CM Solutions Lithium Battery Recycling

LITHIUM BATTERY RECYCLING
Keeping the future fully charged
Benjamin D.H. Knights

Fadeela Saloojee
27 November 2015
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This Research Report was prepared under the Research Funding Programme, ‘Research and Policy Development to
Advance a Green Economy in South Africa'
By:
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GREEN FUND
RESEARCH AND POLICY DEVELOPMENT TO ADVA NCE A GREEN ECONOMY IN SOUTH A FRICA
GREEN ECONOMY RESEA RCH REPORTS
The Government of South Africa, through the Department of Environmental Affairs, has set up the Green Fund to
support the transition to a low-carbon, resource-efficient and pro-employment development path. The Green Fund
supports green economy initiatives, including research, which could advance South Africa’s green economy transition.
In February 2013, the Green Fund released a request for proposals (RFP), ' Research and Policy Development to
Advance a Green Economy in South Africa’, inviting interested parties with relevant green economy research projects
to apply for research funding support. The RFP sought to strengthen the science-policy interface on the green economy
by providing an opportunity for researchers in the public and private sectors to conduct research which would support
green economy policy and practice in South Africa. Sixteen research and policy development grants were awarded in
2013. This peer-reviewed research report series presents the findings and policy messages emerging from the research
projects.
The Green Economy Research Reports do not represent the official view of the Green Fund, Department of
Environmental Affairs or the Development Bank of Southern Africa (DBSA). Opinions expressed and conclusions arrived
at, are those of the author/s.
Comments on Green Economy Research Reports are welcomed, and may be sent to: Green Fund, Development Bank
of Southern Africa, 1258 Lever Road, Headway Hill and Midland 1685 or by email to enquiries@sagreenfund.org.za.
Green Economy Research Reports are published on:
www.sagreenfund.org.za/research
Please cite this report as:
Knights, B.D.H. and Saloojee, F. (2015). Lithium Battery Recycling – keeping the future fully charged. Green
Economy Research Report No. 1, Green Fund, Development Bank of Southern Africa, Midrand.
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EXECUTIVE SUMMARY
CM Solutions has investigated the sustainable management of lithium batteries, with particular focus on recycling of the
batteries. Funding for this project was provided through the Green Fund by the Department of Environmental Affairs,
under the administration of the Development Bank of Southern Africa. This is the final report, showing the results of the
project.
Lithium-ion batteries (LIBs) are a popular energy storage medium due to their high energy density, high voltages and low
weight to volume ratio. Currently they are widely used in portable electronic devices (e.g. cellular phones and laptops).
However, usage is expected to increase in the near future due to migration to electric vehicles which use LIBs as the
power source.
The lifespan of LIBs is 3-5 years, which points to an increasingly large waste stream of LIBs in the next 5-10 years. There is
no recycling facility in South Africa for LIBs. Some attempts were made in the past (e.g. Uniross with Pick n Pay) to
recycle general battery waste. However, the recyclable batteries were shipped to France for recycling, and non-
recycleable batteries went to land-fill.
LIBs contain toxic and flammable components, as well as valuable metals such as lithium, nickel, copper and cobalt.
For these reasons, there are benefits to recycling used LIBs instead of disposal in landfills.
A further benefit to recycling relates to the possibility of developing a local lithium battery manufacturing industry. Since
South Africa does not have a local lithium resource, any attempt to set up local LIB manufacturing will require the import
of lithium. Recycled lithium is able to meet a portion of the lithium feed requirements.
The following research objectives served as a guide for this research project:
a) Develop a core process to extract the valuable material contained in lithium batteries. The process should meet
the following criteria:
i. Be flexible enough to treat a wide range of lithium battery types
ii. Generate a final product which can be traded on the metals market, or used in LIB manufacture
iii. Have minimum capital expenditure.
b) Determine the capital and operating costs of such a process, as well as capture the revenue streams that the
process could generate.
c) Establish whether the disposal of lithium batteries (which forms a critical part of their life-cycle) should have an
impact on legislation and policy associated with battery import, production and sales.
Initial research, including a literature survey and a desktop study pointed to two process options for recycling of lithium
ion batteries (LIBs). These are a hydrometallurgical route and a combined pyrometallurgical and hydrometallurgical
route. Subsequent test work, however, failed to successfully and consistently reproduce the processes. An alternative
process was then explored, using a combination of early-stage research described in literature, and internal experience
within CM Solutions.
The test work showed positive results, and a process model was developed. This culminated in a mass balance, which
considered material flows, chemical build-up and energy requirements. The balance was based on a feed rate of
10 000 t/a LIBs. This figure is the predicted South African consumption rate of LIBs in 2020. The facility would produce
saleable products in the form of lithium carbonate, and hydroxides of copper, cobalt and zinc. The lithium production
rate is 40 t/m of lithium carbonate.
A financial model was then developed, using the mass balance feed rate of 10 000 t/a, and a start date of 1 January
2020. Values from the mass balance, as well as test work, were incorporated to determine revenue and costs. The
process model and mass balance were also used to calculate capital cost estimates. Total capital cost came to R
228M, which when escalated at 6% per annum reached R 295M in 2020. Monthly revenue generated by the recycling
facility was R 6.9M, and costs R 9.3M (in 2020).
The financial model indicated that the recycling facility would never be cash-flow positive, due to the operating costs
exceeding revenue (by 30%). However, by introducing a recycling levy of approximately 3% of the purchase cost of a
new battery, it is possible for the facility to pay off the capital investment in less than 5 years.
This study has been performed as a high-level analysis. There are areas for further optimization, and areas where further
research is necessary. Although the proposed process has been designed to satisfy environmental requirements, there is
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room for improving sustainability further. This includes evaluating alternatives for the roasting step and disposal of the
final residue.
The form and implementation of the proposed battery levy should be investigated, drawing on international best
practice. It would be ideal to use the levy to drive societal behaviour towards the most environmentally responsible
behaviour through the intelligently applied fees and penalties. An example of this would be to link the recycling levy to
the fuel price, or to the purchase of petrol/diesel cars. This may increase the appeal of electric vehicles.
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TABLE OF CONTENTS
EXECUTIVE SUMMARY ................................................................................................................................................................................ 5
LIST OF FIGURES ........................................................................................................................................................................................... 8
LIST OF TABLES ............................................................................................................................................................................................. 8
LIST OF ABBREVIATIONS ............................................................................................................................................................................. 8
RESEARCH TEAM ......................................................................................................................................................................................... 9
1 INTRODUCTION ................................................................................................................................................................................ 10
2 BACKGROUND TO RESEARCH/PROBLEM STATEMENT ............................................................................................................... 10
2.1. Problem Statement ............................................................................................................................................................... 10
3 AIMS AND OBJECTIVES / RESEARCH QUESTIONS ....................................................................................................................... 11
4 LITERATURE REVIEW ......................................................................................................................................................................... 12
4.1. History of Lithium Batteries .................................................................................................................................................... 12
4.2. Battery Chemistry and Design ............................................................................................................................................. 12
4.2.1 Primary lithium batteries ................................................................................................................................................... 12
4.2.2 Lithium-ion batteries (LIBs) ............................................................................................................................................... 13
4.3. Motivation for recycling of LIBs ........................................................................................................................................... 14
4.3.1 Legislation........................................................................................................................................................................... 14
4.3.2 Valuable metal components ......................................................................................................................................... 14
4.4. Consumption of lithium-ion batteries ................................................................................................................................. 14
4.4.1 Global Forecast ................................................................................................................................................................. 14
4.4.2 South African Consumption ............................................................................................................................................ 15
4.4.3 Current commercial processes for recycling of lithium batteries ............................................................................ 16
4.4.4 Experimental processes for recycling of lithium batteries ......................................................................................... 21
5 METHODOLOGY .............................................................................................................................................................................. 23
6 CHALLENGES AND CONSTRAINTS ................................................................................................................................................ 24
7 RESULTS/FINDINGS ........................................................................................................................................................................... 25
7.1. Battery composition .............................................................................................................................................................. 25
7.2. Roasting................................................................................................................................................................................... 25
7.3. Leaching ................................................................................................................................................................................. 26
7.4. Process Development........................................................................................................................................................... 28
7.5. Mass Balance Results ............................................................................................................................................................ 30
7.5.1 Basis of calculation ........................................................................................................................................................... 30
7.5.2 Summary of results ............................................................................................................................................................ 30
7.6. Financial modelling results ................................................................................................................................................... 31
8 CONCLUSIONS ................................................................................................................................................................................ 39
8.1. General conclusions ............................................................................................................................................................. 39
8.2. Key Policy Messages ............................................................................................................................................................. 39
8.3. Recommendations for Further Research .......................................................................................................................... 39
9 REFERENCES ..................................................................................................................................................................................... 41
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LIST OF FIGURES
Figure 1: Schematic diagram of primary lithium manganese battery (Varta, 2014) .................................................................. 13
Figure 2: Schematic diagram of lithium ion battery (Daikin Global, 2014) ................................................................................... 14
Figure 3: Flow diagram for Recupyl process (Tedjar & Foudraz, 2010) .......................................................................................... 17
Figure 4: Temperature zones in the furnace used in Umicore process .......................................................................................... 18
Figure 5: Flow diagram for Umicore process (Buchert et al., 2012) ................................................................................................ 19
Figure 6: Flow diagram for Toxco process (Gaines et al., 2011) ...................................................................................................... 20
Figure 7: Flow diagram for INMETCO process (van der Werf, 2011) ............................................................................................... 21
Figure 8: Main process steps - extended test work campaign ........................................................................................................ 27
Figure 9: Process flow diagram - mass balance ................................................................................................................................. 28
Figure 10: Revenue vs costs (excluding CAPEX and recycling levy) .............................................................................................. 35
Figure 11: Free cash flow - no external revenue ................................................................................................................................ 36
Figure 12: Free cash flow - including recycling levy, targeting zero NPV ...................................................................................... 36
Figure 13: Revenue and costs ............................................................................................................................................................... 37
Figure 14: Sensitivity analysis for CAPEX and OPEX ............................................................................................................................ 38
LIST OF TABLES
Table 1: Most common types of primary lithium batteries currently produced ........................................................................... 12
Table 2: Typical composition of a lithium ion battery ........................................................................................................................ 13
Table 3: Global forecast for consumption of lithium batteries ........................................................................................................ 15
Table 4: South African forecast for consumption of lithium batteries in 2020 ............................................................................... 15
Table 5: Commercial processes for recycling of lithium batteries .................................................................................................. 16
Table 6: Battery bulk composition (w/w%) .......................................................................................................................................... 25
Table 7: Roasted battery (Al and Cu electrodes) composition ...................................................................................................... 25
Table 8: Leaching extents in the low acid concentration leach (1 M HCl, 60°C, 40 mins) ........................................................ 26
Table 9: Leaching extents in the high concentration leach (2 M HCl, 60°C, 60 mins with H2O2) ............................................ 26
Table 10: Leach extent and solids composition - extended test work ........................................................................................... 27
Table 11: Feed rate for mass balance ................................................................................................................................................. 30
Table 12: Summary of mass balance results ....................................................................................................................................... 30
Table 13: Reagent consumption rates ................................................................................................................................................. 30
Table 14: Water balance results ............................................................................................................................................................ 31
Table 15: CAPEX calculation details ..................................................................................................................................................... 32
Table 16: Operating costs, including contingency............................................................................................................................ 33
Table 17: Fixed costs ................................................................................................................................................................................ 33
Table 18: Total monthly costs (1 January 2020) .................................................................................................................................. 34
Table 19: Metal prices and percent value assigned ......................................................................................................................... 34
Table 20: Surcharge calculation as fraction of typical battery cost .............................................................................................. 38
LIST OF ABBREVIATIONS
LIB: Lithium ion battery
NiMH: Nickel Metal Hydride battery
SMM: Shanghai Metals Market
LME: London Metals Exchange
PVDF: Polyvinylidene fluoride
NPV: Nett Present Value
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RESEARCH TEAM
The main research team consisted of Ben Knights, Fadeela Saloojee, Justin Lloyd and Frank Crundwell. Qualifications
and summarised profiles follow.
Benjamin D H Knights
MSc. Chemical Engineering (2001, UCT), BSc. Chemical Engineering (1999, UCT), New Manager’s Programme (2008,
WBS)
Ben combines his thorough knowledge of chemical engineering and computer systems with his enjoyment of hands-on
plant and laboratory work. He has used this skill set to optimise process performance by developing and implementing
advanced control systems for clients in the minerals industry. He has been involved in early-stage design work, mass
balancing, financial modeling and technical due diligence work. He has also run laboratory test work programmes,
including continuous pilot plant studies.
Fadeela Saloojee
MSc. Chemical Engineering (2011, Wits), BSc. Chemical Engineering (2010, Wits)
Fadeela has a passion for consulting work, in which she can use her knowledge of chemical engineering to assist clients
to deliver better results. She uses mathematics and other tools to solve practical problems in the metallurgical industry. In
a short period, she has gained a lot of experience in a vast range of topics, from mine-to-mill optimisation, roasting,
acid-recovery systems through to copper SX/EW plants.
Justin M Lloyd
BSc Chemical Engineering (2005, Wits), Process Design Practices (2010, Korf Technology Ltd)
Justin is a chemical engineer who enjoys applying his theoretical understanding of engineering concepts to actual
plant problems. He has gained both a practical understanding of plant conditions through his operational experience,
as well as a theoretical understanding of engineering design concepts through his work undertaken in a reputable
design house.
Frank K Crundwell
PhD. Chemical Engineering, (1988, Wits), MSc. Chemical Engineering (1986, Wits), BSc. Chemical Engineering (1983,
Wits), BSc. (Hons) Maths of Finance (2001, Wits)
Frank heads up CM Solutions, a consultancy and laboratory offering services in extractive metallurgy. He thrives in an
environment that links commercial and technical knowledge to provide solutions for the client. As a consultant, his
experience includes assisting clients in both the business and technical spheres. He has managed technical projects,
built and led teams, and worked globally. He has an international reputation as an award-winning scientist and
inventor.
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1 INTRODUCTION
The use of lithium-ion batteries (LIBs) in South Africa is expected to increase in the near future. The main reason for this
will be the use of electric cars, which use LIBs as the power source. LIBs are also widely used in portable electronic
devices (e.g. cellular phones and laptops). The popularity of LIBs is due to their high energy density, high voltages and
low weight to volume ratio (Xu et al., 2008).
LIBs have an expected lifespan of 3-5 years. Over the next few years, an increasingly large waste stream of LIBs is
expected in South Africa. LIBs contain toxic and flammable components, as well as valuable metals such as Li, Ni, Cu
and Co. For these reasons, there are benefits to recycling used LIBs, instead of disposal in landfills.
South Africa currently does not have a process for recycling of LIBs. In 2010, Uniross and Pick n Pay initiated a battery-
recycling project. All types of batteries were collected at Pick n Pay stores and then separated into recyclable and non-
recyclable batteries. Non-recyclable batteries were packed into concrete blocks and disposed in landfills. Recyclable
batteries were shipped to France for recycling. Although this is more sustainable than completely discarding the
batteries, it highlights the opportunity to increase and expand the battery recycling effort in South Africa.
2 BACKGROUND TO RESEARCH/PROBLEM STATEMENT

