How to develop post lithium ion battery. based on new concepts

Size: px

Start display at page:

Download "How to develop post lithium ion battery. based on new concepts"

Brenda Morris
6 years ago
Views:

1 How to develop post lithium ion battery based on new concepts A new type Li-Cu battery &Li-Air battery/fuel cell Dr. Haoshen ZHOU (hs.zhou@aist.go.jp) Group Leader of Energy Interface Technology Group Energy Technology Research Institute, AIST, Tsukuba, Japan

2 We face: Energy problem! Environmental problem! Oil problem! To develop the HEV, PHEV, EV

Nissan) The practice application always limited by the

3 A long history of EV, A dream of human being! 1947 Tama Auto-motors EV (From Webs of Wikipedia and Nissan) The practice application always limited by the battery technology at that time. The key technology of EV is battery technology

4 The history of rechargeable batteries (From J.M.Tarascon, M.Armand, Nature, 414, 2001, 359 )

5 e - e - Discharge Negative Positive Discharge charge Negative Positive Charge Carbon Metal Oxide Carbon Metal Oxide What is the necessary energy & power densities for EV? According to NEDO s suggestion! Energy Density Small EV & HEV 150 (Wh/kg) Plug in EV (Wh/kg) EV (Wh/kg)!! Power 400 (W/kg) Density (W/kg) (W/kg) To increase both the energy and power densities! 7-8 time of now s level

The power density has been remarkable improved by nanostructure active material: a AB: 12 wt% b AB: 0 wt% 4.5 2 A/g 1 A/g 0.5 A/g 0.1 A/g 4.0 3.5 3.0 2.5 2.0 1.5 Potential (V, vs.

6 The power density has been remarkable improved by nanostructure active material: a AB: 12 wt% b AB: 0 wt% A/g 1 A/g 0.5 A/g 0.1 A/g Potential (V, vs. Li/ ) 60C Capacity ( mah/g ) a) 83 wt.% LiFePO 4 /C, 12 wt.% AB, 5 wt.% PTFE b) Without acetylene black(ab) Zhou et. al. Angew. Chem. Int. Ed. 47, (2008), 7461 The challenge is how to improve the energy density

7 Is it possible to increase the energy density of now s LIB by 7 or 8 times? e - e - Discharge Negative Positive Rocking Chair Discharge charge Negative Positive Charge Carbon Metal Oxide Carbon Metal Oxide Anode active (mah/g): LiC 6 (372), Li 4.4 Sn(994), Li 4.4 Si(4000), Li(3800) Cathode active (mah/g): LiCoO 2 (130), LiMn 2 O 4 (120), LiFeO 4 (170), VO x (350)etc The Concept of Rocking Chair should be broken to develop next generation battery with large energy density

8 Negative Materials Positive Materials How to develop next generation battery? Capacity (mah g -1 ) Potential ( V, vs. Li/ )

9 How to increase the cathode capacities? The problem is improve the cathode active Generally the theoretical value of cathode active materials LiM x O y (here: M metal; O can be replace by F, S, PO 4 etc.) C = zf/ (weight of LiM x O y ) (mah/g) For strategy design: (a) z > 1.0 (b) use LiM x or M as active M : element active material

10 e E o /V Na + e - Na E o /V Mg + 2e - Mg E o /V Ca + 2e - Ca E o /V Mn + 2e - Mn E o /V Fe + 2e - Fe E o /V Co + 2e - Co E o /V Ni + 2e - Ni E o /V Cu + 2e - Cu E o /V Ag + e - Ag E o /V Au + e - Au E o /V Voltage= 3.4 V Beyond Lithium ion battery

11 Periodic Table of the Elements Anode active material cathode active material Is it possible to design a new type Li-Cu Rechargeable Battery?

12 From Li ion battery into Li-Cu rechargeable battery with hybrid electrolytes

Alessandro Volta John Fredric Daniel Anode: Zn Zn 2+ + 2e - Cathode:

13 Metal-Metal battery Use M (metal) as cathode active Metal-metal battery The first primary battery is Zn-Cu battery. Alessandro Volta John Fredric Daniel Anode: Zn Zn e - Cathode: Cu e - Cu However, this is primary battery!! For charging, Zn will be coated by Cu layer!!

