keeping the future fully charged benjamin d.h. knights ...€¦ · 4.2.1 primary lithium batteries...

LITHIUM BATTERY RECYCLING

1


Keeping the future fully charged

Benjamin D.H. Knights

Fadeela Saloojee

27 November 2015


2



3

This Research Report was prepared under the Research Funding Programme, ‘Research and Policy Development to

Advance a Green Economy in South Africa'

By:


4

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 [email protected].

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.

http://www.sagreenfund.org.za/research


5

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


6

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.


7

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


8

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


9

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.


10

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.


11

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.


12

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 LiCoO2 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 LiPF6, 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

Monofluoride

“BR”

Lithium Metal Carbon

Monofluoride

Lithium tetrafluoroborate in

propylene carbonate,

dimethoxyethane, and/or

gamma-butyrolactone

Lithium Iron

“FR”

Lithium Metal Iron Disulfide Propylene carbonate,

dioxolane, dimethoxyethane


13

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 LiCoO2, 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).


14

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− → 𝐶6𝐿𝑖𝑥 [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.


15

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

2012

Average

battery

weight (g)

Consumption

in 2012

(t/year)

% increase

(year on

year)

Forecast for

2020 (t/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

Appliances

250 0005,6,10 207 5 14.6 15

Hybrid Electric Vehicle

(HEV)

013 22 00014 0 >100% 5 09211,12,14

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%.

http://www.southafrica.info/business/trends/newbusiness/internet-290512.htm

http://www.marklives.com/2012/02/the-most-popular-mobile-phone-in-south-africa-is/

http://www.itweb.co.za/index.php?option=com_content&view=article&id=71104

http://www.idc.com/getdoc.jsp?containerId=prUS24466513

http://www.uniross.co.za/recycling.html

http://en.wikipedia.org/wiki/Lithium_battery

http://en.wikipedia.org/wiki/AA_battery

http://en.wikipedia.org/wiki/Nissan_Leaf


16

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

No. Company/Process Location Material Recycled Capacity

(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

17 Shenzhen Green Eco-manufacturer

Hi-Tech Co. China Li-ion only 20 000

18 Fuoshan Bangpu Ni/Co High-Tech

Co. China Li-ion only 3 600

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 CO2 and 10-35% argon. The CO2 reacts with

any elemental lithium to form Li2CO3, 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 CO2 reacts with LiOH

http://www.tradingeconomics.com/south-africa/car-registrations

http://www.hondanews.ca/en/Honda/civic-hybrid/2014/Specifications


17

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 Li2CO3, 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)


18

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).


19

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, Li2CO3 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 Li2CO3 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).


20

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).


21

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 Li2CO3. 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


22

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 HNO3. 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 (H2O2), was tested by Shin et al.

(2005). In the paper it was claimed that the role of H2O2 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 Co3+ 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.


23

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.


24

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.


25

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%


26

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.


27

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:

Low conc leach 48% 71% -6% -7% 33% 23% 26% 25%

Leach extent:

High conc leach 78% 4% 97% 17% 36% 34% 32% 37%

Solids composition:

Low conc pH adjust 7.83% 14.5% 0.04% 5.11% 4.91% 0.41% 0.21% 0.0%

Solids composition:

High conc solids 2.24% 9.1% 24.9% 1.38% 0.09% 0.50% 0.31% 0.0%

Solids concentration:

Li precipitation 4.16% 1.0% 0.05% 0.10% 20.6% 0.04% 0.0% 0.07%

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 (Li2CO3), 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.

Low Concentration Leach (1M HCl) pH Adjust (LiOH) Li Precipitation (CO2)

14g (Anode + Cathode) N2 LiOH CO2

1 M HCl Recycle (X2 - fresh solids)

11% Solids ICP/Assay pH 9 ICP/Assay

Temp 60oC Temp 60oC Temp 60oC

40 min L 60 min pH 9 L 120 min

60 min MaintainS S

50% H2O2 ICP/Assay ICP/Assay

2 M HCl CaO L

ICP/Assay

S

20% Solids ICP/Assay

Temp 60oC pH 9 ICP/Assay

Time - until all metals L 120 min L

disolve ICP/AssayS S

ICP/Assay ICP/Assay

High Concentration Leach (2M HCl) CaO Precipitation


28

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.


29

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.


30

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.


31

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.


32

Table 15: CAPEX calculation details

Total CAPEX ZAR 228 329 075

Lang factor of 3.15 applied to capital items

below.

