RRL

Introduction

The availability of affordable clean water is one of the key technological, social, and economical
challenges of the 21st century. Clean water, acknowledged as a basic human right by the United Nations
[1], is still unavailable to one out of seven people worldwide. To complicate matters, increasing
groundwater extraction around the globe results in progressive salt water ingress in wells and aquifers.
As a consequence, there is a large interest in the development of economically attractive desalination
technologies. Over the years, a number of desalination methods have been developed among which
distillation, reverse osmosis, and electrodialysis are the most commonly known and widespread
technologies [2]. A common goal for current research is to make these technologies more energy
efficient and cost effective, both for the deionization of seawater and for brackish water.

CDI uses pairs of oppositely placed porous carbon electrodes which store ions upon applying an

electrical voltage difference, see Fig. 1. Such electrodes can be assembled in stacks of multiple pairs.

The ions are harvested from the water flowing through a ‘‘spacer channel’’ in between the two
electrodes and are immobilized in the pores inside the carbon material. This process is based on the
formation of electrical double layers (EDLs) inside the intraparticle pores. EDL formation is the

cornerstone of capacitive energy storage and also the mechanism by which salt ions are immobilized

and selectively extracted from saline water. After some time, all of the accessible intraparticle pore

volume is saturated with electrosorbed ions and the storage capacity of the device is reached. In order

to regenerate the carbon electrodes, the ions are released from the electrode by reducing or even

reversing the cell voltage. In this way, a small stream enriched in ions is produced and the electrodes

regain their initial ion uptake capacity. Ideally, without the presence of chemical reactions, this process
is purely physical in nature and potentially enables CDI devices to have a long service life and low

maintenance.

Compared to the classical work of the 20th century, various modifications and new technologies

are nowadays considered for CDI, such as the inclusion of ion-exchange thin membrane barriers in

front of the electrodes, see Fig. 1b [8–12], and optimized operational modes such as stop-flow operation
during ion release [13], salt release at reversed voltage [12], constant-current operation [14], energy
recovery from the desalination/release cycle [15,16], flow-through electrodes where the water is

directed head-on through the electrodes [17,18], and flow electrodes based on carbon suspensions

[19].

On the materials side, new materials and design strategies for novel and improved electrodes continue
to emerge. Fundamentally, even the very basic question of the ‘‘best’’ material remains unanswered.
Naturally, the choice of electrode material largely depends on required performance
(desalting capacity, final salt concentration), system requirements (flow rate, stack configuration),

and cost considerations (efficiency, material cost, lifetime). However, we are currently only starting

to understand CDI operation on a quantitative and kinetic basis. Ongoing research is not only dedicated
to further optimizing the pore size distribution and chemical composition of already known carbons, but
also expands to novel materials and complex pore and electrode architectures [20–22].

In this review we summarize the basics and theory of CDI. We discuss the range of carbon materials

used for CDI, and provide guidelines and strategies for a rational design of porous carbon electrodes for

desalination applications. Note that in Sections 3–7 the terminology macrospores and micropores is

based on that used in porous electrode theory [23–26], with the term ‘‘macrospores’’ denoting the
electrolyte-filled continuous interparticle space in between carbon particles, serving as transport
pathways for ion transport across the electrode, while the term ‘‘microspores’’ is used for all the pore

space within the carbon particles (intraparticle porosity). In Section 8 the formal IUPAC terminology

for porous material characterization is used where macro-, meso-, and microspores are distinguished

based on the pore sizes in a porous material [27].