Rare Met.
(2020) 39(9):1019–1033
https://doi.org/10.1007/s12598-020-01443-z
Recent progress in plant-derived hard carbon anode materials for
sodium-ion batteries: a review
Peng Yu, Wei Tang, Fang-Fang Wu, Chun Zhang, Hua-Yun Luo,
Hui Liu* , Zhi-Guo Wang*
Received: 17 February 2020 / Revised: 2 March 2020 / Accepted: 28 April 2020 / Published online: 19 June 2020
Ó The Nonferrous Metals Society of China and Springer-Verlag GmbH Germany, part of Springer Nature 2020
Abstract Sodium-ion batteries (SIBs) have been consid-
ered as a promising alternative to the commercialized
lithium ion batteries (LIBs) in large-scale energy storage
field for its rich reserve in the earth. Hard carbon has been
expected to the first commercial anode material for SIBs.
Among various of hard carbon materials, plant-derived
carbon is prominent because of abundant source, low cost
and excellent electrochemical performance. This review
focuses on the recent progress in the development of plant-
derived hard carbon anodes for SIBs. We summarized the
microstructure and electrochemical performance of hard
carbon materials pyrolyzed from different parts of plants at
different temperatures. It aims to present a full scope of
plant-derived hard carbon anode materials and provide in-
depth understanding and guideline for the design of high-
performance hard carbon for sodium ion anodes.
Keywords Sodium-ion battery; Anode material; Hard
carbon; Plant derived; Electrochemical performance
1 Introduction
Energy and environmental problems are critical to human
development. Traditional non-renewable fossil energy will
be exhausted in the near future. At the same time, the
massive consumption of fossil fuels contributes to global
P. Yu, W. Tang, F.-F. Wu, C. Zhang, H.-Y. Luo,
H. Liu*, Z.-G. Wang*
School of Chemistry and Materials Science, Hunan Agricultural
University, Changsha 410128, China
e-mail: liu.hui@hunau.edu.cn
Z.-G. Wang
e-mail: wangzhiguo@hunau.edu.cn
RARE METALS
www.editorialmanager.com/rmet
warming and ocean acidification [1]. Therefore, the
development and utilization of clean and renewable energy
sources are multiplying, such as wind energy, solar energy,
tidal energy and biomass energy. At the same time, it is of
extreme importance to develop energy storage to modulate
these intermittent renewable resources. Among various
energy storage equipment, such as supercapacitors [2, 3],
lithium ion batteries (LIBs) [4], sodium-ion batteries
(SIBs) [5] and potassium ion batteries (PIBs) [6–9], the
former two have been commercialized, and the latter two
have great development prospects. Table 1 compares main
performance parameters for energy storage devices. LIBs
and SIBs have higher energy density than supercapacitors.
At present, LIBs have been widely used in portable elec-
tronic products and electric vehicles. However, the devel-
opment of the LIBs is limited resulted by the lacking and
uneven distribution of lithium resources. Current cost
comparison indicates that the cost of battery does not be
directly reduced when replacing lithium with sodium.
However, the reserve of sodium resources in the earth’s
crust is up to 2.09%, much richer than 0.0065% of lithium.
Therefore, it should be believed that the use of sodium
would bring considerable cost advantages in the case of
lithium shortages and associated price increases in future.
Moreover, the replacement of current collectors from
copper to aluminum in SIBs would also have a positive
impact on the final price of battery [10]. The research and
development of LIBs provides rich experiences to SIBs for
their physicochemical properties are similar. Most of
cathode materials for SIBs, such as oxides, polyanions and
organic compounds, have a similar reproducible develop-
ment to that used in LIBs [11]. Similarly, the main anode
materials for SIBs are divided into metal oxide [12–15],
carbon [16–21], alloy compound [22–27], as shown in
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1020
Table 1 Comparison of main performance parameters of energy storage devices
Energy storage devices Operating voltage/V Energy density/(Whkg-1)
Lithium ion batteries 2.00–3.95 \ 198
Sodium-ion batteries 2.30–3.40 \ 165
Supercapacitors 2.70–6.00 \ 75
Fig. 1 The main anode materials for SIBs
Fig. 1. Furthermore, carbon materials have become the
preferred target for researching anode for SIBs. Carbon
materials are mainly classified into soft carbon, hard car-
bon, graphite and graphene [5, 28]. Except graphite, the
dominant anode of commercial LIBs, it can only deliver
specific capacity of 31 mAhg-1 for sodium storage [29]. It
should be related to that Na? cannot be inserted in the
interlayer spacing of graphite for its radius is 0.102 nm,
greater than that of Li? (0.076 nm) [11]. Previous experi-
ments and simulation results show that other carbon
material with an ordered layer structure and an interface
distance slightly larger than 0.37 nm can function as Na?
similar to graphite inserted by Li?.
Among various carbon materials, hard carbon is the most
suitable for sodium storage. Hard carbon is less graphitized,
and its average spacing is about 0.41 nm, which is larger than
that of graphite [30]. Plus, the disordered structure of hard
carbon can offer more defects and then provide more active
sites for intercalation/deintercalation of sodium ions com-
pared with soft carbon. Therefore, hard carbon shows
excellent electrochemical properties for SIBs. Hard carbon
materials are mainly derived from the pyrolysis of synthetic
organics and biomass. The process of pyrolysis from the
former has already been mature. But the synthetic organics
are high molecular polymer, such as polyacrylonitrile [4],
polyaniline [31, 32], polydopamine [16], phenolic resins [33]
