relib - faraday.ac.uk

RELIB35 Minute Review

20th February 2019

Paul Anderson (Project PI)

TESTING &DISASSEMBLY

SECONDLIFE

BATTERYPACK

RECYCLEPHYSICAL

SEPARATIONLEGAL

LCA &ENVIRONMENTAL

ECONOMICS

POLICY

PYRO

CHEMICAL

BIO

Business & Regulation

Gateway Testing & Dismantling

Characterisation & Recycling

SAFETY TRAINING & ADVICE GATEWAY TESTING &

DISMANTLING

o Provided training on science, technology and safety aspects of lithium ion batteries to Faraday Institution PhD students and Research Associates (2 x 2 day courses).

o Professor Paul Christensen has worked with Nissan’s safety team at their battery production facility in Sunderland and continues ongoing advice and support.

o Invitation to present to insurance company (Allianz) – date to be confirmed

o Developing safety alert for British Metals Recycling Association.

Assisting Fire Brigade to develop their knowledge and procedures

o Presented to Tyne and Wear Fire and Rescue Service (Dec 2018). They have subsequently revised their Safe Operating Procedures for EV fires. Professor Paul Christensen is now a Special Advisor to TWFRS.

o Collaborating with TWFRS to carry out fire safety experiments on battery modules at their facility, and advise on chemical fire safety for training purposes.

o The London Fire Brigade have made initial contact for advice on the management of lithium ion battery fires.

Internal & External

CHARACTERISATION & RECYCLING

WS2

Challenge: Different approach to just acid etch is needed to separate battery materials selectively and efficiently


DELAMINATION - UNWETTED ELECTRODES

Anode: 50x50 µm Cathode: 50x50 µm

Ra: 554 nm Ra: 329 nm

Materials characterisation of the anode and cathode through AFM, SEM and 3DM and scratch testing finds significant differences in mechanical and chemical behaviour between the anode and cathode

o Mechanical data can be obtainedfrom the AFM in order to helpdistinguish between the cathodeactive particles and polymer binder.

o Adhesion of the AFM tip to thepolymer is higher than that of theactive material. This produces brightspots on the adhesion map aroundthe metal oxide particles.


UNWETTED ELECTRODES: MECHANICAL DATA

Adhesion

Ra: 19.1 nm

Height Adhesion

Ra: 19.1 nm

o Overlaying the adhesion data onto the height data shows the bright spots occurring between the metal oxide particles.

o Suggests the polymer is able to fully coat all particles, allowing for strong adhesion to each other and to the aluminium current collector.


UNWETTED ELECTRODES: MECHANICAL DATA

o Scratch testing is a mechanical test that shows that the adhesion of the electrode materials to the current collector is higher for the cathode (metal oxide) than the anode (carbon)

o This is dependent on the particle size and distribution of the polymeric binder. It begins to reveal the mechanism of fragmentation

Average critical load for

Cu/C: 3.7 ± 0.17 N


MECHANICAL CHARACTERISATION

Trench depth measured here, at 3.6 N

3.62 N12.0 mm3.40 N

14.2 mm3.84 N

• Average critical load for Cu/C: 3.7 ± 0.17 N

Scratch direction

3DM Image of Anode

o The process we are developing selectively separates the carbon from the copper, and the metal oxide from the aluminium, through mechano-chemical steps

Space/time yield: 65g/(2000 ml x 10s)

= 3.25 x10-3 gml-1s-1

(100 x increase from current process)

- 1800 anodes an hour – 90 pouch cells an hour –

2160 cells a day (24 hour process)


