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shielding with 2D transition metal breakthrough has been reported thus far. New
EMI shielding materials that can exceed the re-
quirements of next-generation portable equip-
carbides (MXenes) ment and wearable devices are strongly needed.
MXenes are a unique family of two-dimensional
Faisal Shahzad,1,2* Mohamed Alhabeb,3* Christine B. Hatter,3* Babak Anasori,3
(2D) transition metal carbides and/or nitrides
with the formula Mn+1XnTx, where M is an early
Soon Man Hong,1 Chong Min Koo,1,2 Yury Gogotsi3
transition metal (e.g., Ti, Zr, V, Nb, Ta, or Mo) and
X is carbon and/or nitrogen. Owing to the aque-
Materials with good flexibility and high conductivity that can provide electromagnetic
ous medium used during synthesis, MXene flakes
interference (EMI) shielding with minimal thickness are highly desirable, especially if
are terminated with surface moieties (Tx), such
they can be easily processed into films. Two-dimensional metal carbides and nitrides,
as a mixture of OH, =O, and F (12). Metallic
known as MXenes, combine metallic conductivity and hydrophilic surfaces. Here, we
conductivity and good mechanical properties
demonstrate the potential of several MXenes and their polymer composites for EMI
coupled with hydrophilicity make MXenes a good
shielding. A 45-micrometer-thick Ti3C2Tx film exhibited EMI shielding effectiveness
candidate for use in polymer composites (12) and
of 92 decibels (>50 decibels for a 2.5-micrometer film), which is the highest among
energy storage devices (13) as they can intercalate
synthetic materials of comparable thickness produced to date. This performance
E
and polyvinyl alcohol (PVA). The MXene-polymer
lectronic devices are getting smarter, being tiple internal reflections is less studied but con- composites exhibited improved tensile strength,
made smaller, and growing in number every tributes substantially to EMI shielding effectiveness. but good conductivity was maintained at low
day. Any electronic device that transmits, These internal reflections arise from scattering polymer loadings (16, 17). A previous study in-
distributes, or uses electrical energy creates centers and interfaces or defect sites within the corporating a naturally occurring polymer, sodium
electromagnetic interference (EMI) that has shielding material, resulting in scattering and alginate (SA), as a binder for Li-ion batteries (18)
detrimental impacts on device performance and then absorption of EM waves (EMWs) (1, 8, 9). showed retention of electrode conductivity, the
the surrounding environment. As electronics Previously, metal shrouds were the material of primary component for EMI shielding. SA is a
and their components operate at faster speeds choice to combat EMI interference (14) (610), linear polysaccharide copolymer derived from sea-
and smaller size, a substantial increase in EMI but with smaller devices and components, add- weed. Natural biomaterials, like SA, are potentially
results, which can lead to malfunctioning and ing additional weight coupled with susceptibility ideal candidates for polymeric matrices because
degradation of electronics (14). This increase in to corrosion makes metals less desirable (8). they are abundant, do not harm the environ-
electromagnetic pollution can also affect human Lightweight, low-cost, high-strength and easy- ment, and are mechanically robust. SA has oxygen-
health, as well as the surrounding environment, to-fabricate shielding materials are therefore containing functional groups (OH, COO, and
if no shielding is provided (5). needed. Polymer-matrix composites with embedded =O), which can potentially facilitate the forma-
An effective EMI shielding material must both conductive fillers have become a popular alter- tion of hydrogen bonding with the termination
reduce undesirable emissions and protect the com-
ponent from stray external signals. The primary
function of EMI shielding is to reflect radiation
using charge carriers that interact directly with
the electromagnetic (EM) fields (6). As a result,
shielding materials need to be electrically conduc-
tive. However, conductivity is not the only require-
ment. The secondary mechanism of EMI shielding
requires absorption of EM radiation due to the
materials electric and/or magnetic dipoles inter-
acting with the radiation. High electrical conduc-
tivity is the primary factor determining reflectivity
and absorption characteristics of the shield (7).
However, a third mechanism accounting for mul-
1
Materials Architecturing Research Center, Korea Institute of
Science and Technology, 5, Hwarang-ro 14-gil, Seongbuk-gu,
Seoul 02792, Republic of Korea. 2Nanomaterials Science and
Engineering, University of Science and Technology, 217,
Gajung-ro, Yuseong-gu, Daejeon 34113, Republic of Korea.
3
Department of Materials Science and Engineering, and
A. J. Drexel Nanomaterials Institute, Drexel University, 3141
Chestnut Street, Philadelphia, PA 19104, USA.