Feed handling

585 900

Feed silos ZAR 81 900

Scaled from price of 90 m3 silo – existing

quote

Conveyor belts ZAR 504 000

Price at R 16000 per m at 10 m – internal

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

Low concentration leach tanks ZAR 779 625

3X5m3 rubber lined vessels, R 82 500 -

Consulmet

Low concentration leach

agitators ZAR 378 000 3 agitators at R 40 000 each - internal source

Low concentration leach filters ZAR 18 900 000

2 plastic filters at R 3 000 000 each - internal

source

pH adjustment tanks ZAR 1 089 900

2X12m3 SS tanks at R 173 000 each -

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

Li precipitation agitators ZAR 441 000

2 gas-sparge agitators, R 70 000 each -

internal source

Li precipitation filters ZAR 18 900 000


source

High concentration leach tanks ZAR 519 750

2X5m3 rubber lined vessels, R 82 500 -

Consulmet

High concentration leach

agitators ZAR 252 000

High concentration leach filters ZAR 18 900 000


source

Metal precipitation tanks ZAR 1 089 900

2X10 m3 SS tanks at R 173 000 each -

Consulmet

Metal precipitation agitators ZAR 315 000 2 agitators at R 40 000 each - internal source

Metal precipitation filter ZAR 18 900 000


source

Gypsum precipitation tanks ZAR 1 089 900

2X10 m3 SS tanks at R 173 000 each -

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


33

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

Pricing

date

Annual

Inflation

rate

Input

units

Current

price

Final

price

Final price

in model

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

cost2 2015/10/01 6%

ZAR/t

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.

http://www.metal.com/metals/productinfo/201102250281


34

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

Metal prices

Price

% value

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.


35

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.


36

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


37

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


38

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.


39

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.


40

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.


41

9 REFERENCES

Agrawal, R.D. & Kapoor, M.L. (1982) Theoretical considerations of the cementation of copper with iron, Journal of the

South African Institute of Mining and Metallurgy, April 1982 edition, p. 106 – 111

Al-Othman, A. & Demopoulos, G.P. (2009) Gypsum crystallization and hydrochloric acid regeneration by reaction of

calcium chloride solution with sulfuric acid, Hydrometallurgy, 96, p. 95 - 102

Al-Thyabat, S., Nakamura, T., Shibita, E & Iizuka, A. (2013) Adaptation of minerals processing operations for lithium ion

(LIBs) and nickel metal hydride (NiMH) batteries recycling: Critical review, Minerals Engineering, 45, p. 4 – 17

Anderson, E.R. (2014) Shocking future battering the lithium industry through 2020, TRU Group, 3rd Lithium Supply and

Markets Conference

Angerer, G., Marcheider-Weidemann, F., Wendl, M. & Wietschel, M. (2009). Lithium fur Zukunftstechnologien—Nachfrage

und Angebot unter Besonderer Berucksichtigung der Elektromobilitat, Fraunhofer Fraunhofer ISI: Karlsruhe, Germany,

2009

Buchert, M., Manhart, A., Bleher, D & Pingel, D. (2012) Recycling critical raw materials from waste electronic equipment,

OKO-Institut EV, Darmastadt, Commissioned by North Rhine-Westfalia State Agency for Nature, Environment and

Consumer Protection

Castillo, S., Ansart, F., Laberty-Robert, C. & Portal, J., 2002. Advances in the recovering of spent lithium battery

compounds, Journal of Power Sources, 112, p. 247 – 254

Cheret, D. & Santen, S. (2007) Battery recycling, Umicore, US patent 7 169 206 B2

Contestabile, M., Panero, S. & Scrosati, B., 1999. A laboratory-scale lithium battery recycling process, Journal of Power

Sources, 83, p. 75 – 78

Daikin Global (2014) Increasing Battery Capacity and Life with Flourine Compounds. [Online] Available from:

http://www.daikin.com/csr/feature2009/02_2.html [Accessed: 30 October 2014]

Djoudi, W., Aissani-Benissad, F. & Bourouina-Bacha, S. (2007) Optimization of copper cementation process by iron using

central composite design experiments, Chemical Engineering Journal, 133(1-3), p. 1 – 6

Fey, G.T.K. & Huang, D.L. (1999) Synthesis, characterization and cell performance of inverse spinel electrode materials

for lithium secondary batteries, Electrochimica Acta, 45, p. 295 – 314

Gaines, L., Sullivan, J., Burnham, A. & Belharouak, I. (2011) Life-cycle analysis for lithium-ion battery production, paper 11-

3891, 90th Annual Meeting of the Transportation Research Board, Washington D.C.

