlation with biochar specific surface area In agreement with literature specifications Link with biomass properties: Ash amount? 61

63 2. Feedstock 3. Biochar preparation 4. Biochar characterization 5. Electrochemical performances 6. Conclusion Capacity vs cycles Pine = Ash wood Miscanthus Wheat straw Whatever biomass: very slight decrease of capacity along cycles No influence of biomass properties Favourable for process application Higher capacity of pine Due to lower ash amount? Composition in hemicellulose / lignin? 62

64 2. Feedstock 3. Biochar preparation 4. Biochar characterization 5. Electrochemical performances 6. Conclusion Conclusions Can biochars be used as anodes for Na ion battery? Yes! Biochars = promising feedstock for this application Clear differences between biomasses: Resinous wood Pine Agricultural co product Wheat straw Correlation with biochar properties Specific surface area No simple link with biomass properties Ash total amount? Hemicellulose/lignin composition? 63

65 2. Feedstock 3. Biochar preparation 4. Biochar characterization 5. Electrochemical performances 6. Conclusion What s next? Understand and model mechanisms Biomass properties Carbon properties Electrochemical performances Process conditions Optimize and up scale process 64

66 Questions? Details? Please feel free to contact me 65