2.1. Problem Statement
There are two issues associated with the disposal of lithium-ion batteries in landfills:
i. Lithium-ion batteries contain flammable and toxic components. Irresponsible disposal of LIBs in landfills carries a
high risk of explosions or contamination of soil and groundwater.
ii. South Africa does not have a source of lithium and currently imports batteries. Any attempt to set up local LIB
manufacturing will require the import of lithium.
Both of these issues can be addressed by the recycling of lithium-ion batteries in South Africa. However, battery
recycling may not be directly economically viable. This leads to the question as to whether the state (and hence all
citizens of the country) should be responsible for the disposal costs of waste lithium batteries. It is suggested that lithium
batteries need to be managed in terms of their full life cycles, with disposal levies linked to the original purchase costs.
These disposal levies can then be used to support battery recycling activities. The framework for such a levy is already
catered for in the Department of Environmental Affairs Waste Act. “Extended Producer Responsibility” (EPR) has been
established as a regulatory mechanism in the Waste Act. An example of a highly successful EPR initiative is the ROSE
foundation, which handles the recycling of used motor oil.
In order to guide legislation, as well as kick-start the recycling of LIBs, it is necessary to evaluate the viability of recycling
LIB’s, and quantify the economics of the same.
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3 AIMS AND OBJECTIVES / RESEARCH QUESTIONS

The purpose of this project was to determine a method for recycling of lithium batteries, with the primary aim of
recovering the lithium for further battery manufacture. Directly linked to this aim was the goal of sustainably disposing of
the non-recoverable battery waste. Since lithium batteries contain several different value components other than
lithium, a process was needed which would provide an acceptable disposal route for all the battery components.
Central to the aims of the research was to extract as much of the value contained in spent lithium batteries as possible,
thereby increasing the economic viability and sustainability of the process. Any waste streams generated should be
benign, and be disposed of with minimal environmental impact.
The economic viability, and the implications thereof, formed the final aspect of the project aims.
Leading from the aims the following research objectives were generated.
i. Develop a core process which has the flexibility to extract the valuable material contained in a wide range of
lithium batteries. The process should generate a final product which can be traded on the metals market, with
the minimum of capital expenditure.
ii. Determine the capital and operating costs of such a process, as well as capture the revenue streams that the
process could generate.
iii. Establish whether the disposal of lithium batteries (which forms a critical part of their life-cycle) should have an
impact on legislation and policy associated with battery import, production and sales.
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4 LITERATURE REVIEW
4.1. History of Lithium Batteries
Initial experimentation into the use of lithium as a battery component began in 1912 by an American named Gilbert
Newton Lewis (The history of lithium ion batteries, n.d.). Disposable (primary) lithium batteries were then developed in the
1950s. In the 1970s Panasonic was the first company to make primary lithium batteries commercially available.
Rechargeable (secondary) lithium batteries, also known as LIBs, were first studied in the 1970s by M.S. Whittingham at
Exxon. Whittingham’s lithium battery was made of a titanium disulfide cathode and a lithium-aluminium anode. The
instability of metallic lithium presented a safety risk, so focus shifted to the use of LiCoO 2 as the cathode material and
carbon as the anode material (Fey & Huang, 1999). In 1991, LIBs were commercially rolled out by Sony in Japan.
Primary lithium batteries are used in medical devices (e.g. pacemakers and implants), watches, calculators, cameras
and oceanographic instrumentation. The typical lifespan of a primary lithium battery is 15 years. LIBs (i.e. rechargeable
lithium batteries) are mainly used in portable electronic devices, power tools and electric vehicles. They typically offer
up to 1200 recharge cycles. The popularity of these batteries is as a result of them having the highest energy density
(J/kg) compared to all other battery chemistries currently in use.
4.2. Battery Chemistry and Design

The five components which make up a lithium-based battery (both primary and LIBs) are the anode, cathode,
electrolyte, separator and casing. In both primary lithium batteries and LIBs, the electrolyte is made up of a lithium salt
dissolved in an organic solvent. Examples of lithium salts are LiPF 6, LiBF4, LiClO4 and LiSO2; and possible solvents are
ethylene carbonate and propylene carbonate (Al-Thyabat et al., 2013). The reason for the use of an organic solvent
instead of an aqueous solvent is that lithium salts are unstable in aqueous solutions. However, the electrolyte is toxic and
flammable (Xu et al., 2008). The separators are typically constructed from microperforated plastics (e.g. polypropylene)
and the casing is typically made of plastic, aluminium or carbon steel.
The difference between primary lithium batteries and LIBs is in the materials used for the electrodes. The chemistry and
structure of both types of batteries are discussed in the sections following.
4.2.1 Primary lithium batteries

In primary lithium batteries, the anode is lithium metal. The three most common types of primary lithium battery on the
market today are shown in Table 1.
Table 1: Most common types of primary lithium batteries currently produced
Reference Name Anode Cathode Electrolyte
Lithium Manganese “CR” Lithium Metal Manganese Dioxide Lithium perchlorate in

propylene carbonate and
dimethoxyethane
Lithium Carbon Lithium Metal Carbon Lithium tetrafluoroborate in
Monofluoride Monofluoride propylene carbonate,
“BR” dimethoxyethane, and/or
gamma-butyrolactone
Lithium Iron Lithium Metal Iron Disulfide Propylene carbonate,
“FR” dioxolane, dimethoxyethane
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Of the battery types listed in Table 1, the lithium manganese battery accounts for 80% of the primary lithium battery
market. A schematic diagram of a cylindrical lithium manganese battery is shown in (Varta, 2014).
Figure 1: Schematic diagram of primary lithium manganese battery (Varta, 2014)
The overall reaction in a primary lithium battery is shown in Equation 6.1.
𝐿𝑖 + 𝑀𝑛𝑂2 → 𝐿𝑖𝑀𝑛𝑂2 [6.1]