Georgi-Maschler, T., Friedrich, B., Weyhe, R., Heegn, H. & Rutz, M. (2012) Development of a recycling process for Li-ion

batteries, Journal of Power Sources, 207, p. 173 – 182

Haber, S. (2008) Chemetall, the lithium company. [Online] Available from

http://www.rockwoodspecialties.com/rock_english/media/pdf_files/02_04_09_Lithium_Supply_Santiago.pdf [Accessed:

10 November 2014]

Kondas, J., Jandova, J. & Nemeckova, M., 2006. Technical note: Processing of spent Li/MnO2 batteries to obtain

Li2CO3, Hydrometallurgy, 84, p. 247 – 249

Lain, M.J., 2001. Recycling of lithium ion cells and batteries, Journal of Power Sources, 97-98, p. 736 – 738

Legers, L. (2008) The trouble with lithium 2—Under the microscope, Meridian International Research. [Online] Available

from: http://www.meridian-int-res.com/Projects/Lithium_Microscope.pdf> [Accessed: 10 November 2014]

Liotta, J.J., Onuska, J.C. & Hanewald, R.H. (1995) Nickel-cadmium battery recycling through the INMETCO® high

temperature metals recovery process, IEEE, p. 83 – 88

McLaughlin, W & Adams, T.S. (1999) Li Reclamation Process, US Patent 5888463

Mohr, S.H., Mudd, G.M. & Giurco, D. (2012) Lithium resources and production: critical assessment and global projections,

Minerals, 2, p. 65 – 84.

http://www.daikin.com/csr/feature2009/02_2.html

http://www.rockwoodspecialties.com/rock_english/media/pdf_files/02_04_09_Lithium_Supply_Santiago.pdf

http://www.meridian-int-res.com/Projects/Lithium_Microscope.pdf


42

Tedjar, F. & Foudraz, J.-C. (2010) Method for the mixed recycling of the lithium-based anode batteries and cells, US

Patent 7820317B2

N.D. The History of Lithium Ion Batteries. [Online] Available from: http://www.pmbl.co.uk/lithium_ion_battery_history.aspx

[Accessed: 30 October 2014]

Shin, S.M., Kim, N.H., Sohn, J.S., Yang, D.H. & Kim, Y.H., 2005. Development of a metal recovery process form Li-ion

battery wastes, Hydrometallurgy, 79, p. 172 – 181

Sinnot, R.K., 2001 Coulson & Richardson’s Chemical Engineering, Volume 6, Third Edition, Chemical Engineering Design,

Butterworth Heinemann, p. 251

Van der Werf, P. (2011) MHSW processor audit report – INMETCO, SO-MHSW-BAT-01, commissioned by Stewardship

Ontario. [Online] Available from http://envirolaw.com/wp-content/uploads/Inmetco-Audit-Final-Report-1-of-2-files.pdf

[Accessed: 24 October 2014]

Varta (2014) Primary Lithium Cells, LiMnO2, Sales Program and Technical Handbook. [Online] Available from

http://www.varta-microbattery.com/applications/mbdata/documents/sales_literature_varta /HANDBOOK Primary

Lithium_Cells_en.pdf [Accessed: 30 October 2014]

Xu, J., Thomas, H.R., Francis, R.W., Lum, K.R., Wang, J. & Liang, B. (2008) A review of processes and technologies for the

recycling of lithium-ion secondary batteries, Journal of Power Sources, 177, p. 512 - 527

Zhang, P. Yokoyama, T., Itabashi, O. Suzuki, T.M. & Inoue, K., 1998. Hydrometallurgical process for recovery of metal

values from spent lithium-ion secondary batteries, Hydrometallurgy, 47, p. 259 – 271

http://www.pmbl.co.uk/lithium_ion_battery_history.aspx

http://envirolaw.com/wp-content/uploads/Inmetco-Audit-Final-Report-1-of-2-files.pdf

http://www.varta-microbattery.com/applications/mbdata/documents/sales_literature_varta%20/HANDBOOK%20Primary%20Lithium_Cells_en.pdf

http://www.varta-microbattery.com/applications/mbdata/documents/sales_literature_varta%20/HANDBOOK%20Primary%20Lithium_Cells_en.pdf


43

keeping the future fully charged benjamin d.h. knights ...€¦ · 4.2.1 primary lithium batteries...

Documents