14 Developing Hybrid Electrolyte Cu 2+ Cu Organic electrolyte for Li Aqueous electrolyte for Cu LISICON: only can pass through LISICON Hybrid electrolytes Organic-Aqueous Hybrid Electrolyte Liquid-Solid Hybrid Electrolyte

y P 3-y O 12 ) Lithium ion conductivity (1

15 Composition:Li 2 O-Al 2 O 3 -SiO 2 -P 2 O 5 -TiO 2 -GeO 2 (Li 1+x+y Al x (Ti,Ge) 2-x Si y P 3-y O 12 ) Lithium ion conductivity ( S/cm at 25 ) (Provided by Ohara Company)

16 The structure of Lithium Cupper Rechargeable Battery - Discharge + Li e - ClO 4 - Charge Cu 2+ e - Cu Charge: Cathode: Cu Cu e - Anode: + e - Li NO 3 - Anode Organic electrolyte aqueous LISICON Cathode Discharge: Cathode: Cu e - Cu Anode: Li + e - hybrid electrolytes Wang and Zhou, Electrochemistry Communications, 11, (2009), 1834

(Graphite) Positive + (Li x Host ) Non-aqueous Liquid solution - Negative (Graphite)

17 Design rechargeable Li-Cu Battery with hybrid electrolytes Charge e -1 e -1 V Discharge e -1 e -1 V Positive + (Li x Host ) Non-aqueous Liquid solution - Negative (Graphite) Positive + (Li x Host ) Non-aqueous Liquid solution - Negative (Graphite) (a) Lithium ion battery (b) Lithium cupper rechargeable battery Beyond Lithium ion battery

18 Cu dissolution Current ( A ) Cu deposition Potential (V, vs. Li/ ) Wang and Zhou, Electrochemistry Communications, 11, (2009), 1834

19 b Cu Cu 2+ Charge at 1 ma/cm 2 for 16 h Discharge at 1 ma/cm 2 Cu Cu Capaciyt ( mah g -1 ) Potential ( V, vs. Li/ )

20 b Cu Cu 2+ Charge at 1 ma/cm 2 for 16 h 4 ma/cm 2 3 ma/cm 2 2 ma/cm 2 1 ma/cm ma/cm 2 Potential ( V, vs. Li/ ) Discharge at different currents Cu Cu Capaciyt ( mah g -1 ) Wang and Zhou, Electrochemistry Communications, 11, (2009), 1834

21 Cu Cu 2+ Cu Cu Charge-discharge cycle time (hours) Potential (V, vs. Li/ )

22 b Discharge capacity ( mah g -1 ) Coulombic efficiency ( % ) Cycle number Wang and Zhou, Electrochemistry Communications, 11, (2009), 1834

24 Why renewable battery is necessary? Preparation of conventional cathode Extracting the raw materials 70 kg CO 2 per kwh [ Ishihara, K. 5th Int. Conf. Ecobalance, Tsukuba (2002).] High temperature Solid-state reaction

25 Recycling of conventional cathode is very difficult! ( Recycling?

26 Li-Cu rechargeable battery is a renewable (or recyclable) battery e - Charge e - - Discharge + Cu 2+ Charge: Cathode: Cu Cu e - Anode: + e - Li Li Cu Discharge: Cathode: Cu e - Cu Anode: Li + e - Anode Cathode Organic electrolyte aqueous LISICON Wang and Zhou, Electrochemistry Communications, 11, (2009), 1834

27 To develop New Type Li-Air Battery The Li-Cu rechargeable battery can not satisfy 1000Wh/kg for EV. To develop new type Li-Air Battery

28 Metal-Air Battery Theoretically, the capacity of cathode (or air electrode) can be remarkable large because cathode active O 2 is not included in battery package. For energy density: Zn-Air: 2Zn+O 2 =>2ZnO 1350Wh/kg Ca-Air: 2Ca+O 2 =>2CaO 4180Wh/kg Al-Air: 4Al+3O 2 =>2Al 2 O Wh/kg Li-Air: 4Li+O 2 =>2Li 2 O 11140Wh/kg Abraham K.M., et al, ; J. Electrochem. Soc. Vol.143, (1996),1

29 The 1 st paper about Li-Air battery Dr.Abraham K.M., et al, ; J. Electrochem. Soc. Vol.143, (1996),1 Cycle performance has been improved by Bruce s group. Prof. P. G. Bruce, et al, ; J. Am. Chem. Soc. Vol.128, (2006), 1390

30 The problems of conventional Li-Air Battery V V e -1 e -1 e -1 e -1 O 2 O 2 Catalyst Catalyst Carbon Carbon Li 2 O 2 Lithium Organic electrolyte Porous electrode containing catalyst Lithium Organic electrolyte Porous electrode containing catalyst The discharge product Li 2 O 2 or Li 2 O is not soluble in organic electrolyte, which inevitably clogs porous catalytic electrode. After fully clogged by formed Li 2 O 2 deposit, the porous catalytic electrode cannot reduce O 2 from environment any more.