The main disadvantage of primary lithium batteries is the risk of fire or explosion. Metallic lithium is unstable, and if
exposed to air and moisture, it can explode.
4.2.2 Lithium-ion batteries (LIBs)

In an LIB, the cathode is an aluminium plate coated with the cathode material, which is a lithium metal oxide. The
typical composition of LIBs is provided in Xu et al (2008). The most common cathode material is LiCoO 2, but LiNiO2 and
LiMn2O4 are also used. The anode is a copper plate coated with graphite. Polyvinylidene fluoride (PVDF) is used to bind
the electrode coating to the plate.
Table 2: Typical composition of a lithium ion battery
Component Composition (Mass %)

LiCoO2 27.5
Steel/Ni 24.5
Cu/Al 14.5
Carbon 16
Electrolyte 3.5
Polymer 14
The structure of an LIB is shown in Figure 2 (Daikin Global, 2014).
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Figure 2: Schematic diagram of lithium ion battery (Daikin Global, 2014)
The chemical reactions occurring in an LIB during charging are shown in Equation 6.2 and Equation 6.3. The reaction at
the cathode (6.2) is a carbon intercalation reaction. Lithium ions are inserted (intercalated) between oppositely
charged graphite layers. The anodic reaction (6.3) involves dissolution of lithium from the lithium metal oxide (e.g.
LiCoO2). The reverse reactions occur during discharge.
Cathode: 6𝐶 + 𝑥𝐿𝑖 + + 𝑥𝑒 − → 𝐶6 𝐿𝑖𝑥 [6.2]
Anode: 𝐿𝑖𝐶𝑜𝑂2 → 𝐿𝑖(1−𝑥) 𝐶𝑜𝑂2 + 𝑥𝐿𝑖 + + 𝑥𝑒 − [6.3]
4.3. Motivation for recycling of LIBs

Environmental impact of lithium ion battery disposal
There are three potential risks associated with disposal of lithium batteries to landfills. These are listed below:
i. Lithium batteries can explode when damaged or exposed to high temperatures

ii. Heavy metals (such as lead, manganese, nickel, copper and cobalt) used in lithium batteries can contaminate
soil and ground water.
iii. The electrolytes used in the batteries are toxic and flammable
4.3.1 Legislation
At this stage only the European Union has implemented a directive for collection and recycling of batteries (European
Union, 2006). This directive (commonly referred to as the “Battery Directive”) sets a target of 25% collection rate of all
batteries sold in 2012 and a 45% collection rate in 2016. Of the batteries collected, 50% of them need to be recycled.
The majority of lithium battery recycling facilities are found in North America, Europe and Asia. Combined, these
recycling facilities are currently only capable of treating less than 30% of the world’s lithium battery production. There
are currently no reported lithium battery recycling facilities on the African continent.
4.3.2 Valuable metal components

It is claimed (Georgi-Maschler et al., 2012) that more than a third of the production costs for LIBs arise from the cost of
materials. The valuable metals contained in LIBs include lithium, iron, aluminium, cobalt, nickel and copper. The
recovery of cobalt, nickel and copper may affect the economic value of any battery recycling process. However, this
effect needs to be confirmed with a detailed cost analysis of the selected recycling process options.
4.4. Consumption of lithium-ion batteries

4.4.1 Global Forecast
A few authors have estimated the global demand for lithium in future. This demand is expected to rise as a
consequence of the electric vehicles market expanding. The forecasts are shown in Table 3.
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Table 3: Global forecast for consumption of lithium batteries
Forecast year Product Forecast (t/year) Source

2015 Battery grade Li2CO3 111 700 Legers, L., 2008
2020 Lithium-ion batteries 21 000 Anderson, E.R., 2014
2020 Lithium carbonate for batteries 40 000 – 95 000 Haber, S., 2008
2050 Lithium 178 000 – 590 000 Angerer et al., 2009
2050 Lithium for electric vehicle batteries 400 000 Mohr et al., 2012
4.4.2 South African Consumption

The consumption of lithium-ion batteries per application is shown in Table 4.
Table 4: South African forecast for consumption of lithium batteries in 2020
Device Units sold in Average Consumption % increase Forecast for

2012 battery in 2012 (year on 2020 (t/year)
weight (g) (t/year) year)
Mobile phones 10 000 0001 402 400 5.7 623
Portable PC’s 274 0003,4 650 178 5.9 282
Tablet PC’s 340 6373 2009 68 14.6 202
Battery Operated 250 0005,6,10 207 5 14.6 15
Appliances
Hybrid Electric Vehicle 013 22 00014 0 >100% 5 09211,12,14
(HEV)
Electric Vehicles (PHEV, EV) 08 218 0008 0 >100% 3 36411,12
Total 651 40 9 578
Notes:
1. The number of mobile phones sold in South Africa in a year is estimated to be 10 million units with half of these
being smartphones. http://www.southafrica.info/business/trends/newbusiness/internet-290512.htm
2. The four most popular mobile phones sold in South Africa in 2012 was the Samsung E250i, Samsung S52330,
Nokia 1200 series and Nokia 5130 XpressMusic with an average lithium-ion battery weight of 40 grams.
http://www.marklives.com/2012/02/the-most-popular-mobile-phone-in-south-africa-is/
3. A total of 513 000 tablet pcs where sold in South Africa in 2013, a 50.6% increase compared to 2012. A total of
427 000 pcs were sold in 2013, an 18.8% decline compared to the previous year.
http://www.itweb.co.za/index.php?option=com_content&view=article&id=71104
4. In 2012, approximately 54% of total pc sales in emerging markets were for portable pc.
http://www.idc.com/getdoc.jsp?containerId=prUS24466513
5. It is estimated that South African consumes about 50 million batteries each year, with about 90% of these being
in the disposable form. http://www.uniross.co.za/recycling.html
6. In the European Union only 0.5% of total battery sales are primary lithium batteries.
http://en.wikipedia.org/wiki/Lithium_battery
7. In 2011, the AA size battery worldwide was found to account for about 60% of total battery sales.
http://en.wikipedia.org/wiki/AA_battery
8. The Nissan Leaf is the first electric car in South Africa with a lithium ion battery pack. The Nissan Leaf was first
introduced in South Africa in October 2013. The Nissan Leaf battery pack weighs 218 kg
http://en.wikipedia.org/wiki/Nissan_Leaf
9. The three most popular tablet pcs in 2012 (with their respective battery weights) were the Apple IPad 3 (300
grams), Google Nexus 7 (100 grams) and Samsung Galaxy 10.1” (180 grams) with an average battery weight of
200 grams.
10. It was assumed that lithium-ion batteries had a 5% market share of the rechargeable battery market for
electronic appliances (excluding pcs and mobile phones).
11. The Avicenne battery market presentation (2012) indicated the worldwide lithium battery consumption
forecasts. These forecasts indicated that hybrid vehicles will total about 30% of new car sales and electric
vehicles will total 2%.
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12. Total vehicle sales for South Africa in 2012 is 623 914 units, by 2020 it is estimated that new vehicles sales will
reach 771 492. http://www.tradingeconomics.com/south-africa/car-registrations
13. The only two manufacturers of hybrid electric vehicles available in South Africa in 2012 were Toyota and Lexus.
Toyota sells the Prius model and Lexus the GS450h and RX450h models. Both manufacturers used NiMH battery
packs and not lithium ion battery packs in their hybrid vehicles.
14. A typical weight for a lithium ion hybrid vehicle battery pack based on the 2014 Honda civic hybrid is 22 kg.
http://www.hondanews.ca/en/Honda/civic-hybrid/2014/Specifications
4.4.3 Current commercial processes for recycling of lithium batteries