and polyimide [34], so the cost of carbon source materials is
123
P. Yu et al.
Cycle life Cost/($kWh-1)
5000–10,000 234.0–407.0
[ 5000 235.1–331.3
[ 50,000 –
relatively high. Compared with synthetic organic matter,
biomass is much more suitable for carbon source materials,
for it has unique characteristics of diverse types, physico-
chemical properties, environmental friendliness and con-
siderable economic value [35]. Most of biomass-derived
hard carbon can inherit porous microstructure and layered
structure from rich natural microstructure, which facilitates
electrolyte penetration and the diffusion of sodium ions. In
addition, natural biomass usually contains heteroatoms such
as nitrogen [36–38], fluorine [39], sulfur [40, 41], boron [42]
and potassium [43], which have complex effects on the
properties of biomass-derived hard carbon. Many studies
have shown that heteroatoms doping can increase conduc-
tivity, additional defects or the layer spacing of carbon
materials, which is beneficial to improve sodium storage
performance [44, 45]. The biomass can be roughly divided
into three categories to obtain hard carbon: (1) microbial
biomass, such as bacterial cellulose [46]; (2) animal biomass,
such as waste shrimp skin [47] and cuttlebones [48]; (3) plant
biomass, such as lotus petioles [39], ramie fibers [49],
switchgrass [50] and peanut shell [51]. The microbial bio-
mass needs to be cultured artificially, resulting in a long
process cycle and complicated process. And similarly, the
animal biomass is prone to metamorphism and long-term
preservation. Therefore, the microbial biomass and animal
biomass are not good candidates for commercial production
of hard carbon. The plant biomass has a wide range of
sources and is relatively easy to obtain and store. Therefore,
plant-derived carbon materials have been widely studied.
In this review, we systematically summarize the recent
progress in the development of plant-derived hard carbon
materials for SIBs. The microstructure and electrochemical
performance of hard carbon materials prepared from dif-
ferent parts of plants are mainly discussed. In addition, the
applicated problems of plant-derived hard carbon for SIBs
are provided. The opportunities and challenges in future are
also predicted. We aim to present a full scope of the plant-
derived hard carbon anode materials for SIBs.
2 Preparation of plant-derived hard carbon materials
Pyrolysis is the main method to prepare hard carbon
materials derived from plants. Firstly, it is crucial to select
Rare Met. (2020) 39(9):1019–1033
Recent progress in plant-derived hard carbon anode materials
the plant precursors, which must follow some principles.
The plant precursors should be easy to collect and store.
The corn cob [52], rice husk [53], old loofah [54] and
kelp [55] are favorable precursors for plant-derived hard
carbon materials. Secondly, the selected plant precursors
should have high carbon content and low ash content. The
main components of plants are lignin, cellulose, hemi-
cellulose and other substances with high carbon content.
The average carbon content of plant precursors can be up
to 30% [56, 57]. Thirdly, the selected plant precursors
should have porous or multilayered microstructure. The
plant-derived hard carbon materials can inherit the natural
microstructure of the precursor, which affects electro-
chemical performances of the resulting materials. For
instance, a large number of natural pores and channels of
apricot shells serve as the transport channel for water and
nutrients. The microstructure could be well connected and
inherited after carbonization [58]. The shaddock peel has
a white sponge-like layer, which has a rich porous
structure and closely arranged pores. It can play a good
channel for the organic macromolecules to enter the
interior, which is conducive to the formation of adsorp-
tion storage space [59]. The complex and diverse
microstructure of plants can provide more sodium storage
sites, but also bring some disadvantages to the final
materials, such as high initial irreversible capacity and
low initial Coulomb efficiency induced by the high
specific surface area. In general, the choice of plant pre-
cursors affects the sodium storage properties of the
resulting plant-derived hard carbon materials.
Secondly, temperature is also an important factor of
pyrolysis to obtain hard carbon. A temperature of
1000 °C or higher temperature is usually needed. Gen-
erally, the appearance of hard carbon would not change,
but the spacing of carbon–carbon layers would vary
along with pyrolysis temperature change, thereby as-
prepared hard carbon shows different sodium ions stor-
age performance. Table 2 [50, 52, 56–58, 60–80] lists
preparation, microstructure and performances of plant-
derived hard carbon materials studied in recent years. It
is worth mentioning that the hard carbon materials are
synthesized from a variety of plant precursors, and the
corresponding pyrolysis temperatures are different. More
importantly, the hard carbon materials synthesized from
different plant precursors exhibit different microstruc-
tures after carbonization, and there are also large dif-
ferences about sodium storage properties, which will be
discussed in detail next. Certainly, the properties of some
plant-derived hard carbon materials need to be improved.
In particular, various efforts have been attempted, such
as adjusting the surface area, the interlayer spacing, the
number of defects and the pore size of the hard carbon
materials [81, 82].
Rare Met. (2020) 39(9):1019–1033
1021
3 Structure of plant-derived hard carbon materials
As described above, researchers would like to maintain the
natural microstructure of plants after pyrolysis to obtain
high-performance hard carbon materials. Understandably,
the useful parts of a plant are the transport tissues and
nutrition tissues. The transport tissues include roots, stems
and leaves, whose function is to transport water, inorganic
salts and nutrients for the plants. The typical feature is that
the cells are elongated and often connected up and down to
form a conduit suitable for transport. The nutrition tissues
include flowers, fruits and seeds, which often have thin cell
walls, and large vacuoles for storing nutrients.