31 Design new type lithium Air Battery (1) to release soluble discharge product as FC (2) O 2 + 2H 2 O + 4e - 4OH - (3) to use hybrid electrolyte: organic electrolyte for anode area, aqueous electrolyte for cathode area, and LISICON as a separator which only let Li ion pass through it. Wang and Zhou, Journal of Power Sources, 195, (2010), 358

32 How to design the New Type Lithium Air Battery OH - Li Air OH - Anode Organic Electrolyte LISICON Aqueous Catalyst Air Electrode (Porous Carbon) Separate LIB Anode Area FC FC Are 正極側 Electrode Area Area Hybrid Electrolyte Hybrid of LIB and FC

33 The structure of New Type Lithium Air Battery LIB Anode Area Wang and Zhou, Journal of Power Sources, 195, (2010), 358 Discharge e OH - FC Air Electrode Area 金属 Li 空気 Air OH - Anode Air Electrode (carbon porous) Organic electrolyte aqueous LISICON Catalyst Li organic electrolyte LISICON 10ml 1 M KOH Mn3O4 catalytic + C electrode LISICON = OHARA Glass, 0.15 millimeter, 10-4 S cm -1

34 Discharge:Air electrode: O 2 + 2H 2 O + 4e - 4OH - Anode: Li + e - Charge:Air electrode: 4OH - O 2 + 2H 2 O + 4e - Anode: + e- Li Advantages at high ph codition: At high ph condition, the low cost catalysts such as metal oxides can be used. However, at acidic condition, expensive catalyst such as Pt has to be used to reduce O. Now, the LISICION is also weak in strong acidic condition.

35 Continue discharge curve 6 0 Discharge time (hours) OCV Cell Voltage ( V ) Capacity ( mah g -1 ) Current density is 0.5mA/cm 2 Based on the mass of porous catalytic electrode (carbon + binder + catalyst MnO x ) Wang and Zhou, Journal of Power Sources, 195, (2010), 358

36 Comparing with reported capacity of Conventional lithium air battery Based on the mass of only carbon Conventional lithium air battery s results Based on the mass of (carbon + binder + Current density Referenc es catalyst) 1600 mah g mah g mah g mah g mah g mah g -1 Data is not given Data is not given Data is not given Data is not given 730 mah g-1 Data is not given 0.1 ma cm ma cm ma cm ma cm ma g -1 70mA g -1 K.M.Abrah am 1996,JES J.Read 2002,JES Toshiba 2005,JPS J.Read 2003,JES P.G.Bruce 2006,JACS P.G.Bruce 2008,ACIE mah g mah g macm -1 (100mAg -1 )

37 Set up another cathode electrode: (which is only used in charge process) The carbon used in air electrode will be oxidized in charge process to give high charge potential and poor cycle performance. Discharge e Charge Another cathode electrode e - ~V O OH - OH - 金属 Li 空気 Air 金属 Li OH - Anode Organic electrolyte LISICON aqueous Air Electrode (carbon porous) Catalyst

38 6 Charge-discharge curves at aqueous electrolyte Cell Voltage (V,vs. Li/ ) Time (hours) Current density is 0.5mA/cm 2 Based on the mass of porous catalytic electrode (carbon + binder + catalyst) Li organic electrolyte LISICON KOH Gel Mn 3 O 4 catalytic + C electrode

39 The problem of Now s Lithium Air Battery Hz 63 Hz 0.2Hz 0.01Hz 金属 Li Discharge e OH - 空気 Air 10 OH Z' (Ohm) Anode Organic electrolyte LISICON aqueous Air Electrode (carbon porous) Catalyst The problem of Now s Lithium Air Battery Lithium ion conductivity of LISICON is poor ( S/cm at 25 o C)! Wang and Zhou, Journal of Power Sources, 195, (2010), 358 -Z'' (Ohm)

40 Drawback of our developed Li-air batteries The low inherent solubility of Lithium hydroxide The another direction is to develop Lithium Fuel Cell based on Now s concept.

41 Now s problem of H 2 -Air fuel cell (1) safe of H 2 s storage (2)expensive Pt catalyst +

42 New Concept of Li-Air fuel cell H 2 -Air Fuel Cell Li-Air Fuel Cell Wang and Zhou, Journal of Power Sources, 195, (2010), 358

43 The concept for Li Fuel Cell e - e - OH - Reproduce LiOH から金属 Metal Li の再生 Li Li 金属 Li OH - Air 空気 Collection LiOH の回収 of LiOH It requires cooperation works between the researchers in rechargeable lithium battery and Fuel Cell fields Wang and Zhou, Journal of Power Sources, 195, (2010), 358

44 The directions of the new type Lithium Air Battery Discharge e OH - 金属 Li 空気 Air OH - Anode Organic electrolyte LISICON aqueous Air Electrode (carbon porous) Catalyst (1)Rechargeable Li-Air Battery (2)Li-Air Fuel Cell (Lithium Fuel Cell)

45 Conclusion Developed hybrid electrolytes (Organic/LISICON/aqueous electrolyte) Developed Li-Cu rechargeable battery. Developed New Type Li-Air battery. Developed concept for Li-Air Fuel Cell. There are still some problems have to solve. Thank Dr. Y. Wang, Dr. H. Li and AIST, JSPS funds. Thank Ohara company providing LISICON films. Thank all of you for your attentions

Lithium Batteries. Rechargeable batteries

Lithium Batteries. Rechargeable batteries Lithium Batteries One of the main attractions of lithium as an anode material is its position as the most electronegative metal in the electrochemical series combined with its low density, thus offering