Batterifondsprogrammet

Recycling of discarded Li-Ion batteries (LIBs)

Nordic Recycling Day VIII 27th of September 2017

Jakob Kero

PhD student LTU

Batterifondsprogrammet

Outline

• Introduction to Li-ion battery market

• Li-ion battery composition and recycling

• Project: Recycling of spent Li-ion batteries

2

Batterifondsprogrammet

Photo: Ssuaphoto

Introduction - Where are LIBs used? • Li-ion batteries are used in many applications • Increasing political and consumer focus on climate change

• Increase electric vehicle (EV) production • Increased lithium-ion battery (LIB) production

3

Batterifondsprogrammet

Photo: Ssuaphoto

Introduction - Where are LIBs used?

1,67 1,78 1,79 4,04 5,89 12,48 60,65 179,23

383,09

706,77

1256,9

0

200

400

600

800

1000

1200

1400

2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015

Cars

(tho

usan

ds)

Year

Electric car stock (BEV and PHEV), 2005-15 (thousands)

Source: © OECD/IEA 2016, Global EV Outlook 2016, IEA Publishing

Almost 0.9% of

car market

4

• Li-ion batteries are used in many applications • Increasing political and consumer focus on climate change

• Increase electric vehicle (EV) production • Increased lithium-ion battery (LIB) production

Batterifondsprogrammet

Introduction - Why LIBs? • LIB is an important technology for electric vehicle (EV) – high specific

power, energy density and lifetime

• Ongoing development of battery composition

Development of battery energy density and cost

Source: © OECD/IEA 2016, Global EV Outlook 2016, IEA Publishing 5

Batterifondsprogrammet

Introduction - Why LIBs? • LIB is an important technology for electric vehicle (EV) – high specific

power, energy density and lifetime

• Ongoing development of battery composition

Development of battery energy density and cost

Source: © OECD/IEA 2016, Global EV Outlook 2016, IEA Publishing

Energy density: 30-50 Wh/kg Lead acid battery 110-160 Wh/kg Li-ion battery

6

Batterifondsprogrammet

LIB composition – What’s inside? • Cathode

• Lithium metal oxide, LiMeO2, graphite and PVDF binder on Al-foil

• Metals used: i.e. Co, Ni, Mn, Al, Fe

• Anode • Carbon and PVDF binder on Cu-foil

• Electrolyte • Li salts and organic solvents (flammable).

• Casing • Steel (Fe, Cr, Ni), Al

• Complex material to recycle

7

Fig 2: Prismatic design of a battery (Battery, 2003)

Cathode Anode

Batterifondsprogrammet

LIB recycling – challenges!

• Existing high temperature recycling process • Based on Co and Ni recovery

• Short circuiting / thermal runaway • Need of pre-treatment

• Battery chemistries • Development of cathode active material

• What to recycle in the future?

System Electrodes

NCA Graphite LFP(phosphate) Graphite

MS (spinel) Graphite

Positive (Cathode)

LiNi0.8Co0.15Al0.05O2

LiFePO4

LiMn2O4

8

Batterifondsprogrammet

Recycling of spent LIBs project Recap:

• Increasing volumes of end of life LIBs

• Ongoing development of battery chemistry

• Recycling in existing processes

Aim:

• To investigate thermochemical feasibility of the processes – FactSage • To recycle spent LIBs in copper pyrometallurgical process

• Distribution of Li and Co between phases

Cu-system • Slag: Fe2SiO4 +

(CaO) • Matte: Cu2S • Metal: Cu

9

Batterifondsprogrammet

FactSage results

Validation with experimental work!

Li to gas phase: • T increase >1300℃ • CaO addition • <logPO2 (-10)

Co to matte phase: • CaO addition • <logPO2(-10)

Slag

Matte

Atm. Ar

Li

(Li)

Co

(Co)

10

Batterifondsprogrammet

Experimental method

Sample • Slag, Fe2SiO4 50g • Matte, Cu2S 75g • Metal, Cu 25g • 5% LiCoO2 (constant) • CaO addition

Parameter Low value Middle value High value

Temperature 1250℃ 1350℃ 1450℃

Fe/SiO2 1 1.3 1.6

CaO addition 0 wt.% 5 wt.% 10 wt.%

11

• Inert atmosphere

Batterifondsprogrammet

0,00

0,20

0,40

0,60

0,80

1,00

1,20

1,40

N1 N2 N3 N4 N5 N6 N7 N8 N9 N10 N11

Cont

ent (

%)

Samples

Li-content (wt.%)

Li, slag % Li, matte % Li, metal %

Experiment results – Li - CaO add

No CaO

12

CaO add

Lithium in slag phase

Batterifondsprogrammet

Experimental results – Li mass bal.