Owing to many channels and pores inherited from the
transport tissues of plants, hard carbon materials usually
exhibit excellent diffusion kinetics of sodium ions as anode
materials. Among the transport tissues of plants, the studies
on hard carbon derived from stems and leaves are widely
conducted because stem and leaf resources are easier to
collect than root resources. Stem, as an important sup-
porting organ and transport organ of plants, mainly consists
of high carbon material, namely lignin, cellulose and
hemicellulose. Figure 2 shows scanning electron micro-
scopy (SEM) images of hard carbon materials derived from
the stems of different plants [50, 65, 66, 73]. It could be
observed that the original microstructure of the stems is
retained after pyrolysis, which is mostly tubular porous
structure. The Brunauer–Emmett–Teller (BET) surface
area was usually provided as representative of the elec-
trochemical active surface area. The poplar hard carbon
was evaluated to be about 5.8 m2g-1, delivering a high
specific capacity of 330 mAhg-1 and an initial Coulombic
efficiency of 88.3% in half cells [73]. The dandelion hard
carbon has a specific surface area of 4.692 m2g-1. It
performs a capacity of 250 mAhg-1 as the current density
increases from 0.05 to 0.20 Ag-1. Even up to 5 Ag-1, it
still performs 94 mAhg-1 [65]. The lotus stem carbons
show a high specific surface area of 24.37 m2g-1 and
deliver the best rate capability delivering namely reversible
capacities of 351, 290, 240 and 150 mAhg-1 at 40, 100,
200 and 500 mAg-1, respectively [66]. Switchgrass hard
carbon has a specific surface area of 23.1 m2g-1 and
shows less capacity decay of 160, 130, 120 and
110 mAhg-1 with an increasing current density of 0.2, 0.5,
1.0 and 5.0 Ag-1, respectively [50]. In summary, the hard
carbon produced by pyrolysis of the transport tissues has a
relatively small specific surface area and good rate
performance.
Figure 3 shows SEM images of hard carbon materials
derived from nutrient tissues of different plants after car-
bonization. Three-dimensional porous structure and mul-
tilayer structure could be observed, which can provide
excellent channels for sodium ions diffusion. Zhang et al.
123
1022 P. Yu et al.

Table 2 Preparation, microstructure and performances of plant-derived hard carbon materials in recent years
Plant Pyrolysis Structure Specific surface Electrochemical ICE/ D?Na/ Year and
temperature/°C area/(m2g-1) performance/(mAhg-1) % (cm2s-1) references

Banana peel 1100 Loose porous structure 19.300 318.0 (50 mAg-1) 70.00 – 2014 [60]
-1
Shaddock 1200 Honeycomb-like 82.800 430.5 (30 mAg ) 67.70 – 2015 [61]
peel morphology
Switchgrass 2050 Hollow 3D structure of 23.100 225.0 (50 mAg-1) 64.00 – 2016 [50]
large holes
Maple leaf 1000 Nanosheets overlapped 161.000 320.0 (20 mAg-1) 74.80 – 2016 [62]
Corn cob 1300 Irregular granular 4.320 298.0 (30 mAg-1) 86.00 – 2016 [52]
morphology
Hard wood 1000 Highly nanoporous – 270.0 (10 mAg-1) 70.00 – 2016 [63]
block structure
Cotton 1300 Linear fiber shape and 38.000 305.0 (30 mAg-1) 83.00 1 9 10-9 2016 [64]
hollow structure
Dandelion 1200 Smooth hollow tube 4.6920 266.6 (50 mAg-1) 59.40 – 2017 [65]
Lotus stem 1400 Parallel channel array 24.370 250.0 (100 mAg-1) 70.00 – 2017 [66]
structure
Cherry 1000 Uniform honeycomb 1.860 300.2 (20 mAg-1) 67.30 – 2017 [67]
petals structure
Rice husk 1300 Light layered structure 0.270 372.0 (25 mAg-1) 66.00 1 9 10-11 2017 [56]
-1
Argan shell 1200 Sawtooth wall structure 23.000 225.0 (25 mAg ) 83.90 – 2017 [68]
Pinecone 1400 Irregular-shaped 40.000 334.0 (30 mAg-1) 84.50 – 2017 [69]
secondary particles
Macadamia 1400 Irregular layered 32.400 314.0 (30 mAg-1) 91.40 – 2017 [70]
shell structure
Apricot 1300 Well-connected 13.400 400.0 (25 mAg-1) 79.00 2.09 9 10-11 2018 [58]
shell structure
Maple tree 1400 Ordered porous – 332.0 (30 mAg-1) 88.30 – 2018 [71]
structure
Reed straw 1300 Graphite-like 36.200 283.0 (100 mAg-1) 77.03 1 9 10-9 2018 [72]
nanocrystals
Poplar 1400 A honeycomb-like 5.800 330.0 (30 mAg-1) 88.30 – 2018 [73]
wood morphology
Date palm 1400 Smooth porous surface 33.300 300.0 (25 mAg-1) 88.40 – 2018 [74]
Walnut 1300 3D porous 154.000 230.0 (20 mAg-1) 46.00 – 2018 [75]
shell
Pistachio 1000 Lots of curly clusters 137.070 317.0 (30 mAg-1) 62.10 – 2018 [76]
shells
Water 1000 Tight plate structure 9.580 313.9 (100 mAg-1) 84.30 1 9 10-9 2019 [57]
caltrop
shell
Sugarcane 950 A flake-like structure 3.000 290.0 (30 mAg-1) 70.00 1 9 10-11 2019 [77]
bagasse
Lotus 1200 Obvious micro- 140.700 328.8 (50 mAg-1) 50.40 – 2019 [78]
seedpods channels and pores
Oatmeal 1200 Irregular ‘‘stone forest’’ 69.841 272.4 (20 mAg-1) 46.64 1 9 10-14– 2019 [79]
structure 1 9 10-16
Waste tea 1000 Carbon sphere 521.000 190.0 (100 mAg-1) 61.40 – 2019 [80]
bag structures

prepared pine pollen-derived hard carbon with a specific 203.7 mAhg-1 at 0.1 Ag-1 after 200 cycles, and it also
surface area of 171.54 m2g-1. When it was applied as exhibits outstanding rate performance at 5 Ag-1 with
anode material for SIBs, the discharge capacity maintains reversible capacity of 87 mAhg-1 [83]. The residual hard

123 Rare Met. (2020) 39(9):1019–1033

Recent progress in plant-derived hard carbon anode materials
Fig. 2 SEM images of hard carbon materials derived from stems of
different plants: a poplar wood [73] Copyright Elsevier Ltd. All rights
reserved; b dandelion [65] Copyright Elsevier Ltd. All rights
reserved; c lotus stem [66] Copyright Elsevier Ltd. All rights