Commercial processes for recycling of LIBs can be categorised as physical or chemical processes. Physical processes
involve the dismantling of the battery and separation of the battery components. Chemical processes include
leaching, precipitation, refining and pyrometallurgy. Current processes for recycling of lithium batteries are given in
Table 5.
Table 5: Commercial processes for recycling of lithium batteries
Capacity
No. Company/Process Location Material Recycled
(tonnes/year)
1 Sony and Sumitomo Metals Japan Li-ion only 150
2 Dowa Eco-System Co. Ltd. Japan All Lithium Batteries 1 000
3 Toxco Canada All Lithium Batteries 4 500
4 Umicore Belgium Li-ion only 7 000
5 Batrec AG Switzerland Li-ion only 200
6 Recupyl France All Lithium Batteries 110
7 SNAM France Li-ion only 300
8 Xstrata Canada All Lithium Batteries 7 000
9 Inmetco USA All Lithium Batteries 6 000
10 JX Nippon Mining & Metals Co. Japan Unknown 5 000
11 Chemetall Germany Unknown 5 000
12 Accurec Germany Unknown 6 000
13 Stiftung Gemeinsames Germany Unknown 340
14 G&P Batteries UK Li-ion only 145
15 SARP France Li-ion only 200
16 Revatech Belgium Li-ion only 3 000
Shenzhen Green Eco-manufacturer
17 China Li-ion only 20 000
Hi-Tech Co.
Fuoshan Bangpu Ni/Co High-Tech
18 China Li-ion only 3 600
Co.
19 TES-AMM Singapore Li-ion only 1 200
20 BDT USA All Lithium Batteries 350
21 Metal-Tech Ltd Israel All Lithium Batteries
22 Akkuser Ltd Finland All Lithium Batteries 4000
Total 70 595
Some of the processes from Table 5 are discussed in more detail in the following sub-sections.
Recupyl
The Recupyl process, developed by Recupyl SA, was piloted in France and implemented in Singapore. The process is
able to treat 110 tpa of lithium batteries, including primary and secondary battery types. The process uses a
combination of physical and chemical treatment steps to produce lithium carbonate. The battery scrap is first treated
by crushing, magnetic separation and density separation to produce a fine powder. The powder is then fed to a
hydrometallurgical process, consisting of hydrolysis, leaching and precipitation steps. Lithium is recovered as lithium
carbonate (Li2CO3) and cobalt is recovered as cobalt hydroxide (Co(OH)2).
Details of the processing steps are provided in Tedjar and Foudraz (2010). Crushing of the batteries is a two-step process,
taking place in a rotary shredder. The crusher operates in an atmosphere of CO 2 and 10-35% argon. The CO2 reacts with
any elemental lithium to form Li 2CO3, which is less reactive than elemental lithium. The crushed batteries are fed to a
physical separation process. Some of the residual gas from the crushing step is used to create an inert atmosphere
above the hydrolysis reaction. The remaining gas is fed to the lithium precipitation step, where the CO 2 reacts with LiOH
16
in solution, producing insoluble Li2CO3.
The components of the crushed battery scrap are separated by screening, magnetic separation and gravity
(densimetric) separation. For the screening step, vibrating screens of 3 mm and 500 μm are used. The -3 mm fraction
contains metal oxides and carbons. This is further screened on the 500 μm screen, resulting in a -500 μm fraction which is
rich in cobalt. Lithium is also contained in this fraction. The +500 μm fraction is rich in copper. The cobalt-rich fraction is
sent to the hydrometallurgical treatment process and the copper rich fraction is sold along with steel. The +3 mm
fraction is treated by magnetic separation.
The magnetic fraction contains the steel from the battery casings. The non-magnetic fraction is further separated on a
densimetric table. The low-density, non-magnetic fraction contains paper and plastics. Non-ferrous metals report to the
high-density, non-magnetic fraction. Each of these fractions is sold.
The fine material from the physical separation process is treated by hydrolysis. The material is mixed with water. A
solution of lithium hydroxide is added to achieve a pH of 12-13. Lithium from the electrodes dissolves to produce lithium
salts in solution. The hydrolysis reaction generates hydrogen; inert gas from the crushing step is used to safely purge the
hydrogen. The metal oxides and carbon are suspended in solution and are separated out by filtration. The lithium-
containing solution is sent to a lithium precipitation step.
Lithium is precipitated from the alkaline leach solution as either Li 2CO3, using CO2 gas, or Li3PO4, using phosphoric acid.
The source of CO2 is the off-gas from the crushing stage. Precipitation occurs at a pH of 9. The solution from hydrolysis is
a pH 12 – 13, so acid is used to reduce the pH. The precipitate is washed with a CO2-saturated solution and dried at
105°C.
The stream containing residual suspended solids from the hydrolysis step is leached in sulfuric acid at a pH of 3 and a
temperature of 80°C. The metal oxides dissolve, leaving carbon in the residue. The leach product is filtered and the
solution is purified prior to cobalt precipitation.
In the purification process, copper and iron are removed from solution. Copper is cemented out by the addition of steel
shot. Soda is added to increase the pH to 3.85 in order to precipitate iron. The copper- and iron-free solution is fed to
cobalt precipitation.
Cobalt is recovered from solution either by electrolysis, or by precipitation as Co(OH) 3 through the addition of sodium
hypochlorite. The remaining solution contains some lithium and is sent to the lithium precipitation step.
The steps involved in the Recupyl process are shown in Figure 3.
Figure 3: Flow diagram for Recupyl process (Tedjar & Foudraz, 2010)
17
UMICORE
The Umicore process is a pyrometallurgical process which uses a patented ultra-high temperature furnace technology.
The primary aim of this process is to treat LIBs and Nickel Metal Hydride (NiMH) batteries, recovering only certain
valuable metals. There is no pre-treatment of batteries prior to smelting. Cobalt and nickel are recovered from the alloy
phase. Lithium is not recovered, and it reports to the slag.
Batteries are combined with limestone, sand, coke and slag formers and fed into the furnace. The feed should contain
30-50% battery scrap in order to produce a product with an economically viable content of cobalt and nickel (Cheret
& Santen, 2007). Air, pre-heated to 500°C, is fed through the bottom of the furnace. The furnace is divided into three
temperature zones: the pre-heating zone, the plastic pyrolysing zone and the smelting zone. These zones are shown in
Figure 4.
Figure 4: Temperature zones in the furnace used in Umicore process
In the pre-heating zone, at the top of the furnace, temperatures are maintained below 300°C. The furnace feed is
heated in this zone by gas flowing counter-currently from the hotter zones below. The electrolyte evaporates in this
zone. Slow heating of the feed reduces the risk of explosions in the furnace.
The middle zone of the furnace is the plastic pyrolysing zone. The temperature in this zone is around 700˚C. The plastic is
removed from the batteries by pyrolysis. This is an exothermic process, and the energy released is used to heat the gases
which move upward to the pre-heating zone.
The remaining material is reductively smelted in the smelting zone, at the bottom of the furnace. Smelting takes place at
temperatures of 1200-1450°C. In the smelting zone, a flow of pre-heated, oxygen-enriched air is injected via tuyeres into
the bottom of the furnace. Copper, cobalt, nickel and some iron report to the alloy phase. The slag phase contains
lithium oxide, as well as oxides of other metals, including aluminium, silicon, calcium and the remaining iron. The slag is
formed into concrete blocks and sold to the construction industry. The alloy phase is treated in a hydrometallurgical
process.
The off-gas from the furnace is heated in a post combustion chamber to above 1150˚C using a plasma torch. Calcium,
zinc oxide or sodium products are then injected into the combustion chamber to capture halogens evolved from
electrolyte and binder evaporation. Water vapour is then injected into the gases to cool it down to 300˚C. This is also to
avoid recombination of organic compounds with toxic, flammable compounds such as halogens, dioxins and furans.
Copper, cobalt, nickel, zinc and iron are recovered from the alloy phase by dissolution and precipitation. The cobalt
and nickel products are cobalt chloride (CoCl2) and nickel hydroxide (Ni(OH)2), respectively. The CoCl2 can be used as
a feed material for LIB manufacture, to produce LiCoO2.
The Umicore process is shown in Figure 5 (Buchert et al., 2012).
18
Figure 5: Flow diagram for Umicore process (Buchert et al., 2012)
TOXCO
The Toxco process is a hydrometallurgical process for the recycling of spent LIBs. The process entails pre-treatment of the
batteries, separation of battery components, leaching, solution purification and lithium precipitation.
Lithium metal, as well as the by-products which may form during battery reclamation, are highly reactive, toxic and
corrosive (McLaughlin & Adams, 1999). When recycling lithium batteries (primary or LIBs), a pre-treatment step is
necessary to render the lithium and by-products inert. In the Toxco process, batteries are rendered inert by cryogenic
cooling.
The cryogenic cooling process pre-treatment step is patented. In this process, the batteries are cooled to between -
175°C and -195°C with liquid nitrogen. At these temperatures, the reactivity of the battery material is sufficiently low that
there is no risk of explosion. In addition, the low temperatures make the plastic casing of the batteries brittle, so that they
can easily be broken.
The cooled batteries are shredded and sent to a hammer mill, where the batteries are milled in a lithium brine. Lithium
dissolves in the hammer mill. The salts formed in solution include LiCl, Li 2CO3 and LiSO3. The mill is fitted with a screw press,
to separate the lithium-containing solution from the undissolved product, referred to as “fluff”. The solution will contain
some undissolved fine material, consisting of metal oxides and carbon.
The fluff is separated on a shaking table. The separation process produces a low density stream consisting of plastics
and stainless steel, and a high density, copper-cobalt product. Both these products are packaged and sold.
The lithium-containing solution is fed to a holding tank prior to filtration. If necessary, the pH of the solution is maintained
at 10 by the addition of lithium hydroxide (LiOH). This is used instead of cheaper sodium hydroxide (NaOH) to prevent
contamination of the lithium product with sodium.
The material from the holding tank is filtered on a filter press. The cake contains metal oxides. The remaining solution is
fed to dewatering tanks. Water is evaporated from the lithium-containing solution. The concentration of the lithium salts
increases, until the salts precipitate out.
The product from the dewatering tanks is filtered in a filter press and purified with an electrolytic membrane. The filter
cake contains 28% moisture. This is then fed to a purification step. A solution of mild sulfuric acid is added to the filter
cake, resulting in the dissolution of the metal salts. Li + ions pass through the membrane and precipitate as LiOH.
The LiOH is converted to Li 2CO3 by the addition of CO2. The Li2CO3 is filtered, washed, dried and packaged. The
remaining solution is disposed.
Figure 6 is a flow diagram of the Toxco process (Gaines et al., 2011).
19
Figure 6: Flow diagram for Toxco process (Gaines et al., 2011)
INMETCO
The International Metals Reclamation Company (INMETCO) operates a pyrometallurgical facility for treating metal
waste, including spent batteries. The process was initially designed to treat furnace dust, mill scale and swarf (Liotta et
al., 1995). Spent batteries form a secondary feed to the furnace, in addition to waste containing nickel and cadmium
and dolomitic, carbon and chromium refractories (Liotta et al., 1995). Process steps include feed preparation, reduction,
melting and casting. Iron, nickel, copper and cobalt are recovered in an alloy. Lithium is lost to the slag phase, while the
organic electrolyte and the plastic casing are volatilised
The battery feed to the process is prepared by opening up the batteries, removing the plastic and draining the
electrolyte. The batteries are then shredded. The other solid feeds to the process are blended and a carbon-based
reductant is added. The mixture is pelletised. Liquid waste which contains nickel and cadmium is added at the
pelletising stage. The pellets are combined with the shredded batteries and fed to the reduction step.
Reduction takes place in a rotary hearth furnace operating at 1260°C. The residence time is 20 minutes. Metal oxides
are reduced to metals. Off-gas from the rotary hearth furnace is scrubbed and the scrub solution is sent to a wastewater
treatment facility, from which treated water is recycled to the process. Cadmium, zinc and lead are recovered in the
wastewater treatment process, and sent to another facility for metal recovery.
The reduced product from the rotary hearth furnace is fed to a submerged electric arc furnace (SEAF) for smelting. The
SEAF produces an alloy containing iron, nickel, chromium and manganese. The alloy is tapped from the furnace and
fed to a casting step. The slag is sold as an aggregate for building. Off-gas from the SAEF is passed through a baghouse
before it is discharged to the atmosphere.
In the casting step, the alloy is cast into stainless steel “pigs”. The molten metal is poured into moulds, which are cooled
with water. The pigs are sold to the stainless steel industry. The typical composition of pig alloy is 10% nickel, 14%
chromium and 68% iron.
The INMETCO Process is illustrated in Figure 7 (van der Werf, 2011).
20
Figure 7: Flow diagram for INMETCO process (van der Werf, 2011)
4.4.4 Experimental processes for recycling of lithium batteries