*These authors contributed equally to this work. Corresponding
author. Email: gogotsi@drexel.edu (Y.G.); koo@kist.re.kr (C.M.K.) Fig. 1. Schematic of Ti3C2Tx and Ti3C2Tx-SA composite films.
groups of MXenes. To date, no MXene-SA com- (compare the top two patterns in Fig. 2D). This like temperature dependence of conductivity
posites have been reported in the literature. peak corresponds to a Ti3C2Tx interlayer spacing (15, 19).
Here we report highly flexible MXene films of ~10 , a result of SA presence between MXene Electrical conductivities of Ti3C2Tx-SA polymer
(Ti3C2Tx, Mo2TiC2Tx, and Mo2Ti2C3Tx) and nacre- layers. In the case of 30 wt % Ti3C2Tx-SA, the composites are plotted in Fig. 3B. With the addi-
like MXenepolymer composite films (Ti3C2Tx- broad (002) peak is between 4.4 and 6.5, which tion of only 10 wt % Ti3C2Tx, the conductivity of
SA) with excellent EMI shielding performance. is due to the variable interlayer spacings between SA polymer rises to 0.5 S cm1. The large aspect
All free-standing films were made by vacuum- MXene layers, ranging from >10 to 3.5 . This ratio of Ti3C2Tx flakes likely provides a percola-
assisted filtration starting from colloidal solutions shows that although SA molecules are intercalated tion network at low filler loading, thereby in-
of pure MXenes or its composites (fig. S1). The between MXene layers, the latter still retains the creasing electrical conductivity of the composite
schematic representation of the layered struc- ordered layered structure. sample. As filler content is increased, electrical
ture for MXene-SA composites is displayed in Cross-sectional transmission electron micros- conductivity increases and reaches 3000 S cm1 for
Fig. 1. Both Ti3C2Tx film (45 mm) and Ti3C2Tx-SA copy (TEM) images of the Ti3C2Tx-SA composite the 90 wt % Ti3C2Tx-SA composite.
[8 mm, 10 weight % (wt %) SA], in particular, ex- films confirm the intercalation of SA layers in- To explore the EMI shielding properties of
hibit extraordinary EMI shielding effectiveness between MXene flakes. At higher Ti3C2Tx con- MXenes, we compared three MXene film com-
(SE) of 92 and 57 dB, respectively. These MXene tents, mostly stacks of Ti3C2Tx flakes, with some positions with an average thickness of ~ 2.5 mm in
films have additional advantages such as high individual flakes separated with SA, are observed Fig. 3C. EMI SE is directly proportional to electrical
conductivity, easy processing, relatively low den- (Fig. 2E). This feature could be due to MXene conductivity (eq. 2, supplementary materials).
sity, and mechanical flexibility. To our knowledge, restacking during filtration. At lower Ti3C2Tx Consequently, Ti3C2Tx, with the best electrical
this is the highest EMI SE performance reported concentrations, more individual Ti3C2Tx flakes conductivity, gives the highest EMI SE among
for synthetic materials of similar thickness and are separated with SA, and a variety of different the studied MXenes. Because thickness plays
is comparable to the EMI SE performance of pure interlayer spacings are present (Fig. 2F). How- a crucial role in EMI SE of any material, EMI SE
telecommunication applications. Therefore, it is the known synthetic materials and rank at the reducing net weight and volume), oxidation resist-
important to achieve high EMI SE values with top of the comparison chart (Fig. 4A). ance (due to polymer binder), high flexibility (a
relatively thin films. As discussed above, to fur- Recently, the concept of foam structures has feature of 2D films), and simple processing (mix-
ther improve MXenes mechanical properties and gained tremendous interest as a way to reduce ing and filtration or spray-coating). Going a step
environmental stability, and to reduce their weight, the density of shielding materials. Lightweight further, Ti3C2Tx and Ti3C2Tx-SA composites were
we can embed them in polymer matrices. As an materials are a necessity for aerospace applica- compared with pure aluminum (8 mm) and copper
example, we investigated the Ti3C2Tx-SA com- tions; therefore, some metals (such as copper and (10 mm) foils (fig. S6). Ti3C2Tx, which has two orders
posites for EMI shielding. Here, the thickness of silver) that possess high EMI SE values are less of magnitude lower electrical conductivity than
composite films was fixed between 8 and 9 mm. useful (1, 2830). When considering a materials these metals, shows EMI SE values similar to those
With increasing MXene content, EMI SE increased, density, specific EMI shielding effectiveness (SSE) of metals (tables S2 and S3). For comparison, ther-
to a maximum of 57 dB for the 90 wt % Ti3C2Tx-SA is used as a criterion to evaluate different mate- mally reduced graphene oxide film (8.4 mm) that
sample (Fig. 3E). To obtain a clearer picture, we rials. However, SSE alone is not a sufficient pa- possessed lower electrical conductivity is also plotted
plotted the influence of filler content on EMI SE rameter for understanding overall effectiveness, and fell far below the other materials (32).
