Introduction

The present review describes electrochemical methods for the recovery of chemical
feedstocks from waste materials. We emphasize the use of electrical current, fields, and
controlled potentials as sustainable, scalable solutions to impending societal challenges
such as materials recycling and the management of solid wastes. This review focuses on
two facets of electrochemical recycling: the recovery of critical raw materials from
wastes that would otherwise be destined for landfills. This review describes both
technological processes and current research with the goal of catalyzing understanding
towards the mining of valuable materials from complex wastes.

Waste as a source of valuable materials

To meet challenges related to resource conservation, manufacturing costs, and
performance limitations across the technology landscape, innovative manufacturing
methods based on electrochemistry are needed. The purpose of this review is to
highlight electrochemical technology and current research related to such processes in
the context of the recovery of critical raw metallic materials from solid waste. These
methods, deployed in tandem onto a single waste stream, can produce high-dollar
recycled feedstocks from discarded materials and pave the way toward enabling
circularity in our currently linear economic chains. Additionally, chemical conversion
technologies based on electricity benefit from the development of low-cost solar and
wind energy, providing additional financial and environmental incentives.
Although many types of waste, including polymer waste, suffer from a dearth of
established electrochemical recycling methods, other areas of electrochemical recycling
have proven track records of success. As discussed below, certain critical raw materials
successfully undergo industrial-scale electrochemical recycling. The present text seeks
to highlight some mature technologies for electrochemical solid waste recycling as well
as some emergent strategies in the research arena.

What are critical raw materials (CRMs)?

Many modern technologies rely on minerals and metals sourced from around the world.
Although not always in the public eye, some of these minerals are critical for the
manufacturing of items necessary for everyday life. Steel, for example, may contain
nickel, copper, chromium, aluminum, tungsten, molybdenum, cobalt, and vanadium
depending on the specific steel alloy. Many other products and technologies rely heavily
on one or more minerals, such as gallium for backlighting in TVs and phones, graphite
for rechargeable battery electrodes, and cobalt for smartphone batteries. Although
some minerals are abundant and easily sourced domestically, others with less certain
procurement are positioned to severely impact the United States industry, economy,
and military if they become scarcer or even unobtainable.
Due to this fact, organizations in the U.S. maintain lists of critical minerals, which are
minerals that are important for technologies and for which supply chains may be at risk
due to factors such as high import reliance. The United States Geological Survey (USGS)
currently lists mineral commodities as being critical to the economy and nation while
the National Defense Stockpile (NDS) maintains a collection of 38 minerals deemed
critical to defense efforts. With the information collected from various sources including
the USGS, the Department of the Interior periodically releases an updated list of critical
minerals. The list from 2018 includes 35 minerals.
The history of the critical minerals list begins with the establishment of the NDS, which
began in 1939 through the execution of the Strategic Materials Act. The act authorized
funding for purchasing strategic and critical materials for wartime production. The first
acquisitions in 1940 included chromite, manganese, and tin. The list has evolved over
time in response to changing technologies. In 1993, 44 materials in excess or considered
obsolete were sold off to the private sector including aluminum, cobalt, nickel, and
silver. Today the U.S. stockpile contains thirty-seven materials with a value of $1.152
billion. A 2014 congressional act determined the need to acquire rare earth elements
(REEs) and to determine better ways of recycling REEs from scrap and waste. In 2017, an
executive order officially defined a ‘‘critical mineral’’ as being a non-fuel that is essential
to economic and national security, which has an at-risk supply chain, and which would
cause harm to the nation if supply was disrupted. The Department of the Interior and
USGS then, as part of the executive order, published the current list of 35 minerals.
One of the driving forces behind changes in the list is the development of new
technologies, including green technologies, and the change in demand for minerals
based on those developments. This can mean either increased demand, leading to new
critical designation for materials that previously were not critical or decreased demand,
causing a mineral to lose its critical status. Recent changes in demand that may affect
the future of the list include decreased demand for aluminum, chromium, manganese,
platinum, rare earth elements, titanium, and tantalum; slowly increasing demand for
lithium, germanium, and graphite; and rapidly growing demand for tellurium, niobium,
and indium. Additionally, the U.S. has a high import reliance on materials like yttrium,
gallium, magnesium metal, tungsten, bismuth, and rare earth elements, which could be
a security risk and cause concerns with the supply chain in the future.
An increase in mining and other extraction techniques worldwide would increase the
availability of certain critical minerals, but these operations would require time and
capital and are tied to concerns about ethical labor and environmental impact.
Additionally, several critical minerals are not mined in pure form but as a mixture with
other minerals, thus raising the level of complexity of their collection and use. Finally,
although not a requirement for critical mineral status, several of these minerals are
geologically scarce, and global resources may be depleted especially with increased
consumption. Thus, recovery and recycling of the minerals from secondary sources is a
priority to supply minerals and reduce the pollution caused by disposal.
Several types of non-electrochemical CRM recycling methods are used. Pyrometallurgy
and hydrometallurgy are the two most common. Pyrometallurgy primarily uses heat to
extract metals, requiring high energy costs, while hydrometallurgy produces aqueous
solutions from which the metals are extracted, but produces hazardous chemical waste.
These processes are usually followed by a refining process which can also be
pyrometallurgical or hydrometallurgical in nature with the addition of electrochemical
methods. Although less common, electrochemical extraction methods have also been
studied. Electrochemistry offers a green alternative to many techniques, as it uses
electrons, a potentially ‘‘green reactant,’’ and can avoid pollution and waste. This
discussion focuses on technical aspects related to the use of electrochemical methods
for the recycling of certain critical metallic minerals, using the Department of the
Interior’s 2018 final list as the primary indicator of criticality.