reserved; and d switchgrass [50] Copyright Elsevier Ltd. All rights
reserved
Fig. 3 SEM images of hard carbon materials derived from nutrient
tissues of different plants: a pine pollen [83] Copyright ACS
Publications. All rights reserved; b ganoderma lucidum residue [42]
Copyright ACS Publications. All rights reserved; c lychee seeds [84]
Copyright Elsevier Ltd. All rights reserved; and d apricot shell [58]
Copyright Elsevier Ltd. All rights reserved
carbon of ganoderma lucidum inherits the open channel
formed by the porous fungus, which provides a fast
transport channel for sodium ions. The sample shows a
high surface area of 339 m2g-1 and enables a capability of
124 mAhg-1 at 5 Ag-1 [42]. The specific surface area of
lychee seeds is 6.61 m2g-1 [84], while the specific surface
area of apricot shell is 46.1 m2g-1 [58]. It could be con-
cluded that the specific surface area of vegetative tissue-
derived hard carbon is generally larger than that from
transport tissue.
Additionally, it is worth noting that the three-dimen-
sional porous structure of plant-derived hard carbon
Rare Met. (2020) 39(9):1019–1033
1023
materials by pyrolysis has good stability. Figure 4 shows
SEM and transmission electron microscopy (TEM) images
of the hard carbon material derived from rice husk pyrol-
ysis at 1300 °C. The results show that the overall structure
of the hard carbon materials has no obvious change before
and after charging and discharging. In addition, the surface
of the electrode coated with the hard carbon material
derived from rice husk pyrolysis at 1300 °C has a relatively
uniform SEI film with the thickness of approximately
85 nm, which is thinner than the electrodes coated with the
hard carbon materials pyrolysis at 1100 and 1500 °C [56].
As already listed in Sect. 2, hard carbon materials were
pyrolyzed from different plants at different optimal tem-
peratures. Previous research indicates that pyrolysis tem-
perature has a great influence on the structure of plant-
derived hard carbon materials, such as pore size, specific
surface area and degree of graphitization, which further
affect electrochemical performances of the hard carbon
anode materials for SIBs. Figure 5 shows the relationship
between carbonization temperature and the structural
properties of the hard carbon materials derived from dif-
ferent plant precursors listed in Table 2. It can be con-
cluded that the interlayer spacing decreases with the
increase in carbonization temperature for all precursors. In
a large number of literatures, it is reported that the inter-
layer spacing of the prepared hard carbon materials is
mostly greater than 0.37 nm, which just fulfills the mini-
mum size of interlayer spacing for sodium ions intercala-
tion [85–87]. Figure 5b shows the relationship between the
interlayer spacing and the highest reversible specific
capacity of the plant-derived hard carbon materials as
anode materials for SIBs. It is found that the electro-
chemical performances of the prepared materials are
improved with the increase in the interlayer spacing.
Fig. 4 a SEM image and b TEM image of fresh electrode coated
with hard carbon material derived from rice husk pyrolysis at
1300 °C; c SEM image and d TEM image of electrode after 100
cycles [56] Copyright Elsevier Ltd. All rights reserved
123
1024 P. Yu et al.

Fig. 5 Microstructure and capacity of different plant-derived hard carbon: a plots of d002 along with carbonization temperature; b plots of
highest reversible specific capacity versus d002; c plots of specific surface carbonization along with carbonization temperature; d plots of initial
Coulombic efficiency versus specific surface area

However, when the interlayer spacing is greater than
0.40 nm, the highest reversible specific capacity decreases
[88]. The effect of carbonization temperature on the
specific surface area of the plant-derived hard carbon
materials and the effect of specific surface area on the
initial Coulombic efficiency are plotted in Fig. 5c, d. It has
to be noted that the specific surface area of the prepared
materials decreases with the increase in carbonization
temperature, and the initial Coulombic efficiency of the
prepared materials increases when the specific surface area
decreases. It is mainly related to the decrease in the surface
porosity and the formation of the solid electrolyte interface
(SEI) layer [89]. Therefore, it is necessary to reduce the
specific surface area of hard carbon. Then electrolyte
decomposition and consumption on the surface would be
reduced to improve the initial Coulomb efficiency of SIBs.
Zhang et al. [50] prepared hard carbon material with a
hollow three-dimensional structure by tube furnace pyrol-
ysis and Joule heating. The switchgrass-derived hard car-
bon material exhibited an interlayer spacing of 0.376 nm
by pre-carbonizing at 1000 °C and Joule heating treatment
at 2050 °C. It was proved to be able to improve the initial
Coulombic efficiency (from 42% to 64%) and the
reversibility of electrode reaction. Zheng et al. [73]

123 Rare Met. (2020) 39(9):1019–1033

Recent progress in plant-derived hard carbon anode materials
reported a poplar wood-derived hard carbon material,
which is a ‘‘honeycomb-like’’ morphology with a hole,
exhibiting the high specific capacity of 330 mAhg-1 and
the initial Coulombic efficiency of 88.3% in half cells. In
summary, hard carbon with excellent electrochemical
performance could be achieved by adjusting the pyrolysis
temperature to tailor the microstructure of electrode
materials.