SELECTIVE PROCESS DEVELOPMENT - ANODE

Edge of the cleaned area showing after 2 seconds treatment

150 µm

CopperPVDFCarbon

o Cleans both sides of the anode at once

o Delamination starts between the copper and PVDF layer and then tears off

o Cracking can be seen in the carbon layer on the bottom side of the anode

The bigger particle size is influential in propagating lateral cracking within the

anode material


SELECTIVE PROCESS DEVELOPMENT - ANODE


COMPARISON OF SCRATCH TRENCH DEPTHS FROM ANODE & CATHODE

Anode Cathode

Average trench depth (µm) 91 33

Average trench width at base (µm) 132 140

Average trench width at top (µm) 497 270

Thickness of active material (µm) 140 85

Average particle size (µm) 16 ± 2.8 2.3 ± 0.64

o The active material strength increases withdecreasing particle size

o Smaller particles have a higher surface area for agiven load, therefore the load will be spread overa larger area for the cathode, and increase theforce required for delamination

Should be possible to mechanically separate anode andcathode materials but may be made specific with solvent

0

20

40

60

80

100

120

140

160

180

0 200 400 600 800 1000

Dep

th (

µm

)

Distance (µm)

Depth profile of scratch test on unwetted anode and cathode, showing the trench at the same force as the critical load on the anode: 3.7 N. (5A1-C2,A3)

Anode

Cathode

The average trench width at the top of the cathode is 45 % smaller than the anode.The average trench depth for the cathode is 63 % smaller than the anode.

Carbon + CopperSeparated

Water

Froth Flotation

Carbon + Binder

Mechano-catalysed process

Cathode Untouched

Mechano-catalysed process

Acid

Metal Oxide + AluminiumSeparated

Space/time yield: 65g/(2000 ml x 10s)= 3.25 x10-3 gml-1s-1

(100 x increase from current process)

Metal Oxide LeachingAnode + Cathode


TWO-STAGE SELECTIVE RECYCLING PROCESS

Carbon + CopperSeparated

Water

Mechano- catalysed process

Before

After

Separated in 10 seconds


SELECTIVE RECYCLING PROCESS - ANODE

Water


Cathode Untouched


AcidMetal Oxide + Aluminium

Separated

Metal Oxide Leaching

Separated in 20 seconds


SELECTIVE RECYCLING PROCESS - CATHODE


SHORT LOOP RECYCLING UPDATE

o Initially investigated sulphuric/nitric acid (showed some selectivity but also severe delithiation of the remaining LO/Spinel –extra processing would be required to regenerate these materials).

o Looking into organic acids – interesting initial results:

o Results show that the spinel phase can be removed in 3 minutes. Plan is to recoat Al with the material recovered from the acid treatment and see how it performs. Leached solution has been treated through a sol-gel method, shows phase pure recovered spinel (acid acts as leaching agent and facilitates resynthesis). Long term – repurpose leached solutions as NMC.

PXRD of recovered material Phase refinement XRF elemental analysis PXRD of recovered spinel

o From the four bacterial strains used,Desulfovibrio alaskensis G20 is the mostefficient species to bio-precipitate and recovercobalt.

o Trials with nickel were also included as thismetal is present in the battery leachates andexhibit similar chemical behaviour to Co inaqueous solution.

o The recovery of both metals was always higherin the biological fraction containingextracellular medium (Fig. 1 C-D) than with thebacterial cells alone.


BIO-PRECIPITATION TRIALS FORCOBALT AND NICKEL

Fig.1 Recovery of Co (A&C) and Ni (B&D) with a single metal (Co red/Ni blue) and when both metals are present (grey), n=1.

Fig.2 Recovery of Co2+ (A, red) and Ni2+ (B, blue) under different case scenarios and dilutions (1:10 (dark

red/dark blue) and 1:100 (light red/light blue). Values expressed as the Mean ± SD (n=3)

o Trials were performed with a single metal and with both metals basedon the estimated concentrations in battery leachates reported byBirmingham.

o Metal recovery is maximised at higher dilutions (1:100) of the batteryleachates due to the metal toxicity for the bacteria decreases (Fig.2).

o Higher recovery rates observed for nickel than for cobalt (Fig.3).