In addition to commercial processes in operation, there is a reasonable body of research available for alternative
processes tested at the laboratory scale. A literature review was done on a selection of these papers. The review has
been divided into the 3 main sections common to most of the proposed processes. These sections are pre-treatment,
dissolution and metal recovery.
PRE-TREATMENT PROCESSES
PHYSICAL DISASSEMBLY
In most of the laboratory-scale processes that were reviewed, the physical pre-treatment step is a manual process
(Castillo et al., 2002; Contestabile et al., 1999; Zhang et al., 1998). Battery cases are opened and electrodes are
separated from the casings. The electrodes are then cut into pieces.
In some investigations, the physical pre-treatment step was automated. In the AEA process (Lain, 2001), batteries are
mechanically shredded in an inert atmosphere. This prevents exposure of the lithium to air or moisture, which could
react with lithium causing an explosion. The pre-treatment process employed by Shin et al. (2005) is carried out in the
following order: crushing, sieving, magnetic separation, fine crushing and further sieving.
ROASTING
The aim of roasting is to separate the volatile material, such as plastic and electrolyte, from the electrodes. This is usually
achieved at temperatures between 400 and 800°C. At these temperatures the volatile components are converted to
the gas phase. The off-gases from the roaster need to be treated in a gas-handling system, which usually consists of a
cooler and a bag filter. The roaster product needs to be cooled prior to leaching.
Roasting of primary lithium batteries was investigated by Kondas et al. (2006). Temperatures between 450°C and 750°C
were tested in an oxidising environment. During the roasting step, plastic casings burst and the exposed Li was oxidized.
At temperatures below 700°C, the oxidized Li was converted to Li 2CO3. The burst casings were separated from the
electrode material by screening.
DISSOLUTION PROCESSES
Several of the commercial processes make use of an alkaline leach. Several lab-scale processes investigated acid
leaching and hydrolysis (dissolution in water). These are discussed in the sections below.
ACID LEACHING
The metal components in primary and secondary lithium batteries (Li, Co, Cu, Mn) are soluble in acidic solutions. Acid
leaching of lithium batteries has been tested at the laboratory-scale using various acids. These include hydrochloric
acid (HCl), sulfuric acid (H2SO4), and nitric acid (HNO3).
Three reagents for acidic leaching of LIBs were compared by Zhang et al (1998), in terms of recovery of lithium and
21
cobalt. The reagents were sulphuric acid, hydroxylamine hydrochloride and hydrochloric acid. Results showed that HCl
was the most effective, giving over 99% recovery of Li and Co. This was achieved at the following leach conditions:
solution concentration of 4 M HCl, temperature of 80°C, leach time of 60 minutes and solid to liquid ratio of 1:10.
Castillo et al. (2002) investigated acidic leaching of spent LIBs using both HCl and HNO 3. The dissolution of lithium in HCl
solution was 80% at 2 hours, but other metals were also dissolved from the electrodes. In an attempt to improve
selectivity, the concentration of HCl was reduced, but this resulted in large retention times. A solution of nitric acid was
then tested, and this showed high selectivity for lithium and manganese. The lithium and manganese in the product
solution were separated by selective precipitation.
Acidic leaching in a sulfuric acid solution, with the addition of hydrogen peroxide (H 2O2), was tested by Shin et al.
(2005). In the paper it was claimed that the role of H 2O2 is to assist in reduction of Co3+ to Co2+, which is more soluble in
acidic solution. Reduction of Co breaks down the LiCoO2 structure, releasing Li, which dissolves. The improved solubility
of Co2+ under reducing conditions is well documented. The leach process occurred at a temperature of 75°C, acid
concentration of 2 M H2SO4 and a pulp density of 50 g/L.
HYDROLYSIS (WATER LEACHING)
The hydrolysis process entails reaction of lithium with water, to produce an aqueous lithium salt. The reaction may
generate hydrogen gas, and necessary precautions to deal with this should be taken. The hydrolysis reaction can take
place in neutral or alkaline solution.
One precaution to deal with the hydrogen gas is to conduct the leach is a two-phase solution made up of alcohol and
water, as proposed by Contestabile et al. (1999). The researchers used isobutyl oxidation, which allowed for mild
oxidation of the lithium metal.
Hydrolysis of spent Li/MnO2 batteries was investigated by Kondas et al. (2006). The batteries were pre-treated by
roasting, which produced Li2CO3. The Li2CO3 was leached in distilled water, while the manganese remained in the
residue. Leach conditions included a liquid:solid ratio of 25:1, ambient temperature, and leach time of 1-3 hours.
The proposed AEA process (Lain, 2001) also includes a hydrolysis step. In this process spent LIBs go through a pre-
treatment process which includes mechanical shredding, extraction of electrolyte using a solvent, dissolution of the
PVDF binder in a solvent, and separation of electrode material from copper, aluminium, steel and plastic. The
electrodes are then dissolved in water. Electrochemical reduction is used to reduce Co 3+ to Co2+. This releases Li from
the LiCoO2 structure. The hydrolysis products are aqueous LiOH, solid CoO and oxygen gas.
Contestabile et al (1999) advise recycling of the barren solvent mixture back to the leach. The solution is heated to
reduce the solubility of CO2, resulting in the evolution of CO2 gas. The pH of the solution increases as a result.
22
5 METHODOLOGY
The project methodology was chosen with the intention of satisfying the three research objectives listed in section 3.
The first stage of the process involved determining the current state of the art of lithium battery recycling technologies.
The primary mechanism was via the literature review. The review included scientific literature, public information,
company announcements and internal company expertise.
The literature review allowed us to condense the processing options down to clear stages common to the various
methods, and described the approach used currently in the industry. Potential process paths were then selected for
further evaluation.
Test work was then done at a scoping level to determine which methods were successful. The results of these tests fed
back to an iterative approach in finalizing the process route.
Once the scoping tests indicated the merit of a process route, more detailed test work was done to determine
important parameters related to the process. Parameters such as metal recovery, reaction rates and purity were
evaluated to determine if process changes were needed, or incorporated directly into the process model.
The process model converted individual test work results into a consistent interconnected process. The model defined
the equipment required and provided rough sizing information, as well as reagent consumption and energy
requirements. A combination of activities from literature review to completion of the process model was used to
achieve the first research objective listed in section 3.
The process sizing and operational parameters were then used in a costing exercise, and incorporated into a financial
model. Consumption figures and lithium pricing from the literature review were used to determine production rate,
revenue and operating costs. The output of the financial model completed the second research objective, and led
directly to the conclusion applicable to the final research objective.
23
6 CHALLENGES AND CONSTRAINTS

There were a number of challenges associated with this work. Although there are some recycling facilities in operation,
the recycling of lithium batteries is not widespread. Much of the scientific research on the subject has never been tested
on a larger scale, nor have the practical or commercial aspects ever been evaluated. Therefore this work has a high
degree of novelty, with the inherent challenges and delays associated with novel work.
For the test work it was necessary to source suitable feed material. Several avenues were explored, from collecting all
spent lithium batteries internally from company staff members, to liaising with cellphone repair shops to collect old
batteries. These methods were of limited success.
Ultimately feed material was sourced from the University of Port Elizabeth and the University of the Western Cape. These
facilities were able to provide a selection of pouch cells and cylindrical cells (both new and used).
Initial test work attempted to replicate the methods used in industry (sub-sections of the Recupyl and Umicore
processes). However, results were very inconsistent. In the case of the Recupyl process, complete dissolution of the
metals was very difficult to achieve. Since recovering the lithium on its own did not satisfy the aim of recovering all the
valuable components (e.g. copper, aluminium) partial dissolution was not acceptable. Lab-scales tests at the high
temperatures required for the Umicore process were also difficult to achieve. Smelting at the lower ranges quoted for
the Umicore process did not produce a clean separation of metal and slag. Ultimately the failure of these tests led to a
re-evaluation of our approach.
In re-evaluating our approach, we turned to less developed experimental methods reported in the scientific literature.
By combining the basic ideas already explored in literature, and combining it with our own in-house knowledge, we
were able to propose a method that would satisfy the research aims and objectives.
The final challenge was time. Due to the novelty of the approach a lot of lab test work was needed. In many cases the
results were poor, and further, modified, tests were needed. This inevitably led to delays and project extensions.
24
7 RESULTS/FINDINGS
7.1. Battery composition
There is considerable variation in the battery composition, due to different form factors, manufacturing methods and
internal chemistry. The following composition was ultimately selected for the financial analysis and mass balance.
Table 6: Battery bulk composition (w/w%)
Battery composition Electrode ratio

Plastic waste 4.92%
Metal casing 21.7%
Aluminium electrode 46.3% 63%
Copper electrode 27.1% 37%
7.2. Roasting
Each sample was roasted under a nitrogen blanket at 600°C for an hour. The purpose of the nitrogen blanket was to
minimize oxidation of the copper electrode, which improved selectivity in the first stage leach. An average of 16.6%
mass loss was experienced. The chemical composition of each electrode was determined, and is shown in Table 7.
Table 7: Roasted battery (Al and Cu electrodes) composition
Al electrode Cu electrode Combined

Al 11.0% 0.0% 6.93%
Ca 0.0% 0.0% 0.04%
Co 0.0% 0.0% 0.00%
Cu 0.0% 34.9% 12.89%
Fe 26.7% 0.1% 16.85%
Li 3.0% 0.5% 2.09%
Mg 0.3% 0.0% 0.19%
Mn 0.1% 0.0% 0.05%
Na 0.0% 0.0% 0.02%
Ni 0.0% 0.0% 0.00%
Zn 0.0% 0.0% 0.01%
25
7.3. Leaching
The first stage of leaching was done on the roasted product. The purpose of this leach was to selectively dissolve lithium,
with minimal dissolution of other metals. Leaching was done at 60°C in 1 M hydrochloric acid (HCl). The solid to liquid
ratio was 1:10. Agitation was achieved by swirling every 10 minutes. Leaching was done for varying lengths of time. It
was found that 40 mins of leaching resulted in the highest lithium extraction, with the lowest copper dissolution.
Table 8: Leaching extents in the low acid concentration leach (1 M HCl, 60°C, 40 mins)
Element Leach extent