4 Electrochemical performances of plant-derived hard
carbon materials
Figure 6 shows the electrochemical performances of hard
carbon derived from different plants. The hard carbon
materials derived from the transport tissues (reed straw and
dandelion) and the nutrient tissues (apricot shell and water
caltrop shell) of plants by pyrolysis at 1300 °C exhibit
excellent rate performance (Fig. 6a) [57, 58, 65, 72]. These
materials deliver a specific capacity of about 350 mAhg-1
at the current density of 0.05 Ag-1 and a specific capacity
of about 100 mAhg-1 at the current density of 1.00 Ag-1.
As can be seen from Fig. 6b [57, 60, 65, 66, 72, 74], the
ratio of platform capacity to the total capacity increases
when the pyrolysis temperature increases except the dan-
delion-derived and reed straw-derived materials. However,
the interlayer spacing of the hard carbon material would
decrease when the pyrolysis temperature was too high, as
shown in Fig. 5a. It is difficult for sodium ions insertion
and deinsertion, which would lead to poor electrochemical
performance. Figure 6c shows voltage platform of sodium
storage for the hard carbon materials obtained from dif-
ferent plants by direct pyrolysis
[42, 50, 52, 56–58, 61, 64–66, 69–72, 74–78]. It should be
an assurance for high working voltage of SIBs that most of
hard carbon shows a platform voltage of about 0.1 V
during the charge and discharge process.
Fig. 6 a Rate performance of hard carbon derived from transport tissues (reed straw and dandelion) and nutrient tissues (apricot shell and water
caltrop shell); b ratio of platform capacity to total capacity for hard carbon; c voltage platform of sodium storage for hard carbon
Rare Met. (2020) 39(9):1019–1033
1025
Cyclic voltammetry (CV) test is commonly used to
characterize the electrochemical performances of the plant-
derived hard carbon materials. Most of the results show
that a pair of sharp oxidation and reduction peaks appear
around 0.1 V, representing the insertion and deinsertion of
sodium ions during the charge and discharge process. In the
initial cycle, all of the hard carbon anode materials showed
a loss of irreversible capacity derived from the formation of
SEI layer, mainly related to electrolyte decomposition on
the electrode surface. As the carbonization temperature
increases, the irreversible capacity decreases. It indicates
that the electrolyte is less decomposed and the initial
Coulombic efficiency is higher, which is consistent with
the lower specific surface area [90]. In addition, the con-
tribution of redox tantalum capacitor to sodium storage
performance was analyzed by CV test, separation of
capacitance and diffusion control capacitance. Analysis of
the relationship between scan rate and peak current in CV
test [91]:
i ¼ amb ð1Þ
where i is the peak current, v is the voltage sweep rate,
a and b are constants associated with the reaction mecha-
nism. In particular, the b value of 0.5 means that the current
is controlled by semi-infinite linear diffusion. The prepared
SIBs are the behavior of battery, and the main mechanism
is intercalation. The b value of 1.0 indicates that the current
is controlled by the surface, and the battery is mainly
capacitive behavior and adsorption. The area enclosed by
the CV curve represents the total amount of stored charge
produced by the Faraday and illegal pull reaction pro-
cesses. a and b are constants related to the reaction
mechanism. For example, the cherry petals-derived hard
carbon material was fitted with a CV curve and a peak
current at different scan rates, and the resulting b value was
0.484, which indicates that the sample has been controlled
by semi-infinite linear diffusion in the low voltage region
123
1026
as anode material for SIBs [67]. Yang et al. [92] reported
that the pristine plant-derived carbon materials exhibited
all battery behavior, but the hard carbon materials modified
by heteroatom doping or activators exhibited completely
different CV curves. For the cotton-derived hard carbon
material modified by nitrogen and sulfur doping, the ratio
of capacitance can reach 57.7%. At a sweep speed of
10 mV, the ratio of capacitance is 96.9%. The sodium
storage behavior is mainly capacitive behavior.
Electrochemical impedance spectroscopy (EIS) mea-
surement was used to study the kinetics of electrochemical
reaction. Similarly, galvanostatic intermittent titration
technique (GITT) was used to detect the sodium ion dif-
fusion coefficient. According to Fick’s second law [93, 94],
the formula is as follows:
    which can be used for the adjustment of sodium ion
4 mB V m 2 DES
DNaþ ¼ pffiffiffi ð2Þ
p MB S sðdEs =d sÞ
where mB is the weight of hard carbon materials coated on
the current collector, Vm represents the molar volume of
carbon, MB represents the molecular mass of carbon, S
represents the area of the active materials on a single pole
piece, s represents the pulse time, Es represents the voltage
at the pulse time, DES represents the voltage difference at
the time when the voltage reaches the steady state in a
single GITT process, and DNaþ is expressed in logarithmic
form. Through the GITT test, the general sodium ion dif-
fusion coefficient of the current hard carbon materials used
as anode materials for SIBs is 1 9 10-9–1 9 10-10 cm2s
-1
. When the voltage is above than 0.1 V, the diffusion
coefficient is 1 9 10-9 cm2s-1. When the voltage is lower
than 0.1 V, DNaþ drops sharply and is approximately
1 9 10-10 cm2s -1, indicating that the diffusion of
sodium ions has changed, and the storage mechanism has
also changed [57, 79]. The difference in the coefficient of
diffusion coefficient between the slope zone and the pla-
teau indicates that the sodium-carbon interaction has dif-
ferent binding energies. In combination with the previous
reports about lithium ion diffusion in graphite, the curves
are very similar, indicating that in the low pressure range of
less than 0.1 V, graphite carbon combines with sodium
ions to form Na–graphite intercalation compounds(Na–
GICs), which is a reversible structural phase transition
[95, 96]. The sharp change in DNaþ may be due to a large
amount of sodium ions leave the surface at the beginning of
charge process, the DNaþ increased rapidly. With the
reaction proceeding, the sodium ions on the surface became
less and less, so the sodium ions embedded in the inter-
granular graphite crystallites began to detach and the DNaþ
decreased. However, Hu et al. found that DNaþ dropped
sharply in the platform area through GITT, but they did not
think that sodium ions were embedded in graphite
123
P. Yu et al.
crystallites [64]. It was founded that the interlayer spacing
did not increase after sodium insertion, measured by TEM
and X-ray photoelectron spectroscopy (XPS). The edge of
carbon layer and the nanopore have changed, and there is
no high change in binding energy at 0.1 V. Combined with
above analysis, they concluded that the mechanism of
sodium storage is that sodium ions filled into the holes.
5 Sodium storage mechanism of plant hard carbon
Hard carbon is non-graphitizable and presents a disordered
structure that is much more complex than the long-range
ordered layer structure of graphite. The special structure
causes hard carbon to have more types of storage sites,
reversible capacity. Unlike graphite, the sodium storage
mechanism of hard carbon is still elusive and controversial.
The hard carbon shows a charge–discharge curve different
from the other carbon-based materials, which is mainly
divided into a low potential plateau region of 0.01–0.10 V
and a high potential ramp zone above 0.1 V. It is crucial to
define the sodium storage mechanism of hard carbon for
the development of high-performance hard carbon
materials.
Until now, there are mainly the following sodium stor-
age mechanisms of hard carbon: (1) deintercalation
between graphite layers, (2) storage of defective layers, (3)
surface adsorption and (4) nanopore filling. However, there
are still a lot of controversies about the way of sodium
storage in the platform and slope zone (Fig. 7). (i) Dahn
et al. first proposed the ‘‘insertion-filling’’ mechanism
when studying the sodium storage mechanism of glucose-
derived hard carbon [97]. The slope region is designated as
sodium ions embedded in the graphite layer, and the plat-
form region is filled with sodium ions and electroplated
into the nanovoids. Komaba et al. reported that the hard
carbon material carbonized from argan shell exhibited a
reversible specific capacity of 330 mAhg-1. Through
X-ray diffraction (XRD) and pore size distribution analy-
sis, it was proved that the parallel relationship between the
slope and the graphene layer spacing (d002) with the pore
size increasing, the platform capacity increases linearly.
The mechanism of sodium storage in hard carbon was
described as two steps, one is the slope region (0.15–1.20
V) when the reduction reaction of sodium ions insertion in
graphene layers, and the other region (0–0.15 V) due to
sodium ions insertion in micropores [68]. (ii) Cao et al.
[98, 99] proposed the ‘‘adsorption–insertion’’ mechanism,
that is, the low potential region corresponds to the dein-
tercalation behavior of sodium ions in the graphite layers,
while the high potential slope region corresponds to the
adsorption behavior of sodium ions on the surface of hard
Rare Met. (2020) 39(9):1019–1033
Recent progress in plant-derived hard carbon anode materials
Fig. 7 Schematic diagrams of sodium storage mechanisms for hard carbon materials: a ‘‘intercalation–adsorption’’ mechanism; b ‘‘adsorption–
insertion’’ mechanism [99] Copyright Wiley-VCH. All rights reserved; and c ‘‘adsorption-filling’’ mechanism [100] Copyright Wiley-VCH. All
rights reserved
carbon. The sodium storage mechanism of most plant-
derived carbon materials conforms to ‘‘adsorption–inser-
tion’’ mechanism. The sodium storage mechanism of the
hard carbon materials obtained from banana peel [60],
water chestnut shell [57], cherry petals [67] and reed straw
[72] was explained as: the platform region for sodium ions
embedded in the graphite layer was below 0.1 V, and the
slope region for sodium ions adsorbed in micropores,
defects or holes was higher than 0.1 V. The capacity in the
slope region is mainly attributed to the micropores and
defect sites inside the material, and the capacity in the
platform region is closely related to the size of the gra-
phite-like nanocrystals. When the pyrolysis temperature
increases, the capacity in the platform region that plays an
important role in the total capacity increases significantly.
