Carbon 164 (2020) 317e323

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Carbon
journal homepage: www.elsevier.com/locate/carbon

Yttrium trihydride enhanced lithium storage in carbon materials

Xinyao Zheng a, Guoling Li b, Yanru Guo a, Hongen Yu a, Shuan Li a, Rui Xiao a,
Jie Zheng a, c, *, Xingguo Li a, **
a
Beijing National Laboratory for Molecular Science (BNLMS), College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, PR China
b
College of Materials Science and Engineering, Qingdao University, Qingdao, 266071, China
c
Guangdong Provincial Key Laboratory of Advance Energy Storage Materials, South China University of Technology, Guangzhou, 510640, China

a r t i c l e i n f o a b s t r a c t

Article history: Metal hydrides (MHx) are gaining increasingly interest as anode materials for lithium ion batteries. The
Received 5 February 2020 most widely accepted lithium storage mechanism for MHx is the conversion mechanism to form LiH. Our
Received in revised form previous study suggested a different lithium storage mechanism of rare earth trihydride (REH3, RE ¼ Y, La
2 April 2020
and Gd)-graphite composite: the reactive H released from the REH3-REH2 conversion may enhance the
Accepted 7 April 2020
Available online 10 April 2020
lithium storage capacity of graphite by forming a LieCeH composite. In this work, this interesting
phenomenon is further studied by comparing the lithium storage performance of YH3/carbon composite
using different carbon materials: graphite, acetylene black, activated carbon and commercial graphene.
The enhanced lithium storage capacity by YH3 addition is only observed for graphite, indicating the
essential role of the intact layered graphene structure in this new lithium storage mechanism.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction by controlling the nanoscale morphology, the exact lithium storage

As widely used in digital products and electric vehicles for many
years, lithium ion batteries (LIBs) have been regarded as the most
successful invention of modern society. Although three scientists
won the Nobel Prize for the development of LIBs [1e4], the further
research of LIBs to improve the energy density, safety and life time
has never ended. Many advanced anode materials with much
higher capacity than that of the current graphite based anode were
developed, such as various carbon-based, Sn-based, Al-based, Si-
based and MOx-based materials etc [5e17], providing the oppor-
tunity to further enhance the energy storage density of LIBs.
Recently, MgH2 and other metal hydrides like AlH3, TiH2,
Mg2NiH4, Mg2CoH5 and Mg2FeH6 were studied as conversion type
anode materials. The most widely accepted lithium storage mech-
anism of metal hydrides is formation of LiH and the corresponding
metal/alloy [18e29]. However, metal hydrides always showed
much lower cycling capacity than the high theoretical capacity
[21,25,30]. In addition to the efforts to improve the cyclic stability
* Corresponding author. Beijing National Laboratory for Molecular Science
(BNLMS), College of Chemistry and Molecular Engineering, Peking University, Bei-
jing, 100871, PR China.
** Corresponding author.
E-mail address: zhengjie@pku.edu.cn (J. Zheng).
mechanism in hydrides is also of high fundamental interest.
Rare earth (RE) and related hydrides is widely studied and used
in various fields [31e34]. Our previous work demonstrated that
rare earth trihydrides (REH3, RE ¼ Y, La and Gd) can convert to
dihydrides (REH2) reversibly during lithiation/delithiation, REH2
cannot further convert to RE, due to the high binding energy with
hydrogen [35]. We observed that the YH3/graphite nanocomposite
with a mass ratio of 1:2 shows high capacity of 720 mAh g1 after
250 cycles, which is far higher than that predicted by the conven-
tional conversion mechanism. The unexpected high capacity was
explained by the enhanced lithiation of graphite by the hydridic H
released from the REH3-REH2 conversion, which mitigates the
repulsive interaction of the positively charged Li and allows more Li
binding.
The above results suggest that the lithium storage mechanisms
of metal hydrides could be quite complicated. Particularly, the
carbon material in the electrode may also plays an important role in
the lithium storage. The lithium storage property of carbon poly-
morphs varies significantly. In this work, we study the lithium
storage properties of several YH3/carbon composite with different
carbon materials, including graphite (G), acetylene black (AB),
activated carbon (AC) and commercial graphene (GN). Only YH3/G
composite shows hydrogen-enhanced capacity in both half-cell and
full-cell, while no capacity enhancement is observed for YH3/AB,