Al 85.8%
Ca 27.7%
Co 17.0%
Cu 4.2%
Fe 40.2%
Li 76.0%
Mg 71.0%
Mn 83.2%
Na 42.5%
Ni 6.4%
Zn 90.0%
After filtration, the residue from the low concentration leach was then re-leached in 2M HCl, with hydrogen peroxide
(50%) added to oxidise the copper. The leach extents (based on the composition of the solids exiting the low
concentration leach) are shown in Table 9.
Table 9: Leaching extents in the high concentration leach (2 M HCl, 60°C, 60 mins with H2O2)
Element Leaching Extent

Al 96.7%
Ca 63.3%
Co 29.5%
Cu 99.2%
Fe 39.4%
Li 82.5%
Mg 76.4%
Mn 93.5%
Na 93.1%
Ni 8.5%
Zn 100.0%
The scoping tests indicated the technical viability of the two-stage leach process. An extended test campaign was then
run, incorporating all the main processing steps. The elements of this extended campaign are shown in Figure 8.
26
Low Concentration Leach (1M HCl) pH Adjust (LiOH) Li Precipitation (CO 2 )
14g (Anode + Cathode) N2 LiOH CO2

1 M HCl Recycle (X2 - fresh solids)
11% Solids ICP/Assay pH 9 ICP/Assay

Temp 60 oC Temp 60 oC Temp 60 oC
40 min L 60 min pH 9 L 120 min
60 min Maintain
S S
50% H2 O2 ICP/Assay ICP/Assay

2 M HCl CaO L
ICP/Assay
S
20% Solids ICP/Assay
Temp 60 oC pH 9 ICP/Assay
Time - until all metals L 120 min L
disolve ICP/Assay
S S
ICP/Assay ICP/Assay
High Concentration Leach (2M HCl) CaO Precipitation
Figure 8: Main process steps - extended test work campaign
The results from this campaign are shown in Table 10 for the main elements of interest. The table shows both the leach
extents for the main metals of interest, as well as the composition of the solids that exit the process.
Table 10: Leach extent and solids composition - extended test work
Al Ca Cu Fe Li Mg Mn Zn
Leach extent:
48% 71% -6% -7% 33% 23% 26% 25%
Low conc leach
Leach extent:
78% 4% 97% 17% 36% 34% 32% 37%
High conc leach
Solids composition:
7.83% 14.5% 0.04% 5.11% 4.91% 0.41% 0.21% 0.0%
Low conc pH adjust
Solids composition:
2.24% 9.1% 24.9% 1.38% 0.09% 0.50% 0.31% 0.0%
High conc solids
Solids concentration:
4.16% 1.0% 0.05% 0.10% 20.6% 0.04% 0.0% 0.07%
Li precipitation
The lithium leach extents achieved in the extended test work were lower than those achieved in the initial tests. This may
be due to incomplete roasting, or variation the feed material. For the modeling and mass balance it was assumed that
it should be possible to achieve the higher extents previously achieved through process optimization.
The low copper dissolution in the first stage is an excellent result, followed by a high leach extent in the high
concentration leach. Such targeted leaching is highly beneficial to the final process.
The lithium precipitation solids contains 20.6% Li. The solids are expected to be lithium carbonate (Li 2CO3), which in pure
form contains 19% Li. It can be concluded that apart from the 5% aluminium contamination, the final lithium
precipitation is quite pure. Further optimization may be able to decrease the aluminium contamination, with the final
lithium product being suitable as a battery manufacture feed material.
27
7.4. Process Development
Figure 9: Process flow diagram - mass balance
The intention of the test work conducted by CM Solutions was to develop a process for the sustainable recycling of
primary lithium and lithium ion batteries. The product of the recycling process should contain as much of the value
contained in the spent batteries as possible. The process developed by CM Solutions entails the following steps: battery
dismantling, inert roasting to remove volatiles, selective leaching in two stages at different acid concentrations, pH
adjustment and lithium precipitation, and finally precipitation of other metals. Each of these steps is discussed in more
detail below.
STEP 1: BATTERY DISMANTLING
The process development in this project did not focus on battery dismantling. Several methods are described in
literature, and follow-up testwork has been recommended as part of finalising this process. It is assumed that batteries
can be safely dismantled, and the main components separated. The steel casings can be sent to scrap metal
consumers (e.g. iron smelters), and the plastic to suitable recyclers. The electrodes form the main feed to the recycling
process, and are fed first to the roasting step.
STEP 2: ROASTING
Electrodes are roasted in a furnace at 600°C, for 1 hour. The roasting step removes the organic material (electrolyte and
binder) from the electrodes. Nitrogen gas is passed through the roaster to exclude oxygen and hence create an inert
environment. This has two main purposes. It prevents combustion of the organic material and the lithium, which is a
safety benefit. It also ensures that copper is not oxidised, which improves the selectivity of the primary leach. The
roasted material is cooled under nitrogen, prior to leaching. Typical mass loss in the roasting step was 16.6%
STEP 3: LEACHING
Leaching is done in HCl solution in two steps. The first leaching step is at a lower concentration of HCl. The aim of this
step is to dissolve as much lithium as possible while not dissolving the other metals. The second step is at a higher
concentration of HCl, in order to dissolve the remaining lithium and other metals.
28
In the first leaching stage, the electrodes are leached in a solution of 1 M HCl. This leach solution is a combination of
water, concentrated HCl and recycled solution from the lithium precipitation step. The leach temperature is 60°C.
Lithium dissolves from the electrodes to form lithium chloride in solution. The extent of lithium dissolution is approximately
76%. The other metals also dissolve to some extent. The leach product is filtered. Solution is sent to the pH adjustment
and lithium precipitation steps, while the leach residue (undissolved remnants of the battery electrode material) is fed to
the second leaching stage.
In the second leaching stage, the remaining lithium and other metals dissolve. The concentration of the leach solution is
2 M HCl, and hydrogen peroxide is added as an oxidising agent. The leach temperature is again 60°C in this step. The
product is filtered and the final solid residue is disposed. Very little of the original electrode should remain, and the bulk
of the solid residue will be inert carbon black. It may be possible to supply this to the tyre industry. The leach solution is
treated in a precipitation step to recover the dissolved metals.
STEP 4: PH ADJUSTMENT
Solution from the first leaching stage is fed to the pH adjustment step. The pH of the leach solution is increased prior to
the lithium precipitation step. This is achieved by adding lithium hydroxide. The target pH is 9. As a result of the increase
in pH, copper, aluminium, iron, magnesium and manganese precipitate from solution. These precipitates are removed
by filtration. The filtrate solution is fed to lithium precipitation.
STEP 5: LITHIUM PRECIPITATION
In this step, CO2 gas is bubbled through the lithium-containing solution. Lithium precipitates as lithium carbonate. The
precipitation reaction produces HCl. The product is filtered and the solution is recycled to the first leach stage as a
source of HCl. The cake is dried to form the lithium carbonate product. Part of this product can be treated to produce
LiOH needed in the pH adjustment step. The remaining product can be used to regenerate cathode material.
STEP 6: METAL PRECIPITATION
Solution from the second leach stage is treated in the metal precipitation step, in order to recover dissolved copper. The
pH of the leach solution pH is adjusted to 9 by the addition of hydrated lime. This results in precipitation of copper,
aluminium, iron, manganese and magnesium as hydroxides. The product is filtered and can be sold to copper smelters.
The solution is then passed on to acid regeneration.
STEP 7: ACID REGENERATION
Calcium remains in solution after metal precipitation, along with chloride ions. To remove calcium it is precipitated as
insoluble gypsum (calcium sulfate). The gypsum is formed by adding sulfuric acid, and hydrochloric acid is generated as
a by-product (Al-Othman, A. & Demopoulos, G.P., 2009). The gypsum is filtered, and may be a valuable product stream
if the purity is sufficiently high. The solution, which is free of metals and high in hydrochloric acid (approximately 56 g/L),
can be recycled to the plant feed as acid make-up.
STEP 8: FINAL LEACH RESIDUE DISPOSAL
The final leach residue will consist mainly of inert carbon. The solid-liquid separation stage includes washing to remove
any residual leach liquor (which will contain dissolved metals). The final filter cake should be an inert material consisting
primarily of carbon. This should be easy to dispose of, or possibly form a feed stream for other industries such as tyre
manufacture.
29
7.5. Mass Balance Results

7.5.1 Basis of calculation
The mass balance is based on a feed of 10 000 t per annum of anode and cathode material. The forecast for South
African consumption of lithium batteries in 2020 is just under 10 000 t/a (Table 4). Assuming an annual growth of 10%,
over five years the consumption will reach 16 000 t/a. Anode and cathode material make up 73% of the battery mass,
and hence a design capacity of 10 000 t/a of this material is equivalent to 13 600 t/a raw battery feed. This is the
average of the battery consumption rate in South Africa between 2020 and 2025. Details of the feed flowrate are
provided in Table 11.
Table 11: Feed rate for mass balance
Parameter Units Value

Nominal feed rate t/a 10000
Mass ratio of aluminium to copper electrodes 1.6
Plant availability and utilisation % 90
Design flowrate of aluminium electrodes t/h 0.78
Lithium composition in aluminium electrodes % 2.51
Design flowrate of copper electrodes t/h 0.49
Lithium composition in copper electrodes % 0.37
7.5.2 Summary of results

The main results from the mass balance are summarised in Table 12.
Table 12: Summary of mass balance results
Parameter Units Value

Feed rate of solids to process Dry t/h 1.268
Lithium carbonate product flowrate Dry t/h 0.0857
Lithium composition in product % 18.78
Net lithium production t/h 0.0161
Lithium recovery % 74.9
Metal precipitate flowrate Dry t/h 0.712
Gypsum production rate Dry t/h 0.777
Residue flowrate Dry t/h 0.679
Table 13 lists the net reagent consumption figures calculated from the mass balance.
Table 13: Reagent consumption rates
Reagent Units Value