Zhang et al. [66] deepened the understanding of the sodium
storage mechanism of lotus stems-derived hard carbon. In
the platform region, sodium ions were not only inserted in
the graphite layer, but also deposited in the micropores. At
the end of the platform at about 0.01 V, sodium ions were
filled into the layered nanocrystallites. The rice husk-
derived hard carbon has the same sodium storage mecha-
nism. As the carbonization temperature increases, the ini-
tial discharge capacity in the slope region decreases
gradually, indicating that the slope region is related to the
oxygen-deficient defect for hard carbon [56]. Xu et al. used
ginkgo leaves as the precursor, a series of hard carbon
materials with different microstructures were prepared by
regulating the pyrolysis temperature in a wide temperature
range of 600–2500 °C, presenting an improved ‘‘adsorp-
tion–insertion’’ mechanism [88]. When the layer spacing is
greater than 0.4 nm, sodium ions can enter freely in it,
showing the behavior of ‘‘quasi-adsorption’’ of sodium
storage, similar to the traditional ‘‘hole, edge, heteroatom’’
and other defects, which is reflected in the oblique area on
the charge–discharge curve. The layer spacing is between
0.36 and 0.40 nm, suitable for the insertion/ejection of
sodium ions. It is the ‘‘interlayer insert’’ sodium storage
Rare Met. (2020) 39(9):1019–1033
1027
mechanism, which is reflected in the platform area on the
charge and discharge curve. When the layer spacing is less
than 0.36 nm, sodium ions cannot enter due to the too
small layer spacing, so there is no platform area and only a
small amount of defective adsorption and storage of
sodium. The improved ‘‘adsorption–insertion’’ model can
well explain the evolution process of hard carbon
microstructure and sodium storage behavior with pyrolysis
temperature. (iii) Tarascon et al. reported that the platform
at the low voltage was due to neither sodium ions insertion
or sodium ions adsorption, and the ‘‘adsorption-filling’’
mechanism was proposed. The slope region between 0.1
and 1.0 V was related to the adsorption of defects by hetero
atoms, which was caused by the adsorption of sodium ions
on the surface of graphene sheet. The plateau region
around 0.1 V was attributed to ‘‘nanohole filling’’ [100]. Li
et al. [64] prepared the hard carbon microtube materials
from the natural cotton precursors and explored the sodium
storage mechanism. The adsorption of sodium ions in the
disordered layer corresponds to the slope region at the high
potential above 0.12 V in the charge–discharge curve,
while the filling of nanopore by sodium ions corresponds to
the plateau region at the low potential closed to 0 V.
6 Modification of plant-derived hard carbon materials
To meet the high performances, such as high reversible
capacity, high initial Coulombic efficiency and long cycle
life for the practically applications of SIBs, it is essential to
modify the current plant-derived hard carbon materials.
The pristine materials typically have a porous or multi-
layered structure of more functional groups and active
sites, which may be destroyed when the carbonization
temperature is too high. However, synthesis of hard carbon
must occur at relatively high temperature. Therefore, var-
ious modification methods have been attempted to improve
the electrochemical performance or reduce the
123
1028
carbonization temperature of the plant-derived hard carbon
materials, including heteroatom doping and activator
modification.
It is reported that the relatively common and effective
modification method is heteroatom doping, which can
increase the content of organic functional groups, defects
on the surface and the carbon layer spacing of the pristine
hard carbon materials. These conditions can change the
local electronic environment around the carbon atom and
the electron distribution on the surface of the hard carbon
material, thereby increasing reactivity and electronic con-
ductivity [101]. It further affects electrode storage capacity,
surface wettability, electrode/electrolyte interaction and
charge transfer [102]. The common heteroatoms used in
hard carbon doping are mainly N [103], S [92], P
[104, 105], etc. The doped heteroatoms may be single or
multiple. The pyrolysis temperature of heteroatomic dop-
ing is obviously lower than that of the hard carbon prepared
without doping, which is generally below 900 °C, it can
reduce energy consumption.
Gaddam et al. [106] used ethylenediamine to dilute
mango dry powder with nitrogen to prepare hard carbon
materials. The cell fabricated with nitrogen-doped hard
carbon as anode material exhibited excellent capacity and
cycling stability. The reversible specific capacity was about
520 mAhg-1 at the current density of 20 mAg-1 along
with a high rate performance. Zhao et al. investigated the
potential of hierarchical nitrogen-doped porous hard car-
bon derived from jackfruit rags through a facile pyrolysis
without any chemical or physical activation as anode
material for SIBs [107].
Compared with N, S has larger size and less elec-
tronegativity. Doping S helps to further enlarge the inter-
layer spacing, generate active sites and improve the
electrochemical performance of hard carbon materials.
Zhao et al. [108] prepared the durian shell-pretreated car-
bon with high specific surface area, which was further
employed as carrier and template for the synthesis of
S-doped carbon materials with outstanding sodium storage
performance. In addition, S doping can induce the
enlargement of carbon interlayer spacing, which not only
increases the amount of stored sodium ions but also
accelerates the speed of sodium ions insertion or deinser-
tion. That is, the electrode kinetics was enhanced, which
insures the high initial Coulombic efficiency of 56.02% and
the reversible capacity of 264 mAhg-1 at 0.1 Ag-1 after
200 cycles and 100.2 mAhg-1 at 5 Ag-1 even after 4500
cycles.
Also, many heteroatoms are also present in plants. The
plant-derived hard carbon materials can be modified by
self-doping. For instance, Wu et al. [43] chose naturally
K-rich coconut endocarp as precursor to prepare K-doped
hard carbon material. The results show that K-doping can
123
P. Yu et al.
improve the electrochemical performance of the hard car-
bon material, including a high initial reversible capacity of
314 mAhg-1 and a high capacity retention of 92.1% after
200 cycles. It mainly depended on the effectively increase
in interlayer spacing in carbon layers after K-doping.
On the other hand, some researchers have also studied
the effect of multiple heteroatom co-doping. Qin et al.
[109] used carbon flakes derived from corn stalk and
ammonium dibasic phosphate ((NH4)2HPO4) as precursors
to synthesize N and P co-doped hard carbon by
hydrothermal reaction. The resulting carbon sheet with a
loose sheet-like morphology was obtained. It exhibited the
specific capacity of 277 mAhg-1 at 0.25 C rate after 100
cycles, the specific capacity of 202 mAhg-1 at 1.00 C rate
after 200 cycles (Fig. 8b) and the specific capacity of 105
mAhg-1 even at 5.00 C rate after 2000 cycles, indicating
good cycle stability and superior rate capability (Fig. 8a).