https://doi.org/10.1016/j.carbon.2020.04.020
0008-6223/© 2020 Elsevier Ltd. All rights reserved.
318 X. Zheng et al. / Carbon 164 (2020) 317e323
YH3/AC and YH3/GN. The results indicate that the H enhanced
lithiation may only be effective for the intercalation mechanism
with intact multilayer structure.
2. Experiment
2.1. Materials preparation and characterization
YH3 were prepared by direct hydrogenation of an yttrium ingot
(99.9%, Trillion Metal Co., Ltd) under 4 MPa H2 at 623 K for 4 h. The
YH3 samples were collected and grounded to powder in an Ar-filled
glovebox. Commercial graphite powder (300 meshes, Sinopham
Chemical Reagent Co., Ltd), activated carbon powder (Sinopham
Chemical Reagent Co., Ltd), acetylene black powder (Sinopham
Chemical Reagent Co., Ltd) and commercial graphene powder (The
Sixth Element Co., Ltd) were mixed with the YH3 powder or NaCl
respectively at mass ratio of 2:1 (C: YH3 or C: NaCl) by ball-milling
under 0.4 MPa H2 at rotation speed of 200 rpm for 150 min. The
ball-to-material ratio is 60:1. The obtained samples were collected
and stored in an Ar-filled glovebox, marked as YH3/G, YH3/AC, YH3/
AB, YH3/GN and NaCl/G, NaCl/AC, NaCl/AB, NaCl/GN respectively.
Materials were characterized by scanning electron microscopy
(SEM, Hitachi S4800), X-ray diffraction (XRD, PANalytical X’Pert3,
Cu Ka), micro Raman spectroscopy (ThermoFisher DXRxi) and ni-
trogen adsorption-desorption isotherms (Quantachrome NOVA
2200e) at 77 K.
2.2. Electrochemical measurement
The electrode was fabricated by coating a slurry of YH3/C or
NaCl/C, acetylene black and polyvinylidene difluoride (PVDF)
(80:10:10 mass ratio) dispersed in N-methylpyrrolidone on copper
foil. The mass loading of the active materials was around
1.2 mg cm2. Coin-type cells were assembled in an Ar-filled glo-
vebox and consisted of a polypropylene film (Celgard 2400) as the
separator, 1 M LiPF6 in ethylene carbonate/dimethyl carbonate (EC/
DMC, 1:1 in volume) as the electrolyte and a lithium foil counter
electrode as the working electrode for half-cells or a commercial
LiFePO4 electrode (PULEAD Technology Industry Co., Ltd) as the
cathode electrode for full-cells. The cells were tested at current
density of 100 mA g1 for both charge and discharge at room
temperature and in the voltage range of 0.005 Ve3.0 V or 0.005
Ve2.0 V for half-cells and 1.0 Ve3.6 V for full-cells (vs. Liþ/Li).
3. Results and discussion
We prepare YH3/C and NaCl/C composites using four different
carbon materials and compare their electrochemical performance
to investigate the effect of YH3 on lithium storage mechanism of
different carbon materials. NaCl/C composites are used as a control
group to evaluate the effect of ball-milling on the capacity.
The SEM images of the samples are showed in Fig. 1. Pristine AB
is composed of ultrafine particles with about 50 nm diameter. The
size and morphology show no significant change after ball-milling
with NaCl or YH3. NaCl and YH3 particles are 200 nm-1 mm with
irregular morphology well dispersed in AB. (Fig. 1aec). AC is a
microporous amorphous carbon with high specific surface area of
1367 m2 g1 (Fig. S1). In the SEM image, pristine AC appears in large
particles over 5 mm and the micropores are barely observed in the
SEM image. After ball-milling, the large AC particles are broken into
<1 mm particles, homogenously mixed with NaCl or YH3 particles