at a constant frequency of 8.2 GHz (see fig. S4). as a higher SSE can simply be achieved at a larger The massive EMI SE of MXene can be under-
Shielding mechanism from absorption (SEA) and thickness, which directly increases the weight of stood from several proposed mechanisms shown
reflection (SER) in the Ti3C2Tx (6 mm) and 60 wt % the final product. Therefore, a more realistic pa- in Fig. 4B. The EMI shielding originates from the
Ti3C2Tx-SA (~8 mm) films were plotted in Fig. 3F rameter is to divide SSE by the material thick- excellent electrical conductivity of MXene and
at 8.2 GHz. Shielding due to absorption was the ness (SSE/t) (27, 31). Such a parameter is highly partially from the layered architecture of the
dominant mechanism, rather than reflection in valuable for determining the effectiveness of a films. A potential mechanism can be explained as
pristine MXene and its composites. material by incorporating three important factors: follows: As EMWs strike the surface of a MXene
A comprehensive literature review of previously EMI SE, density, and thickness. Interestingly, SSE/t flake, some EM waves are immediately reflected
studied materials for EMI SE (table S2) clearly values for MXene and MXene-SA composites are because of abundant free electrons at the surface
indicates that MXenes and their composites are much higher than those for other materials of of the highly conductive MXene (9, 10). The re-
the best EMI shielding materials known to date. different categories (table S3). As a representa- maining waves pass through the MXene lattice
So far, most research has focused on graphene tive example, a 90 wt % Ti3C2Tx-SA composite structure where interaction with the high electron
(11, 21, 22), carbon nanotubes (23), iron oxides (24), sample gives a SSE/t of 30,830 dB cm2 g1, which density of MXene induces currents that contrib-
ferrites (25), iron-aluminum-silicon alloys (26), is several times higher than those of the other ute to ohmic losses, resulting in a drop in energy
and metallic-based filler (27) polymer composites. materials studied thus far (fig. S5). This finding of the EMWs. The surviving EMWs, after passing
However, to satisfy the common commercial EMI is notable because several commercial require- through the first layer of Ti3C2Tx (marked as I in
shielding requirements (above 30 dB) (2), large ments for an EMI shielding product are engrained Fig. 4B), encounter the next barrier layer (marked
thicknesses, usually more than 1 mm, are needed. in a single material, such as high EMI SE (57 dB), as II), and the phenomenon of EMW attenua-
Ultrathin MXene films clearly outperform all of low density (2.31 g cm3), small thickness (8 mm, tion repeats. Simultaneously, layer II acts as a
reflecting surface and gives rise to multiple in- very thin films for device shielding to help elim- 22. F. Shahzad, P. Kumar, Y.-H. Kim, S. M. Hong,
ternal reflections. The EMWs can be reflected inate EM radiation as miniaturization of elec- C. M. Koo, ACS Appl. Mater. Interfaces 8, 93619369
(2016).
back and forth between the layers (I, II, III, and tronics progresses. This study is set to pave the 23. Z. Zeng et al., Carbon 96, 768777 (2016).
so on) until completely absorbed in the structure. way for a large family of 2D materials that are 24. S. Varshney, A. Ohlan, V. K. Jain, V. P. Dutta, S. K. Dhawan,
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We have shown here that flexible Ti3C2Tx films (2016). SUPPLEMENTARY MATERIALS
16. Z. Ling et al., Proc. Natl. Acad. Sci. U.S.A. 111, 1667616681
with thicknesses ranging from 1 to 45 mm exhibit (2014).
www.sciencemag.org/content/353/6304/1137/suppl/DC1
excellent electrical conductivity and EMI shield- Materials and Methods
17. M. Boota et al., Adv. Mater. 28, 15171522 (2016).
Supplementary Text
ing capabilities. The reported EMI SE values are 18. I. Kovalenko et al., Science 334, 7579 (2011).
Figs. S1 to S6
the highest of any known synthetic materials with 19. B. Anasori et al., Nanoscale Horizons 1, 227234
Tables S1 to S3
(2016).
similar thickness. Moreover, excellent shielding 20. M. Khazaei et al., Adv. Funct. Mater. 23, 21852192
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SUPPLEMENTARY http://science.sciencemag.org/content/suppl/2016/09/07/353.6304.1137.DC1
MATERIALS
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