The cotton was pretreated with magnesium nitrate
(Mg(NO3)2) and carbonized at high temperature. Then, the
obtained carbon was mixed with thiourea solution to pre-
pare N and S co-doped hard carbon. C0, C15 and NS-C15
represent samples treated in 0, 15 mmol Mg(NO3)2 solu-
tions and sulfur co-doped C15 sample. NS-C15 had a
specific surface area of 1595 m2g-1 and a layer spacing of
0.415 nm and shows a much higher initial Coulombic
efficiency of 83.5% than the other two samples. As the
current density increases (Fig. 8d), NS-C15 still shows a
better cycling stability than C0 and C15 with a reversible
specific capacity of 324.1 mAhg-1 at 10.0 Ag-1 (Fig. 8c)
[92].
It is reported that the plant-derived hard carbon mate-
rials can also be modified by activators, which may adjust
the pore structure, increase the specific surface area and
defects of the material. KOH is the commonly used
chemical activator. The activation method is mainly to
directly mix KOH with the precursor or to soak the pre-
cursor in solution and then carry out high temperature
pyrolysis in the inert gas. Hydrogen and carbon dioxide
produced during the reaction process of KOH and carbon at
high temperature promote the formation of porous structure
in the resulting materials. Fu et al. [110] employed apple
pomace as precursor to synthesize hard carbon anode
materials via an activation–carbonization method for SIBs.
The material exhibited a promising areal capacity of
1.91 mAhcm-2 (208 mAhg-1) with a high mass loading
after 200 cycles, indicating a good material utilization.
KOH activation method can prepare hard carbon with
excellent sodium storage performance by pyrolysis at
800 °C, not above 1000 °C, which effectively decreases
the pyrolysis temperature and reduces energy consumption.
KOH was used to treat the porous structure of orange peel
[111], peanut shell [112] and pine nut shell [113] to obtain
the hard carbon material with a specific surface area of
Rare Met. (2020) 39(9):1019–1033
Recent progress in plant-derived hard carbon anode materials 1029

Fig. 8 a Long-term cycling performance of N, P-CS (N, P dual doping carbon sheets named as N, P-CS); b cycling performance of N, P-CS
anode for initial 100 cycles at a rate of 0.25 C and following 200 cycles at a rate of 1.00 C [109] Copyright Elsevier Ltd. All rights reserved;
c rate performance of C0, C15 and NS-C15 electrodes; d cycling performance of C0, C15 and NS-C15 at 1.0 Ag-1 [92] Copyright Elsevier Ltd.
All rights reserved

400 m2g-1 or even 1500 m2g-1. The prepared hard car-
bon materials contained a large amount of microporous
structure, which was favorable for electrolyte penetration
and provided a place for sodium storage. H3PO4 is another
common activator, which can not only promote the for-
mation of pore structure, but also form phosphorous
functional groups on the surface of carbon materials. Hong
et al. [104] prepared microporous citron peel-derived hard
carbon material modified by H3PO4 activator. The obtained
material had a three-dimensional porous structure with a
specific surface area of 1272 m2g-1. It was also confirmed
the presence of oxygen and phosphorus functional groups.
Owing to the unique three-dimensional porous structure
and special functional groups, the carbon material exhib-
ited excellent cycle and rate performance. However, the
initial Coulombic efficiency is only 27%, which was
mainly caused by the formation of SEI film and side
reactions with functional groups. Thus, the activator can
promote the porous structure of hard carbon materials,
which is beneficial to the cycle and rate performance, but
can also lead to some adverse factors, such as an increase
in specific surface area and the initial irreversible capacity.
7 Conclusion and prospects
SIBs are an ideal replacement of LIBs as power resources
for low-speed electrical vehicles and grid-scale energy
storage. Like graphite anode for commercial LIBs, hard
carbon is the most promising anode for SIBs. In this
review, we focus on the recent progress in plant-derived
hard carbon as anodes for SIBs. Preparation, microstruc-
ture, electrochemical performances and modification of
plant-derived hard carbon materials have been systemati-
cally summarized.
Pyrolysis is a simple method to prepare plant-derived
hard carbon. The natural compact porous morphology of
plant precursors could be maintained in hard carbon during
pyrolysis. At the same time, the layer spacing of carbon–
carbon could be tailored to an optimal value of
0.38–0.40 nm by adjusting pyrolysis temperature. This
unique microstructure of hard carbon would shorten dif-
fusion path of Na? and benefit the extraction and insertion
of Na?. Porous microstructure could provide more storage
sites to enhance capacity for hard carbon as sodium ion
anodes. Nevertheless, low ICE would be induced by elec-
trolyte decomposition on large specific surface area of

Rare Met. (2020) 39(9):1019–1033 123

1030
porous structure. Hence, an excellent anode of plant-
derived hard carbon could be prepared via accurate selec-
tion of plant precursors and suitable pyrolysis process
setting. Besides, heteroatoms doping or activators modifi-
cation of hard carbon could remarkably improve its specific
capacity and high C rate performance. But it also would
increase defect voids, resulting in large specific surface
area and low ICE. Therefore, the amount of heteroatoms or
activators added should be controlled to balance electro-
chemical properties. It is expected that this review would
provide in-depth understanding and guideline for the
design of high-performance hard carbon anode materials
from plant resources at low cost. Finally, the comprehen-
sive utilization of high value-added waste resources will be
realized.
Acknowledgements This study was financially supported by the Key
Research and Development Project of Hunan Education Department
(No. 18A114), the Joint Natural Science Project of Hunan-Changde
(No. 2018JJ4001), the Youth Fund of Hunan Agricultural University
(No. 18QN01) and the Funding for the Major Scientific Research and
Innovation Team Cultivation at Hunan Agricultural University (No.
2018).
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5(46):24353. School of Chemistry and Mate-
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toward high performance sodium-ion batteries anode. Carbon. interests focus on energy mate-
2018;130:664. rials, including Li-ion batteries,
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