which are around 200 nm (Fig. 1def). The commercial graphene is
claimed to be prepared by Hummer’s method from graphite [36],
which is composed of thin crumpled sheets with around 2 mm
width and around 260 m2 g1 in specific surface area (Fig. S2). The
graphene sheets are broken into smaller one mixed with 200 nm
NaCl or YH3 after ball-milling (Fig. 1gei). Graphite is thick intact
flakes with around 10 mm width. After ball-milling, graphite flakes
become crinkled, mixed with ~200 nm NaCl or YH3 particles
homogenously (Fig. 1j-l). The effect of the ball-milling is similar for
different carbon materials except for AB. The micrometer scale
particles of AC, GN and G are all broken into small fragments, while
AB which is already in the fine nanoparticles shows no significant
change.
Fig. 2a shows the XRD patterns of each sample. The character-
istic peaks of YH3 of each sample become weaker and wider after
ball-milling, but is still corresponding to JCPDS No.12-0385, which
means that ball-milling does not change the crystalline structure of
YH3. Besides, YH3/G also shows characteristic peaks of graphite
(JCPDS No.65-6212). No carbon related peaks are found for AB, AC
and GN due to their amorphous nature.
Fig. 2bee shows the Raman spectra of each sample. As for car-
bon materials, G band is related to the sp2 C atoms and D band is
related to the sp3 C atoms. Generally, the higher the relative in-
tensity of D band is, the more amorphous structures or defects exist
[37,38]. The intensity ratio of G band and D band in both YH3/AB
and NaCl/AB is around 1:1, in good agreement with the soft carbon
characteristics of AB [39]. It also indicates that the effects from ball-
milling with NaCl and YH3 on the structure of AB are nearly the
same (Fig. 2b). The effects from ball-milling with NaCl and YH3 on
the structure of AC are also close, as indicated by the same shapes of
the Raman spectra. The intensity of G band is slightly higher than D
band, indicating more sp2 carbon atoms exist in AC (Fig. 2c). In the
spectra of YH3/GN and NaCl/GN, the D band is higher than the G
band, which means that more amorphous structures exist in gra-
phene than other carbon samples (Fig. 2d). The slight defects of
graphite attributed to ball-milling can be observed in the spectra of
YH3/G and NaCl/G, corresponding to the low D band. (Fig. 2e).
Generally, it is proved by the Raman spectra that ball-milling can
pulverize carbon materials and introduce defects, whether the
carbon materials are mixed with YH3 or NaCl.
The lithium storage behaviors of the carbon samples are
investigated by galvanostatic charge/discharge at current density of
100 mA g1 within 0.005 V-3.0 V. The electrochemical behaviors of
pristine AB, AC and GN samples are first studied (Fig. S3). The initial
discharge capacity of pristine AB is about 600 mAh g1 and the
cycling capacity stays around 300 mAh g1. The potential profile of
pristine AB shows typical feature of soft carbon, which is usually
formed by decomposition of small organic molecules. The initial
discharge/charge capacity of pristine AC is about 1200 mAh g1 and
462 mAh g1 respectively, with low initial coulombic efficiency
about 38.5%. Due to the large specific surface area of AC, the for-
mation of more solid electrolyte interface (SEI) introduces more
irreversible capacity [40,41]. The stable cycling capacity of pristine
AC is about 330 mAh g1. The potential profile of AC seems to be the