Overview of electrochemical recycling techniques for CRM

recovery
Some of the minerals in the CRM lists have few to no methods of recycling in active,
large-scale use such as the antimony used in flame retardants or gallium in LEDs and
solar cells. For others, established recycling practices are usually included in the two
categories of pyrometallurgy and hydrometallurgy which require high temperatures or
hazardous solvents. Electrochemistry is a green alternative to many of these techniques
and can recover materials from complex critical mineral mixtures for which traditional
methods, such as hydrometallurgy and pyrometallurgy, are less effective or non-
existent. For example, techniques such as slurry electrolysis and electrodeposition have
been used to collect minerals like manganese, aluminum, and antimony from complex
mixtures. Because many metal ions have different deposition voltages, electrochemical
techniques can successfully separate mixed wastes containing a variety of metal ions,
presenting an advantage over techniques that are sensitive to other metal ion content.
Additionally, combining electrochemical methods with some selective chemical
deposition can further improve selectivity toward certain metal ions. Especially when
used in combination, these two methods may help with the separation and purification
of products. Similarly, electrical fields can be used to collect indium from indium tin
oxide on a broken glass substrate. Continued developments in these types of methods
are necessary. Of special interest are methods that can retrieve valuable products out of
end-product wastes that combine both metallic and organic components.
Electrochemistry is therefore uniquely poised to address some of the complex
challenges associated with mixed wastes, but the field of electrochemical methods for
the recovery of organic materials remains in its infancy. This section highlights mature
technological recycling methodologies in the field of CRMs that may cross-pollinate
interest in the field of mining organic materials from complex mixtures.

Common techniques
Some common electrochemical techniques applicable to CRM recycling are briefly
defined below for brevity in later discussions.
 Electrostatic separation applies constant currents to two electrodes. The
difference in electrical conductivity of materials (metal and non-metal) leads to
the separation of materials.
 Electrodeposition is the use of electric current to deposit solid metal on the
cathode of an electrochemical system.
 Electrocoagulation is used to produce metal ions in solution simultaneously with
the generation of hydroxyl groups and hydrogen gas. Electrons affect the charges
of suspended solids and oils. These species all coagulate to form flocs which can
then be removed from the solution and processed.
 Electrodialysis (ED) uses ion-exchange membranes and electrical driving forces to
transport aqueous ions, such as transporting cations into catholyte and
restricting the flow of anions.
 Electrochemical ion exchange is a combination of electrodialysis and ion
exchange.
 Electro-electrodialysis (EED) combines electrolysis and ED, allowing the
separation of ions from solutions and then the regeneration of oxidation or ionic
forms through electrolysis.
 Electro deionization is set up similarly to electrodialysis but uses ion-exchange
resins in the dilute compartment.
 Electro-flotation uses uniform and tiny bubbles of hydrogen and oxygen
generated by water splitting to cause the flotation of all solid particles in a
solution, thus enabling the easy removal of solids. Electro-flotation produces
smaller bubbles compared to other flotation techniques, can be placed to cover
the entirety of tanks, is safe to use, and produces easily monitored visible
results.
 Slurry electrolysis is a method that can convert solid metal-containing particles
first by anodic electro dissolution followed by electrodeposition.