CO2 kg/t feed 66.4
50% H2O2 kg/t feed 244
33% HCl kg/t feed 356
98% H2SO4 Kg/t feed 392
Hydrated lime kg/t feed 453
The process is a net water producer. The water consumption and production figures are provided in Table 14. Apart
from direct water addition to the low concentration leach, water is required for dilution of the sulfuric acid. Water is also
added to the process through hydrochloric acid and hydrogen peroxide.
All the solid products and residue contain moisture, typically 15%. However, the final water stream from the gypsum
filtration is sufficient to satisfy the feed requirements. Therefore there will be a net production of water.
30
Table 14: Water balance results
Parameter Unit Value

Water addition to low concentration leach l/h 239
Water addition to high concentration leach l/h 0
Water addition to sulfuric acid dilution l/h 4280
Total water addition l/h 4519
Water reporting to recycle l/h 5258
Net water consumption l/h -739
7.6. Financial modelling results

A high-level financial model for the process was compiled, to determine the financial implications and viability of the
recycling process.
The model evaluates the process over 5 years, starting from January 2020. All costs were escalated at 6% per annum,
except for labour which increased at 8%. Rates of exchange were kept at current (October 2015) levels.
The details of the CAPEX estimate are shown in Table 15. The capital cost for the plant was estimated using the factorial
method (Sinnot, 2001). In this method, the purchase costs of major equipment items are obtained and the other costs
are estimated as factors of those costs. The cost factors are known as Lang factors. The physical plant cost can be
determined from the following equation:
Physical plant cost = Lang factor X Delivered cost of major equipment.
For a fluid-solids process such as this, the Lang factor is 3.15. This factor takes into account equipment erection, piping,
instrumentation, electrical costs, process buildings, utilities, storage facilities, site preparation and ancillary buildings.
31
Table 15: CAPEX calculation details
Lang factor of 3.15 applied to capital items

Total CAPEX ZAR 228 329 075 below.
Feed handling 585 900
Scaled from price of 90 m3 silo – existing
Feed silos ZAR 81 900 quote
Price at R 16000 per m at 10 m – internal
Conveyor belts ZAR 504 000 source
Splitting/grinding/pulversing 18 900 000
Mill ZAR 15 750 000 Equipment cost of R 5 000 000 - internal source
Screen ZAR 2 362 500 Equipment cost of R 750 000 - internal source
Mill ancillaries (sump, etc) ZAR 787 500 Equipment cost of R 250 000 - internal source
Roasting 33 500 000
Nitrogen generator ZAR 2 000 000 Atlas Copco
Roaster ZAR 15 750 000 Equipment cost of R 5 000 000 - internal source
Off-gas handling ZAR 15 750 000 Equipment cost of R 5 000 000 - internal source
Leaching and precipitation 121 793 175
3X5m3 rubber lined vessels, R 82 500 -
Low concentration leach tanks ZAR 779 625 Consulmet
Low concentration leach
agitators ZAR 378 000 3 agitators at R 40 000 each - internal source
2 plastic filters at R 3 000 000 each - internal
Low concentration leach filters ZAR 18 900 000 source
2X12m3 SS tanks at R 173 000 each -
pH adjustment tanks ZAR 1 089 900 Consulmet
pH adjustment agitators ZAR 315 000 2 agitators at R 50 000 each - internal source
pH adjustment filters ZAR 18 900 000 source
Li precipitation tanks ZAR 1 808 100 2X30m3 SS tanks - Consulmet
2 gas-sparge agitators, R 70 000 each -
Li precipitation agitators ZAR 441 000 internal source
Li precipitation filters ZAR 18 900 000 source
2X5m3 rubber lined vessels, R 82 500 -
High concentration leach tanks ZAR 519 750 Consulmet
High concentration leach
agitators ZAR 252 000
High concentration leach filters ZAR 18 900 000 source
2X10 m3 SS tanks at R 173 000 each -
Metal precipitation tanks ZAR 1 089 900 Consulmet
Metal precipitation agitators ZAR 315 000 2 agitators at R 40 000 each - internal source
Metal precipitation filter ZAR 18 900 000 source
2X10 m3 SS tanks at R 173 000 each -
Gypsum precipitation tanks ZAR 1 089 900 Consulmet
Gypsum precipitation agitators ZAR 315 000 2 agitators at R 40 000 each - internal source
Gypsum precipitation filter ZAR 18 900 000 source
Drying and packaging Unit 53 550 000
Lithium carbonate drying ZAR 15 750 000 Equipment cost of R 5 000 000 - internal source
Mixed metal drying ZAR 15 750 000 Equipment cost of R 5 000 000 - internal source
Residue drying ZAR 15 750 000 Equipment cost of R 5 000 000 - internal source
Packaging system ZAR 6 300 000 Equipment cost of R 2 000 000 - internal source
32
CAPEX has been included for an off-gas handling section in the roasting stage. This equipment will ensure the gas
emissions meet environmental requirements. The precipitation stages ensure the final discharge water is free from
contaminants, and meets environmental legislation.
All operating costs were escalated from the date of known pricing, to 1 January 2020. A contingency operating cost for
reagents was included, at 15% of the total estimated reagent cost. Electricity prices from the Middleburg municipality
were used, which represents a typical industrial complex where a facility such as this could be based.
Table 16: Operating costs, including contingency
Operating Costs Annual Final price

Pricing Inflation Input Current Final in model
date rate units price price units Final units
Electricity prices1
Off-peak 2015/07/01 6% ZAR/kWh 0.431 0.56 0.56 ZAR/kWh
Standard 2015/07/01 6% ZAR/kWh 0.727 0.95 0.95 ZAR/kWh
Peak 2015/07/01 6% ZAR/kWh 1.057 1.37 1.37 ZAR/kWh
Grinding media ZAR/t
cost2 2015/10/01 6% feed 6.500 8.33 8.33 R/t feed
Nitrogen cost2 2014/07/01 6% ZAR/m3 2.500 3.44 3.44 R/m3
Reagents - costs
- LiOH3 2015/07/01 6% RMB/lb 46500 60441 282487881 ZAR/t
- HCl4 2015/10/01 6% ZAR/t 1580 2024 2024 ZAR/t
- H2O24 2015/10/01 6% ZAR/t 400 512 6661 ZAR/t
- CO24 2015/10/01 6% ZAR/t 1500 1922 24980 ZAR/t
- Lime2 2015/06/01 6% ZAR/t 3700 4833 4833 ZAR/t
- Contingency 15% %
1 Middleburg municipality
2 Internal sources
3 http://www.metal.com/metals/productinfo/201102250281
4 Alibaba
Fixed costs primarily took the form of labour. However, to account of additional fixed costs as well as support staff, a
salary contingency of 30% was included. The values are shown in Table 17
Table 17: Fixed costs
Fixed costs (monthly) ZAR/m 775 667

Labour (note, per annum):
- Plant manager ZAR/a 2015/10/01 900 000
- Plant metallurgist ZAR/a 2015/10/01 500 000
- Operators (4 x shifts of 6 staff) ZAR/a 2015/10/01 5 760 000
Fixed cost contingency % of labour 30%
Feed rate of batteries started at 10,000 tonnes per annum, escalating by 10% per annum (compounded monthly).
Total monthly costs for the first month are shown in Table 18.
33
Table 18: Total monthly costs (1 January 2020)
Splitting/grinding/pulversing
Electricity consumption ZAR/m R 60 156
Grinding media ZAR/m R 6 939
Roasting
Electricity costs ZAR/m R 300 778
Nitrogen costs ZAR/m R 402 590
Leaching and precipitation
Electricity costs ZAR/m R 60 156
Reagents - monthly costs
HCl ZAR/m R 740 390
H2O2 ZAR/m R 1 353 168
CO2 ZAR/m R 1 382 474
Lime ZAR/m R 1 824 732
H2SO4 ZAR/m R 1 108 506
Other reagents: cost ZAR/m R 961 391
General costs and expenses
Fixed costs ZAR/m R 1 075 786
Sales prices were taken from the Shanghai Metals Market and Alibaba. They were escalated at 6% per annum. Value
was only assigned to copper, lithium, cobalt and zinc. Lithium was priced based on the metal content lithium
carbonate. Prices for lithium carbonate were determined by averaging three offers on Alibaba (www.alibaba.com).
Table 19: Metal prices and percent value assigned
% value
Metal prices Price assigned Source
- Cu ZAR/t 86 277 80% http://www.metalprices.com/p/CopperFreeChart
- Al ZAR/t 26 067 - http://www.metalprices.com/p/AluminumFreeChart
- Li2CO3 ZAR/t 65 837 Average of 3 prices for lithium carbonate, Alibaba
- Equivalent Li ZAR/t 455 183 80% http://www.metal.com/pricing/minor-metals
- Co ZAR/t 477 278 80% http://www.metalprices.com/p/CobaltFreeChart
- Mn ZAR/t 13 951 - http://www.metalprices.com/p/ManganeseFreeChart
- Zn ZAR/t 27 535 80% http://www.metalprices.com/p/ZincFreeChart
The financial analysis was conducted over 5 years, with all capital expenditure occurring at the start of the project. To
determine a project’s overall value, a terminal value of the asset is often calculated or estimated. The challenge with
this approach is that it is very difficult to predict the final value (or returns) of an asset far into the future. The terminal
value can also often form a significant portion of overall asset value, making the asset seem highly appealing primarily
due to the terminal value estimate. A conservative approach was adopted in this case, using a terminal value of zero
for the plant, after 5 years. This ensured that the final financial evaluation of the facility is not heavily influenced by a
financial estimate that attempts to predict asset value far into the future.
34
Figure 10: Revenue vs costs (excluding CAPEX and recycling levy)
Figure 10 presents the revenue and the costs associated with the process, excluding CAPEX or any recycling levy. It is
clear that over the 5 year period of the model the facility does not generate a profit.
Figure 11 shows the free cash flow, including capital cost allocation. Initial cash flow is strongly negative, primarily due to
the capital being allocated upfront. Monthly and cumulative free cash flow (non-discounted) is shown for the full 5 year
period of the analysis. The blue bars show that the facility never records positive cash flow, and the cumulative cash
flow is less than ZAR -470 million over five years. Discounting the future cash flows at a rate of 9% results in a net present
value of ZAR -440 million.
35
Figure 11: Free cash flow - no external revenue
To improve the economics of the process, a facility for cash injection was investigated. This may be in the form of a
surcharge/levy on battery purchases, or a recycling fee. It was found that a fee of R 8.12 per kg of battery was able to
return a zero NPV over 5 years, using a discount rate of 9%.
Figure 12: Free cash flow - including recycling levy, targeting zero NPV
36
The cash flow analysis with the battery levy included is shown in Figure 12. The monthly cash flow values are positive for
the life of the project (excluding the first month), and the cumulative cash flow is positive after approximately 4 years.
The model only assigns value to copper, lithium (as lithium carbonate), cobalt and zinc. It is assumed that the contained
metals can be sold for 80% of their market price. Figure 13 shows the revenue break-down by metal, and the overall
operating costs. It’s clear that the levy contributes slightly more than half of the total revenue, with the bulk of the
battery value in the copper and lithium. With the levy included, the total revenue exceeds the costs and this profit is
used to pay back the capital costs.
Figure 13: Revenue and costs
37
Figure 14: Sensitivity analysis for CAPEX and OPEX
Figure 14 presents the results of a sensitivity analysis on the overall CAPEX and OPEX values. CAPEX and OPEX were
independently varied between -30% and +30%. For each variation the battery levy was adjusted to produce a net
present value (NPV) of zero. The effect on the required battery levy at the commencement of operation is plotted
against the percentage variation. The battery levy is far more sensitive to the operating costs than the capital cost. This
leads to two conclusions: optimization efforts would be better spent on decreasing operating costs, and spending
additional capital to save operating costs is likely to have a net positive effect. Examples of capital expenditure that
might reduce operating costs include improved automation and more energy-efficient units.
Table 20: Surcharge calculation as fraction of typical battery cost
Typical lithium battery Model 18650