most sloping one in the three carbon materials, without any
obvious plateau. The commercial GN initially discharge/charge to
1220 mAh g1 and 428 mAh g1 respectively, also indicating low
initial coulombic efficiency about 35%. The cycling capacity before
50 cycles is around 400 mAh g1. After that, the cycling capacity
steadily increases along with the cycle number. The phenomenon
so-called “pseudo-capacitance-type behavior” is observed in many
anode materials, overstating the true capacity, which can be pre-
vented by adopting lower current density and lower upper voltage
limit [42,43].
Secondly, the cycling performance and potential profiles of the
YH3/C and NaCl/C samples are investigated for AB, AC and GN. As
shown in Fig. S4, in the same measurement condition, YH3/C and
NaCl/C samples with all the three carbon materials shows
enhanced capacity compared with the pristine carbon materials.
 X. Zheng et al. / Carbon 164 (2020) 317e323
Fig. 1. The SEM images of a)-c) pristine AB, NaCl/AB and YH3/AB, d)-f) pristine AC, NaCl/AC and YH3/AC, g)-i) pristine commercial graphene, NaCl/GN and YH3/GN, j)-l) pristine
graphite, NaCl/G and YH3/G.
However, no significant difference is observed between the YH3/C
and NaCl/C samples in all the three carbon materials, in terms of
both the cycling performance and the potential profiles. Thus, the
slight capacity enhancement compared to the pristine carbon is
attributed to the effect of ball-milling. Indeed, the enhanced ca-
pacity is mainly in the high potential region which is attributed to
the pseudo-capacitance-type behavior, as many defects are intro-
duced by ball-milling, especially in YH3/AB and NaCl/AB.
The similarity between the YH3/C and NaCl/C samples for AB, AC
and GN remains the same when the upper voltage limit is set to
2.0 V to eliminate the possible electrolyte decomposition. (Fig. 3).
The initial capacity of YH3/C is slightly higher than NaCl/C. We
propose that YH3 is active for lithium storage intrinsically but with
poor stability, which leads higher initial capacity and more SEI
formation. Nevertheless, the stable cycling capacity shows no sig-
nificant difference between YH3/C and NaCl/C, which is around
300 mAh g1 for YH3/AB and NaCl/AB, 280 mAh g1 for YH3/AC and
319
NaCl/AC and 230 mAh g1 for YH3/GN and NaCl/GN respectively. As
for the potential profiles, the charge curve of NaCl/AB is more
sloping than YH3/AB, especially above 1.0 V while there is no
obvious difference between YH3/AC and NaCl/AC, as well as YH3/GN
and NaCl/GN. The above results again indicate that YH3 has no
enhancement effect on AB, AC and GN other than ball-milling.
In our previous work, significant capacity enhancement of YH3
on graphite has been observed [35]. In this work, we further
compare the electrochemical performance between YH3/G and
NaCl/G in the voltage range between 0.005 V and 2.0 V to prevent
the influence from the pseudo-capacitance-type behavior so that
the YH3 effect can be observed and analyzed more clearly. At
100 mA g1, YH3/G obtains stable capacity of over 430 mAh g1
after 100 cycles, which is approximately 200 mAh g1 higher than
that of NaCl/G, showing significant promotion over 86% (Fig. 4a).
The result is also in agreement in our previous work which was
tested within 0.005 Ve3.0 V. The capacity is 720 mAh g1 of YH3/G
320 X. Zheng et al. / Carbon 164 (2020) 317e323

