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Jason Zhang Pacific Northwest National Laboratory Richland, WA Presentation in METS 2012 Taipei, Taiwan Nov. 11-14, 2012. HIGH ENERGY BATTERIES FOR ELECTRIC VEHICLE APPLICATIONS. Outline. Nano-structured Materials for Li-ion batteries 1.1 High capacity anode 1.2 High voltage cathode

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slide1

Jason Zhang

Pacific Northwest National Laboratory

Richland, WA

Presentation in METS 2012

Taipei, Taiwan

Nov. 11-14, 2012

HIGH ENERGY BATTERIES FOR ELECTRIC VEHICLE APPLICATIONS

slide2

Outline

    • Nano-structured Materials for Li-ion batteries
    • 1.1 High capacity anode
    • 1.2 High voltage cathode
  • 2. Energy Storage beyond Li-ions
      • 2.1 Highly Stable Li-S batteries
      • 2.2 High Capacity Li-air batteries
      • 2.3 Li-Metal Batteries
  • 3. Summary

2

slide3

LiMnPO4

Nano-structured Electrodes for Li-Ion Batteries

LiNi0.5Mn1.5O4

TiO2

Si

Tarascon & Armand, Nature2001 414, 359-367

3

self assembly of nano transition metal oxide graphene composite
Self Assembly of Nano-transition Metal Oxide/Graphene Composite

Self-assembly with graphene

Nanosynthesis: TiO2, SnO2, and other cathode materials

  • The self-assembled structure composed of ordered “super-lattice” nanocomposite with alternating layers of graphene nanosheets and metal oxides
  • Direct manufacturing of electrodes and batteries without binders and
  • other additives.

1.1 High Capacity Anodes

4

slide5

High Performance Nano-TiO2/Graphene Composite

1C

C/5

  • Best rate capability reported on anatase TiO2 with only 2.5wt% graphene.
  • Excellent cycling stability: ~ 170 mAh/g at 1C (PHEV constant output).

5

slide6

Conductive Rigid Skeleton Supported Silicon as High-Performance Li-ion Battery Anodes

B4C

Si

a)

c)

b)

Planetary ball milling

High energy ball milling

+ Graphite

Graphite

B4C

Si

  • Use conductive B4C as nano-/micro- millers to synthesize nano Si (< 10 nm ).
  • Use rigid skeleton to support in-situ generated nano-Si.
  • Use conductive carbon to coat the rigid skeleton supported silicon to form Si/Core/graphite (SCG) which can improve the structural integrity and conductivity of silicon anode.

6

slide7

Effects of Composition and Synthesis Condition on the Electrochemical Performances of Si Anodes

  • The ratio of Si, Core material and graphite are important to the electrochemical performance. Si:Core:graphite = 4:3:3 is the optimized ratio.
  • Ball milling time is also important to the electrochemical performance. 8 hr milling is good for HEBM and PBM.

7

limnpo 4 synthesized in molten hydrocarbon has preferred growth orientation
LiMnPO4 Synthesized in Molten Hydrocarbon Has Preferred Growth Orientation
  • Oleic acid was used as a surfactant and paraffin acts as a non-polar solvent that facilitate thermodynamically preferred crystal growth without agglomeration.
  • Pure phase of LiMnPO4 was obtained after 550ºC calcination.
  • As-prepared LiMnPO4 nanoplates are well dispersed without stacking.
  • LiMnPO4 nanoplates consists of a porous structure formed by self-assembled nanorods aligned in a preferred orientation with high specific surface area of 37.3m2/g.

1.2 High Voltage Cathodes

8

high performance limnpo 4 synthesized in molten hydrocarbon
High Performance LiMnPO4Synthesized in Molten Hydrocarbon

constant charge rate at C/25

constant charge rate at C/25

  • Specific capacity of 168mAh/g was achieved which is close to the theoretical capacity of LiMnPO4.
  • Flat voltage plateau at ~ 4.1 V indicates the phase transition between LiMnPO4 and MnPO4.
  • At 1C and 2C rate (PHEV constant output) capacity retention is 120 mAh/g and 100 mAh/g,
  • respectively.
  • Ragone plot indicates that the discharge power density is close in LiMnPO4 and LiFePO4
  • when fully charged at C/25; At low power (< 30 W/kg), energy density of
  • LiMnPO4 becomes comparable or higher than LiFePO4.
slide10

1.2 High Voltage Cathode: LiNi0.45Cr0.05Mn1.5O4

a

b

c

d

e

f

g

h

i

Doping significantly improve the performance of high voltage spinel

Cr-substituted spinel

LiNi0.5Mn1.5 O4

Annealed

LiNi0.5Mn1.5O4

Cr-substituted spinel

Annealed

LiNi0.45Mn1.5Cr0.05O4

  • The relative content between ordered and disordered phase can be tuned by changing synthesis condition.
  • Cr-substituted spinel LiNi0.45Cr0.05Mn1.5O4 exhibit stable cycling and excellent rate performance.

10

slide11

Conventional Electrolytes are Stable up to 5.2 V

  • Cutoff voltage ≤ 5.2 V: Very similar long cycling performance for the three carbonate mixtures.
  • Cutoff voltage = 5.3 V: EC-DMC is still stable but EC-DEC degrades fast.
  • Rate capability: EC-DMC and EC-EMC is similarly but EC-DEC is poorer.