BIO-PRECIPITATION TRIALS WITH COBALT AND NICKEL AND BACTERIAL CELLS

Estimated concentration of Ni and Co in battery leachates

case1 case2 case3 case4 case5

Ni:

Co

reco

vere

d m

ass r

ati

o

0

5

10

15

20

Fig.3 Recovery ration Ni:Co (dilution 1:10). Mean ± SD (n=3). No

statistically significant differences.

case 1 2 3 4 5

Ni (g/L) 0.66 1.06 0.60 0.53 0.66

Co (g/L) 0.14 0.29 0.29 0.39 0.24

Ni/Co 4.6 3.7 2.1 1.4 2.8

o Samples of bio-precipitated Co and Ni were delivered to the University of Liverpool for characterisation (Nigel Browning group) using ultra high resolution scanning transmission electron microscopy (STEM) and spectroscopic techniques (e.g. EELS, EDS).

o The production of Co/Ni-based nanoparticles was confirmed.

o The particle size depends on the biological fraction - extracellular medium (Fig.4) vs bacteria (Fig.5) - used during the bio-recovery process.


PRODUCTION OF Co/Ni – BASED NANOPARTICLES

Fig.4 Bimetallic Co/Ni oxide particles synthesised in the extracellular medium produced by D. alaskensis

G20 analysed by STEM (left) and EELs (right). Images facilitated by UoLi.

O-K

Co-LNi-L

Fig.5 Extremely small nanoparticles of Ni (left) and Co (right) produced when

bacterial cells are present. Images facilitated by UoLi.

o An in-situ TEM stage has been purchased and tested and is starting to be used to examine the dynamic chemical changes at the anode and cathode during the charge/discharge process.

o An in-situ SEM/Helium ion microscope (HIM) stage has been designed and is being constructed to allow diffusion effects to be monitored for both chemical systems and biological systems.

o Initial post-mortem studies of electrode materials have identified chemical changes that exist in the materials after cycling that can be studied by in-situ methods.

o Post-mortem studies of biological systems have shown the precipitation of metal nanoparticles –the first step in understanding how metals can be leached from battery components and recovered.

o All the characterisation work is being performed in collaboration with the degradation project (Dr.B. Layla Mehdi, UofLi) to establish connectivity between the various stages of life cycle in Li-ion batteries


CHARACTERISATION

To assess the ability of the in-situ methods to study the dynamic processes involved with bacteria recovery of transition metal elements such as Co, Fe and Ni, the first stage of the experiments focused on understanding what the samples looked like post-mortem.


CHARACTERISATION

STEM images of cells exposed to 10 mg L-1 Ni (II) for 20h. Nanoparticles can be seen at various locations and in particular1nm arrays of particles can be seen at locations that may correlate with crystalline protein surface layers.

WS1

GATEWAY TESTING &

DISMANTLING

GATEWAY TESTING &

DISMANTLING

SECOND LIFE APPLICATIONSApplication Power range C-rate In service depth of discharge Frequency of events Minimum 2nd service life

Peak shaving (PS) 10 kW - 10 MW 0.5 - 2 5-90% 1 or 2/day in season 5-years

Voltage control (VC) 10 kW - 100 kW 1 5-80% Continuous 5-10 years

Operating reserves (OR) Minimum aggregation of 3

MW

0.5 High Up to 3/day 2-years

Frequency response (FR) Minimum aggregation of 1

MW

1 - 4 Typically low

- moderate

Continuous - dynamic services. Daily

- static services

3-years

Triad avoidance (TA) 100 kW - 1 MW 1 90% ~40 during season 3-years

Capacity Market (CM) 2 MW - 10 MW 0.25 - 1 90% Few per year (system stress events) 5-years

Arbitrage (Ar) 1 kW - 10 MW 2 90% 1-3/day 2 or 3-years

Energy imbalance (EI)

exposure

1 kW - 10 MW 1 90% 1-3/day 2 or 3-years

Renewables firming (RF) 1 kW - 10 MW 0.5 - 2 50% Daily or weekly 5-years

Un-interuptable power supply

(UP)

1 kW - 10 MW 0.25 - 2 75% Rarely to daily (depending on

location)