Fig. 2. a) the XRD patterns of pristine YH3, YH3/AB, YH3/AC, YH3/GN and YH3/G. the Raman spectra of b) YH3/AB and NaCl/AB, c) YH3/AC and NaCl/AC, d) YH3/GN and NaCl/GN, e)
YH3/G and NaCl/G. (A colour version of this figure can be viewed online.)

Fig. 3. The cycling performance of a) NaCl/AB and YH3/AB, b) NaCl/AC and YH3/AC, c) NaCl/GN and YH3/GN respectively at 100 mA g1. The potential profiles of e) NaCl/AB and YH3/
AB, f) NaCl/AC and YH3/AC, g) NaCl/GN and YH3/GN respectively during the 20th discharge/charge process at 100 mA g1. The test voltage range is 0.005 Ve2.0 V, while the initial
three cycles are tested in 0.005 Ve3.0 V. (A colour version of this figure can be viewed online).

and 400 mAh g1 of NaCl/G respectively and the shapes of potential
profiles are also similar regardless of the upper voltage limit [35].
To test the practical performance of the YH3/G anode, we
assemble a full-cell using LiFePO4 cathode. It is delightful that YH3/
G shows stable cycling performance of around 500 mAh g1 after
100 cycles at 100 mA g1. The YH3 enhanced capacity is still
observed in the full-cell despite of the low coulombic efficiency
(Fig. 4c). We present the 10th charge/discharge potential profiles in
Fig. 4d. The charge/discharge plateau is obvious over 3.0 V,
contributing to over 50% of the whole capacity, which is originated
from the low delithiation plateau of the YH3/G anode.
The Cyclic Voltammetry (CV) curves of the YH3/C samples are
shown in Fig. 5. Two wide cathodic peaks at 0.75 V and 1.03 V are
observed in all the four YH3/C samples in the first cycle, attributed
to the formation of SEI of carbon-based anode materials [44]. As
shown in Fig. 5a, three pairs of sharp redox peaks at the cathodic
potential of 0.25 V, 0.17 V, 0.05 V and the anodic potential of 0.11 V,
0.17 V, 0.24 V respectively are observed in YH3/G, which are asso-
ciated to the stepwise lithiation and phase transformation steps of
YH3/G. Compared to CV curves of pristine graphite [45], the first
two cathodic peaks of YH3/G appear at higher potential, while those
of graphite are at 0.19 V and 0.09 V, indicating that lithiation is
easier in YH3/G. Other redox peaks of YH3/G are at similar potential
with pristine graphite [45]. However, the sharp redox peaks of
graphite are absent in the CV curves of YH3/AB, YH3/AC and YH3/GN
(Fig. 5bed). The different shapes of the CV curves between YH3/G
and YH3/AB, YH3/AC, YH3/GN show different types of lithiation
mechanism of carbon-based materials.
The cycling capacity within 0.005 Ve2.0 V of each sample
summarized in Fig. 6a clearly demonstrates the different roles of
YH3 on the lithium storage capacity of the four different carbon
materials. Consequently, it is proved that YH3 can only enhance the
 X. Zheng et al. / Carbon 164 (2020) 317e323 321

Fig. 4. a) the cycling performance and b) the potential profiles during the 20th discharge/charge process of YH3/G and NaCl/G at 100 mA g1. The test voltage range is 0.005 Ve2.0 V.
c) the cycling performance and d) the potential profiles during the 10th discharge/charge process of the full cell composed by YH3/G versus LiFePO4 at 100 mA g1. The test voltage
range is 1.0 Ve3.6 V. (A colour version of this figure can be viewed online.)

Fig. 5. a)-d) the CV curves of YH3/G, YH3/AB, YH3/AC and YH3/GN respectively, the scan rate is 0.1 mV s1, the potential range is 0 Ve2 V. (A colour version of this figure can be
viewed online.)