Nominal voltage 3.7 V
Nominal capacity 1500 – 3400 mAh
Typical mass 40 g
Typical price R 13.00 (listed as USD 1 -3, USD 1 = ZAR 13)
Battery levy R 8.12
Applied levy R 0.32 (40 g battery)
Percentage surcharge on total price 2.5%
This financial analysis indicates that as a stand-alone entity the recycling facility is likely to be loss making. However, the
calculations in Table 20 show that a levy of less than 3% of the battery cost would enable the facility to be self-sustaining
over a 5 year period. This levy could fall under the “Extended Producer Responsibility” framework in the Waste Act. As
such, it could take the form of a battery sales surcharge/tax, on every battery sold (as is done in the tyre industry).
Alternatively it could be used to influence behaviour towards increased environmental responsibility. An example of this
would be to add this surcharge to the fuel levy, or as a licence fee for fossil-fuel vehicles. This may encourage increased
adoption of electric vehicles.
38
8 CONCLUSIONS
8.1. General conclusions
Test work has confirmed that the proposed recycling process is technically viable. The test work results were able to be
incorporated into a continuous process model, and the resultant mass balance was feasible.
A financial model indicates that the revenue from the product is only able to cover half of the expenses associated with
recycling the batteries. By providing support funding to the value of approximately R 7.94 per kg processed, the
recycling facility would be self-sustaining. Over 5 years, the net present value would be zero (at a 9% discount rate).
Although in this project it has been possible to develop, test and economically evaluate a viable recycling process,
there remain several areas of improvement and optimization. No value has been assigned to some of the products, for
example the battery casings, the carbon waste and the gypsum precipitate. The lithium carbonate value is directly
linked to its purity, and a detailed financial analysis might reveal that there is a strategic benefit to extending the
process to produce such a product. Further test work might also reveal methods to improve lithium recovery, and
possibly alternatives to the roasting section.
8.2. Key Policy Messages

It does not seem likely the lithium battery recycling would be financially viable as a stand-alone process. A recycling fee
would need to be charged to cover approximately half of the costs of the recycling process. The final feed may vary,
depending on a more detailed financial evaluation. This fee could be charged as a levy on all batteries imported into
the country. Alternatively, it could be used to encourage further adoption of electric vehicles, for example by including
a battery recycling charge in the petrol and diesel fuel levy. The framework for levies linked to waste disposal is already
in place in the Waste Act. “Extended Producer Responsibility” (EPR) is incorporated into the act as a regulatory
mechanism to integrate the environmental costs associated with the life cycle of a product into the overall cost of that
product. The proposed battery levy may be well catered for within the EPR mechanism.
8.3. Recommendations for Further Research

Due to the size and complexity of this project, research was focussed on aspects with the biggest unknowns. Broadly this
included the processes involved in treating the battery electrodes, and producing a saleable product. However, it
excluded the pre-preparation stages such as battery disassembly and component separation. Descriptions of several
possible methods were found during the literature review. However, it is still important to characterise and optimise these
methods. Should this research be extended, it is recommended that the pre-preparation methods be included in the
study.
Product value increases substantially as purity improves. There are likely to be several methods available to improve the
purity of final product. It is recommended that these be investigated further, including a cost-benefit analysis.
The current flowsheet includes a roasting step. CAPEX was included for all the necessary processes to ensure
environmental constraints are met. This includes off-gas handling and precipitation stages for discharge water.
Nonetheless the roasting step consumes significant energy, and produces significant emissions. It is highly appealing to
eliminate this step, replacing it with a more sustainable alternative. This may also lead to the possibility of recycling more
of the battery components.
The proposed process is expected to produce a reasonably inert and non-toxic residue. However, more test work,
including possible pilot-plant work, is suggested to confirm the nature and toxicity of any waste products.
The financial evaluation to date has included the key big-ticket items, and conservative estimates for revenue and
costs. However, it also excludes some of the administrative and logistic costs such as battery collection, waste disposal,
marketing etc. The estimates for processing capacity are also based on predicted total consumption figures. A more
detailed investigation is needed to estimate battery consumption rates, rates at which waste batteries are generated,
collection efficiency and waste stockpiles that may need to be processed. This information is needed to improve both
the process design and the financial evaluation.
39
Investigations should be done into the international best practice regarding funding (statutory or otherwise) for
necessary but uneconomical processes such as this. Directly linking the battery surcharge to the battery price may add
significant costs to the purchase of electric vehicles. This may discourage the adoption of electric vehicles. Linking the
recycling cost to the purchase of fossil fuel, or fuel-based vehicles, may have the positive effect of shifting the market to
electric vehicles. Of course this would only be sustainable while there are sufficient sales in the fossil fuel market to
collect the surcharge.
40
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42
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LITHIUM BATTERY RECYCLING

LITHIUM BATTERY RECYCLING

Keeping the future fully charged

Benjamin D.H. Knights

LITHIUM BATTERY RECYCLING

GREEN ECONOMY RESEA RCH REPORTS

Green Economy Research Reports are published on:

Please cite this report as:

2 BACKGROUND TO RESEARCH/PROBLEM STATEMENT

3 AIMS AND OBJECTIVES / RESEARCH QUESTIONS

4.2. Battery Chemistry and Design

4.2.1 Primary lithium batteries

Table 1: Most common types of primary lithium batteries currently produced

Reference Name Anode Cathode Electrolyte

Lithium Manganese “CR” Lithium Metal Manganese Dioxide Lithium perchlorate in

Figure 1: Schematic diagram of primary lithium manganese battery (Varta, 2014)

The overall reaction in a primary lithium battery is shown in Equation 6.1.

𝐿𝑖 + 𝑀𝑛𝑂2 → 𝐿𝑖𝑀𝑛𝑂2 [6.1]

4.2.2 Lithium-ion batteries (LIBs)

Table 2: Typical composition of a lithium ion battery

Component Composition (Mass %)

The structure of an LIB is shown in Figure 2 (Daikin Global, 2014).

Figure 2: Schematic diagram of lithium ion battery (Daikin Global, 2014)

Cathode: 6𝐶 + 𝑥𝐿𝑖 + + 𝑥𝑒 − → 𝐶6 𝐿𝑖𝑥 [6.2]

Anode: 𝐿𝑖𝐶𝑜𝑂2 → 𝐿𝑖(1−𝑥) 𝐶𝑜𝑂2 + 𝑥𝐿𝑖 + + 𝑥𝑒 − [6.3]

4.3. Motivation for recycling of LIBs

i. Lithium batteries can explode when damaged or exposed to high temperatures

4.3.2 Valuable metal components

4.4. Consumption of lithium-ion batteries

Table 3: Global forecast for consumption of lithium batteries

Forecast year Product Forecast (t/year) Source

4.4.2 South African Consumption

Table 4: South African forecast for consumption of lithium batteries in 2020

Device Units sold in Average Consumption % increase Forecast for

4.4.3 Current commercial processes for recycling of lithium batteries

Table 5: Commercial processes for recycling of lithium batteries

in solution, producing insoluble Li2CO3.

The steps involved in the Recupyl process are shown in Figure 3.

Figure 4: Temperature zones in the furnace used in Umicore process

The Umicore process is shown in Figure 5 (Buchert et al., 2012).

Figure 5: Flow diagram for Umicore process (Buchert et al., 2012)

Figure 6 is a flow diagram of the Toxco process (Gaines et al., 2011).

Figure 6: Flow diagram for Toxco process (Gaines et al., 2011)

The INMETCO Process is illustrated in Figure 7 (van der Werf, 2011).

4.4.4 Experimental processes for recycling of lithium batteries

HYDROLYSIS (WATER LEACHING)

6 CHALLENGES AND CONSTRAINTS

Table 6: Battery bulk composition (w/w%)

Battery composition Electrode ratio

Table 7: Roasted battery (Al and Cu electrodes) composition

Al electrode Cu electrode Combined

Element Leach extent

Element Leaching Extent

Low Concentration Leach (1M HCl) pH Adjust (LiOH) Li Precipitation (CO 2 )

14g (Anode + Cathode) N2 LiOH CO2

11% Solids ICP/Assay pH 9 ICP/Assay

50% H2 O2 ICP/Assay ICP/Assay

High Concentration Leach (2M HCl) CaO Precipitation

Figure 8: Main process steps - extended test work campaign

7.4. Process Development

Figure 9: Process flow diagram - mass balance

STEP 1: BATTERY DISMANTLING

STEP 5: LITHIUM PRECIPITATION

STEP 6: METAL PRECIPITATION