2 - 5-years

Off-grid power (OP) 50 kW - 10 MW 0.1 - 0.5 60% Daily 2 - 5-years

Solar-home system (SH) 100 W - 10 kW 0.1 - 0.5 70% Daily 2 - 5-years

Low-range mobility (LM) 10 kW - 100 kW 0.5 - 5 70% 0.5 - 4/day 2 - 5-years

Working in conjunction with

gateway testing to identify the optimum

2nd Life Application based on the

measured properties of the

cells/modules/pack

WS3

BUSINESS & REGULATION


o Presentation by Hans Eric Melin of Circular Energy Storage Research & Consulting

o Attended by 30 delegates including representatives from JLR, Cawleys, JM.

o Highlighted:

1. Rapid developments in Chinese market

2. Need for effective collection and sorting systems to maximise value recovery

3. Slow build up of EoL EV battery packs in Europe – and UK

o In other countries the processing of LiBs from smaller consumer products (phones, laptops, etc) is conducted in the same facilities as EV batteries. Currently there are no such facilities in the UK.

REVIEW LiB EoL MARKET 2018 -2025


WORKSHOP ON RECYCLING & 2nd LIFE LiBs

o Large market for second life applications in China- demand for one specific application exceeds current availability of second life batteries.



Second life potential and initiatives in Europe

MakerTotal

MWh

MWh until

2015

Est MWh

EOL 2018End-of-life strategy Key partners

Tesla 6397 2143 5 Remanufacturing, recycling

Nissan 3098 1292 5 Remanufacturing, residential and C&I ESS Mobility House, Eaton, SNT

Renault 3911 1287 4 Remanufacturing, residential ESS Powervault, Connected Energy

Volkswagen 2080 734 1 Directly to recycling

BMW 2729 657 <1 Utility grid ESS Mobility House, Vattenfall

Daimler 2641 135 <1 Utility grid ESS Mobility House

Mitsubishi 1319 717 1 C&I ESS Forsee Power

Volvo 590 258 <1 Remanufacturing, residential ESS Box of Energy

Kia 534 169 <1 May follow Hyundai in utility grid ESS Pot. Greensmith Energy

Audi 248 111 <1 C&I ESS N‑ERGIE/Covalion

Peugeot 153 92 <1 C&I ESS Forsee Power

Citroën 135 89 <1 C&I ESS Forsee Power


CHINESE RECYCLING PROGRAMME

o China produced 413,200 new energy vehicles (NEV) in first six months of 2018, up 94.9% compared with a year earlier. Sales more than doubled to 412,000 units over the period.

o China produced 37.35 million kilowatt hours of NEV batteries in 2017, with overall prices declining by a quarter to about 1.45 yuan ($0.2143) per Watt-hour.

o Experts have warned that annual lithium battery waste could reach around 170,000 tonnes by 2020.

o China will launch a pilot electric vehicle battery recycling scheme in 17 cities and regions, the industry ministry said, with Beijing keen to head off an emerging pollution threat.

o The ministry has already published draft rules to create a “traceability management platform” aimed at tracking the entire life cycle of electric car batteries from production to disposal.

o The ministry also promised to draw up policies to support battery recycling, making full use of existing tax incentives and creating innovative new financing methods.

https://uk.reuters.com/article/us-china-autos-batteries/china-launches-pilot-ev-battery-recycling-schemes-idUKKBN1KF375


PYROMETALLURGICAL FACILITIES

o Several Pyrometallurgical facilities are currently processing EV batteries

o Umicore (Belgium) has developed an industrial pilot plant that has the capacity to treat 7,000 tonnes/year (they also have battery pack dismantling facilities in Germany). We have had preliminary discussions with Umicore who are interested to explore collaboration.

o Other smelting companies process batteries as part of their feed materials (e.g.)

Glencore | Canada & Norway

NickelHutte | Germany

o No suitable primary metallurgical facilities in the UK.

o At present all EoL EV batteries are exported from the UK for reprocessing

o Should the UK rely on exporting EoL EV Batteries?