• No CaO addition • 88% Li in slag

• CaO addition 10% • 35% Li loss

• CaO addition 5% • 56% Li loss

• No/small effect

of Fe/SiO2 ratio

2,02 2,74 1,77 2,25 1,91 2,78 3,09 6,29 2,71 1,82 2,67

88,0 89,1 89,1 86,1

58,1 61,4 49,3

53,5

35,2 40,7 34,5

10,0 8,1 9,2 11,6

40,0 35,8 47,7

40,1

62,0 57,5 62,8

0

10

20

30

40

50

60

70

80

90

100

N1 N2 N3 N4 N5 N6 N7 N8 N9 N10 N11

Phas

e di

strib

utio

n (%

)

Sample

Li – mass balance (%) Li metal Li matte Li slag Li gas

CaO add 5 % CaO add.10 % No CaO add.

13

Batterifondsprogrammet

Experimental results – Li

• Middle-point samples N9-N11

• Glassy amorphous slag • Verified by XRD and SEM • Consistent for all 3 samples • Most of Li reported as loss

(58-63 mass%)

Position [°2Theta] (Copper (Cu))

20 30 40 50 60 70

Counts

0

500

1000

Fredrik run 1580 1 hour ny_N9_slagg_1timme

Homogeneous phase

Conditions • T 1350°C • Fe/SiO2 1.3 • CaO add 5%

14

Batterifondsprogrammet

0,00

1,00

2,00

3,00

4,00

5,00

6,00

7,00

N2 N4 N6 N8 N1 N3 N5 N7 N9 N10 N11

Cont

ent (

%)

Samples

Co, slag % Co, matte % Co, metal %

Experiment results – Co - Temp

15

1450°C

1250°C

Cobalt in metal phase

Batterifondsprogrammet

0,00

1,00

2,00

3,00

4,00

5,00

6,00

7,00

N2 N4 N6 N8 N1 N3 N5 N7 N9 N10 N11

Cont

ent (

%)

Samples

Co, slag % Co, matte % Co, metal %

Experiment results – Co - Temp

16

1250°C

1450°C

Cobalt in slag phase

Batterifondsprogrammet

Experimental results – Co mass bal. • 1450°C

• 66% Co in metal

• 1250°C • 52% Co in

slag

• No/small effect of Fe/SiO2 ratio and CaO add

28,2 29,0 37,4

22,3 20,8 23,1 26,5 24,1 21,2 28,1

20,0

63,4 65,2 57,8

76,9

11,1 12,4

16,8 11,0

33,5 23,8

56,2

6,3 2,6 1,3 1,3

48,7 39,7

53,6 65,6 16,4

32,6

10,4

2,1 3,2 3,5

19,4 24,8

3,1

28,9 15,4 13,3

0,0

10,0

20,0

30,0

40,0

50,0

60,0

70,0

80,0

90,0

100,0

N2 N4 N6 N8 N1 N3 N5 N7 N9 N10 N11

Phas

e di

strib

utio

n Co

(%)

Samples

Co - mass balance (%) Matte Co distr(%) Metal Co distr(%) Slag Co distr(%) Loss Co distr(%)

T 1350°C T 1250°C T 1450°C.

17

Batterifondsprogrammet

Summary

• Li is distributed between slag and gaseous phases (loss)

• CaO addition reduces the amount of Li reported to the slag phase

• Co is distributed between slag, matte and metal(mainly) phases

• Co is at 1250⁰C dissolved into the main slag phase • Co is at 1450⁰C in the metal phase and as diffused

metal droplets in the slag and matte phase • Co in matte phase as inclusions (metal droplets) –

no dissolution.

18

Batterifondsprogrammet

Further work

• Investigate the influence of adding other metals as Al, Mn, Ni to the system

• Further investigation with spent LIBs instead of LiCoO2 addition to the Cu-system

• Pre-treatment of batteries, physical separation

19

Batterifondsprogrammet

Thank you for your attention!

Project partners: Stena Recycling AB

KTH Chalmers