capacity of graphite, but cannot influence that of AB, AC and gra-
phene. We propose that the unique phenomenon of YH3 enhanced
lithium storage is related to the multilayer structure of graphite,
which is absent in other three carbon materials [46]. Lithium
storage in graphite follows the intercalation mechanism forming
LiCx compounds (x ¼ 6~24). Lithium intercalation beyond Li/C ¼ 1/6
is energetically unfavorable, probably due to the repulsion of the
intercalated Li. We have proposed a H-enhanced Li-binding
mechanism to explain the REH3-enhanced lithium storage in
graphite. During lithiation, the REH3 converts to REH2 and release
one active H, which is partially negatively charged. The negatively
charged H will mitigate the repulsive interactions of the positively
charged Li and allows more Li binding. The stable structure with
maximum Li bonding is Li5C16H instead of LiC6 for unmodified
graphite (Fig. 6b) [35]. This mechanism requires graphene layers to
provide binding sites for both Li and active H. So the intact multi-
layer structure is essential.
On the contrary, other three types of carbon, AB, AC and gra-
phene, have different lithiation mechanism. Both of AB and AC are
classified as disordered carbon without multilayer structure. The
322 X. Zheng et al. / Carbon 164 (2020) 317e323
Fig. 6. a) Comparing the stable cycling capacity within 0.005 Ve2 V of different YH3/C
with NaCl/C, showing the enhancement effect on graphite from YH3. b) the schematic
of Li5C16H formed through H-enhanced mechanism, simulated by DFT calculation, c)
schematic illustration of the lithium storage mechanism of disordered carbon mate-
rials (such as AB and AC), d) schematic illustration of the lithium storage mechanism of
single-layer graphene. (A colour version of this figure can be viewed online.)
lithium storage mechanism of disordered carbon includes storage
in defects, cavities and pores, wrinkled and buckled structural
segments, as well as interfaces and surfaces, instead of lithium
insertion [39]. The lithium storage mechanism of these disordered
carbon is shown in Fig. 6c, which also is also observed in various
carbon nanomaterials [15,47,48]. Lithium storage in graphene is
generally considered as a “house of cards” model, suggested by
Dahn et al. [39,46,49] As shown in Fig. 6d, the lithium could be
adsorbed on both sides of the single-layer sheet. Due to the excess
lithium storage, graphene usually shows higher capacity than
graphite. However, the commercial graphene used in this study
failed to show high capacity, which is probably due to the incom-
plete exfoliation of the graphene layers. The commercial graphene
can also be regarded as a disorder carbon, containing voids of
different size due to the wrinkles and stacking of the graphene
sheets and also heteroatoms during the exfoliation using the
Hummer’s method. As a result, the lithium storage behavior is
similar to that of AB and AC. For these disorder carbon materials, Li
is bond to the defect sites or the voids via a pseudo-capacitive
mechanism. The potential profile usually shows no well-defined
plateau and the capacity strongly depends on the upper voltage
limit. In this case, the negatively charged H will not provide addi-
tional bonding sites. Thus, it is not surprising that the active H
released from YH3 have no effect on promoting the lithium storage
capacity.
4. Conclusion
In summary, the lithium storage properties of YH3/carbon
composites prepared by ball-milling using four different carbon
materials, including acetylene black (AB), active carbon (AC),
commercial graphene (GN) and graphite (G) are compared. YH3
significantly enhances the capacity of graphite. The cycling capacity
of YH3/G at 100 mA g1 is 430 mAh g1 in half-cell within 0.005
Ve2.0 V and 500 mAh g1 in full-cell within 1.0 Ve3.6 V respec-
tively. The high capacity of YH3/G further confirms the H- enhanced
Li bonding model proposed in our previous study, i.e. the negatively
charged active H released from the YH3-YH2 conversion leads to
more Li intercalation into the interlayer space of graphite. YH3
shows no capacity enhancement for AB, AC and GN, which is
attributed to the absence of the lithium intercalation mechanism in
AB, AC and GN. The results indicate the importance of intact gra-
phene layers for the H- enhanced Li bonding phenomenon.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
CRediT authorship contribution statement
Xinyao Zheng: Conceptualization, Methodology, Software, Data
curation, Visualization, Investigation, Writing - original draft,
Writing - review & editing. Guoling Li: Investigation, Software.
Yanru Guo: Investigation, Software. Hongen Yu: Investigation.
Shuan Li: Resources. Rui Xiao: Resources. Jie Zheng: Conceptual-
ization, Supervision, Writing - review & editing. Xingguo Li:
Supervision.
Acknowledgements
The authors acknowledge MOST of China (No. 2018YFB1502102),
NSFC (No. 51971004, 51771002, 21771006 and U1607126) and the
Open Fund of the Guangdong Provincial Key Laboratory of Advance
Energy Storage Materials, China.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.carbon.2020.04.020.
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