TETRONICS: PYROMETALLURGICAL STUDY

o Conducting techno-economic study of the economics of a bespoke pyrometallurgical facility for battery recycling in the UK.

o Typical input data and thermodynamic modelling to determine consumption rates and yields.

o Preliminary design for 7,000 tonnes/year (same as Umicore demo plant). Costings for a industrial pilot plant in the UK prepared – process economics now being analysed.

o The product from the furnace is a non-standard Co-Ni-Cu alloy so revenue estimates must be adjusted to reflect need for downstream refining costs

o Preliminary evaluations from the Tectonics study will be used to benchmark alternate process routes (economics and LCA).

BACKGROUND WORK

o This work gathers information on volumes, costs, infrastructure etc. in relation to the management of waste lithium ion batteries and considers present position under e.g. the Batteries Directive

o It considers the security of critical materials

o It reviews the environmental impact of this volume of waste

MAKING THE CASE FOR RE-USE & RECYCLING OF LITHIUM-ION BATTERIESBUSINESS & REGULATION

REGULATORY REQUIRMENTS

o Like any other product lithium ion batteries will be subject to broad regulation (e.g. on product recall)

o Regulation will extend across the life cycle of the product from its placing on the market until end of life

o BUT is all of this regulation sufficiently well tailored to EV batteries or are there gaps or inconsistencies?

REGULATORY GAP ANALYSISBUSINESS & REGULATION

LIABILITY

o This involves both contractual and tortious liability for batteries in use and at end of life

o It includes issues of harm e.g. in the event of accident or within a waste recycling centre

o Reviewing liability structures may help us consider other issues – such as labelling or transportation

DO WE NEED TO THINK LIABILITY STRUCTURES FOR LITHIUM-ION BATTERIES?BUSINESS & REGULATION

BREXIT

o This may well depend on the type of Brexit

o On one hand we could regulate free from the Batteries Directive which in any case was devised without EV batteries in mind

o On the other hand trans-border waste shipments post-Brexit may be more problematic

BUSINESS & REGULATIONWHAT ARE THE LIKELY IMPACTS OF BREXIT ON THE WASTE MANAGEMENT OF LITHIUM-ION BATTERIES?

PRIORITIES FOR YR 2

o Support for the development of operating procedures for the management of EV accidents for Fire Brigades

o Build demonstration unit for scale-up of delamination processo Review of Flow sheets of existing recycling processes for techno-economic evaluation and comparison

with pyrometallurgy based on Tetronics studyo Streamlining of gateway assessment through generation of prioritised and scaled testing methods, sensor

technologieso Demonstration of robotic dismantling techniques using the small robot armo Direct recycling and ‘upcycling’ of recovered cathode materialso Biological metal recovery and nanoparticle synthesis with real samples, including characterisation of

nanoparticle bioproduction in real time and assessment of their potential applicationso Correlation of electrochemical testing with structural failure of battery packs at multiple length-scaleso Development of Argonne Laboratories LCA model (EverBatt – previously known as RECELL) for the UK

context, modifying the model from US and Korea to the UK case using UK specific parameterso Review of liability structures and Extended Producer Responsibility; impact of Brexit

INDUSTRY ENGAGEMENT

o Strong links with Nissan/AESC via team at Newcastle University – plus contact with 4R (Nissan/Sumitomo JV) regarding battery re-manufacturing

o Dialogue with JLR regarding battery pack dismantling and management (some changes at JLR) – access to 5 teardown reports acquired from A2Mac1 (Nissan Leaf (2), Tesla, Mitsubishi and Geely)

o Industrial partners attended LiB Global Market Workshop

o Worked with authorised company for battery pack removal (video produced)

o Continued dialogue with companies engaged in battery management/logistics (EcoBat, Cawleys, Autocraft)

o Initial contact made with Umicore and opportunity to visit them in Belgium

o Finalising arrangements with Benchmark Mineral Intelligence for access to batter materials market data

o Exploring use of Blockchain technology for component & material tracking (Everledger)

o Venture capitalists interested in development of robotic dismantling systems (Shield Investments)

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