11

slide12

2. Energy Storage beyond Li-ions

Comparison of Specific Energy of Various Batteries

Li-Metal

Batteries

12

slide13

2.1 Highly Stable Li-S Batteries

Potential: 3-4x improvement over Li-ion

Barrier: Li2S deposition on Li metal

slide14

Optimization of mesoporous carbon structures

MC.

MC with pores completely filled with sulfur.

(c)MC with pores partially filled with sulfur.

self breathing conductive polymer to encapsulate sulfur
Self-breathing Conductive Polymer to Encapsulate Sulfur

polymer hollow nanowire

S/polymer composite

Composite discharged to 1V

Composite recharged to 3V

  • At C/10, initial discharge capacity is 755 mAh/g with an activation process in the following cycles.
  • Even after 500 cycles at 1C the capacity retention reaches 76%.

15

slide16

2.2. High Capacity Li-Air Batteries

Non-Aqueous Li-air Batteries

Aqueous Li-air Batteries

2Li++ 2e− + O2 ↔ Li2O2 (2.96 V)

Alkaline: O2 + 2H2O + 4e−↔ 4OH− (3.43 V)Acid: O2+ 4e− + 4H+ ↔ 2H2O (4.26 V)

16

16

slide17

High Capacity Primary Li-air Batteries

2340 mAh/g carbon

Zhang et al, J. Power Sources 195:4332–4337 (2010).

17

slide18

Hierarchically Porous Graphene as a Lithium-Air Battery Electrode

a and b, SEM images of as-prepared graphene-based air electrodes

c and d, Discharged air electrode using FGS with C/O = 14 and C/O = 100, respectively.

e, TEM image of discharged air electrode.

f, Selected area electron diffraction pattern (SAED) of the particles: Li2O2.

  • Xiao et al. Nano Lett., 2011, 11 (11), pp 5071–5078.

18

slide19

Graphene as a Lithium-Air Battery Electrode

  • Record Capacity of 15,000 mAh/g
slide20

2.3 Li-Metal Batteries

  • Rechargeable Li-metal batteries are considered the “holy grail” of energy storage systems due to the high energy density.
  • However, Li dendrite growth in these batteries has prevented their practical applications inspect of intensive works in this field during the last 40 years.
  • Dendrite-free Li metal deposition is needed for rechargeable Li-metal batteries, Li-S batteries, Li-air batteries.

GM estimate on HE NMC/Li metal system: 540 Wh/kg, 1050 Wh/L in cell level (2012)

Classical Li dendrite growth

(Chianelli, Exxon, 1976)

slide21

Effect of CsPF6 Additive on

The Morphology of Li Deposition

a

b

c

20 µm

20 µm

20 µm

20 µm

20 µm

d

e

  • Control electrolyte: 1 M LiPF6 in PC.
  • CsPF6 concentration in the electrolyte: (a) 0 M, (b) 0.001 M, (c) 0.005 M, (d) 0.01 M, and (e) 0.05 M.
  • Cs+ additive can effectively suppress Li dendrite growth.
effect of current density on li deposition

a

b

20 µm

20 µm

20 µm

20 µm

d

c

Effect of Current Density on Li Deposition
  • Electrolyte: 1 M LiPF6 in PC with 0.05 M CsPF6 as additive.
  • Current density (mA cm-2): (a) 0.1, (b) 0.2, (c) 0.5, and (d) 1.0.
  • SHES mechanism is effective at different current densities.
morphology changes during long term cycling of li electrode in li lto cells

b

a

20 µm

20 µm

Morphology Changes During Long Term Cycling of Li Electrode in Li/LTO Cells

Surface morphologies of Li electrodes after 100 cycles in coin cells of Li|Li4Ti5O12 system containing electrolytes without (a) and with (b) Cs+-additive.

  • SHES mechanism is effective during long term cycling.
slide24

Excellent Long Term Stability of Li-Metal Batteries

Using Cs+ Additive

Cell: Li/Li4Ti5O12

1 M LiPF6 in PC with 0.05 M CsPF6

  • Columbic efficiency: 99.97%
  • Cycling stability: Only 3.3% capacity fade in 660 cycles
summary
Summary
    • Si electrode prepared by a cost effective method (ball milling)
      • 822 mAh/g and a capacity retention of ~ 94% in 100 cycles.
  • 2. High voltage, highly stable cathode
    • Retain more than 80% capacity after 500 cycles.
  • 3. Highly stable Li-S batteries
    • 650-800 mAh/g after 400 cycles.
  • 4. High capacity Li-air batteries
    • Li-air batteries operate in ambient air for 33 days with a specific energy of
    • ~362 Wh/kg for the complete battery.
    • Graphene based air electrode (~ 15,000 mAh/g).
  • 5. Dendrite-Free Li-Metal Batteries
    • Novel additives (Cs, Rb, etc.) based on the SHES mechanism can effectively suppress Li dendrite growth on Li metal batteries.
    • ~99.97% Coulombic efficiency and ~4.2% capacity fade in 610 cycles for Li-metal batteries.
slide26

Acknowledgments

  • Technical Team:
  • Wu Xu, Jie Xiao, Xiaolin Li, Yuyan Shao, V. Viswanathan, Jianzhi Hu, Vijayakumar Murugesan, Silas A. Towne, Phillip Koech, Donghai Mei, Fei Ding, Zimin Nie, Yuliang Cao, Yufan Xiao, Eduard Nasybulin, Jian Zhang, Dehong Hu, Gordon L. Graff, and Jun Liu
  • Financial support:
      • DOE/EERE/Office of Vehicle Technology
      • Laboratory Directed R&D Program of PNNL