Hydrometallurgy 201 (2021) 105553

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Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

A review of hydrometallurgy techniques for the removal of impurities from

metallurgical-grade silicon
Fengshuo Xi a, b, Shaoyuan Li a, c, *, Wenhui Ma a, *, Zhengjie Chen a, Kuixian Wei a, Jijun Wu a
a
Faculty of Metallurgical and Energy Engineering/State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and
Technology, Kunming 650093, China
b
School of Chemical Engineering/Australian Institute for Bioengineering and Nanotechnology, The University of Queensland, Brisbane 4072, Australia
c
Australian Centre for Advanced Photovoltaics/School of Photovoltaic and Renewable Energy Engineering, University of New South Wales, Sydney 2052, Australia

A R T I C L E I N F O A B S T R A C T

Keywords: Hydrometallurgy is considered a promising method to produce solar-grade silicon (SOG-Si) from metallurgical-
Hydrometallurgy grade silicon (MG-Si) due to its advantages of low cost, simple operation, and easy control. Researchers have
Metallurgical-grade silicon investigated different hydrometallurgy techniques for impurity removal from MG-Si. This study systematically
Acid leaching purification
reviews hydrometallurgy techniques for the removal of impurities from MG-Si and provides perspectives in this
Impurity removal efficiency
Solar-grade silicon
field. Traditional leaching techniques, including single-acid leaching, successive acid leaching, and mixed acid
leaching, are summarized. These methods face challenges for preparing high-purity silicon because of the
insoluble impurities in MG-Si. Intensive methods for improving impurity removal in hydrometallurgical pro­
cesses, including adding oxidizing agents, introducing external fields, and increasing the impurity exposure to
the etchants, are classified and discussed. The combinations of secondary refining processes and hydrometal­
lurgical processes are efficient in removing insoluble impurities from MG-Si. Representative research topics and
the results of these combination methods are classified and summarized. It is expected that this review will help
researchers select appropriate hydrometallurgy techniques for producing low-cost SOG-Si.

1. Introduction energy consumption structure are current worldwide energy develop­

Metallurgical-grade silicon (MG-Si) is required to produce silicon
products, including organosilicon, silicon alloys, monocrystalline sili­
con, and polysilicon (Dosaj et al., 2005; Hsieh et al., 2020; Li et al., 2018;
Xakalashe and Tangstad, 2011). Various products based on these silicon
materials are produced, creating the MG-Si industrial chain (Fig. 1). The
commercial production of MG-Si primarily uses the reduction of silicon
oxide (silica) with carbon materials in submerged arc furnaces, resulting
in impurities in the MG-Si products (Takla et al., 2013; Børset et al.,
2015). The quality of MG-Si is critical in the silicon industry with respect
to the levels of impurities. Generally, the applications of MG-Si for the
organosilicon and silicon alloy markets are not as stringent, and purity
of only >98.5% has to be met (Gordon et al., 2009; Bablin et al., 2003).
However, the monocrystalline silicon and polysilicon products require
higher purity as raw materials for the silicon solar photovoltaic (PV)
industry (Braga et al., 2008).
The development of renewable energy and its increased share in the
ment trends. The advanced silicon technology has significantly reduced
solar electricity costs, making large-scale applications of solar renewable
energy possible (Yoshikawa et al., 2017). Therefore, solar PV power is
regarded as the most likely candidate to meet energy demands due to
abundant resources worldwide (Fu et al., 2015). It has been predicted
that solar PV energy will account for more than 50% of the worlds’
electricity consumption by 2050 (IRENA, 2019). It can be expected that
the demand for monocrystalline silicon and polysilicon products will
keep rapidly growing in the future. Nevertheless, the PV conversion
efficiency of silicon solar cells can be reduced by the presence of im­
purities in the silicon. Thus, the impurity content of monocrystalline
silicon or polysilicon for silicon solar cells should meet the requirements
of solar-grade silicon (SOG-Si) (Lei et al., 2019; Ren et al., 2019), as
listed in Table 1 (Chigondo, 2018).
The mainstream technology of SOG-Si production is dominated by
the modified Siemens process (Ni et al., 2014). However, the high en­
ergy consumption, complex chemical reactions, and significant

* Corresponding authors at: Faculty of Metallurgical and Energy Engineering/State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization,
Kunming University of Science and Technology, Kunming 650093, China.
E-mail addresses: lsy415808550@163.com (S. Li), mwhsilicon@126.com (W. Ma).

https://doi.org/10.1016/j.hydromet.2021.105553
Received 30 July 2020; Received in revised form 25 November 2020; Accepted 10 January 2021
Available online 12 January 2021
0304-386X/© 2021 Published by Elsevier B.V.
F. Xi et al. Hydrometallurgy 201 (2021) 105553

Fig. 1. Overview of metallurgical-grade silicon industrial chain.

Table 1
Maximum concentrations of impurities in MG-Si and SOG-Si. (Chigondo, 2018).
Elements Al Fe Ca Mg Mn Cr Ti V Zr Cu B P C O

MG-Si ‰ 2 5 1 0.1 0.05 0.05 1.6 0.01 0.01 0.01 0.08 0.05 0.6 3
SoG-Si ppmw 0.1 0.1 0.3 0.1 0.1 0.1 0.01 0.1 0.1 0.1 0.3 0.1 3 10

environmental pollution. Metallurgical refining treatments usually

Fig. 2. Solar grade silicon production by metallurgical refining process.
environmental pollution of the Siemens processes have limited the
development of the SOG-Si industry (Chen et al., 2018). To overcome
the SOG-Si industry limitations, metallurgical refining processes have
been used to produce SOG-Si due to their low cost and less
consist of several physical refining processes to remove impurities from
MG-Si in an optimized sequence (Morita and Miki, 2003; Chen et al.,
2019), which typically include oxidization refining (Heuer, 2013; Ding
et al., 2012; Chen et al., 2017), hydrometallurgical processes (Hunt
et al., 1976; Dietl, 1983), vacuum refining (Wei et al., 2015), and
directional solidification (Tan et al., 2013; Qian et al., 2020). As shown
in Fig. 2, the nonmetallic elements (C and B) can be volatilized and
removed from the MG-Si during the oxidization refining process. Be­
sides, most of the soluble impurities can be eliminated in the hydro­
metallurgical process. The vacuum refining process is highly effective
for removing the insoluble and volatile impurities (i.e., P, Ca, Al).
Finally, the remaining residual impurities can be removed by directional
solidification. After these processes, the final product (SOG-Si) is

2
F. Xi et al.
Fig. 3. Schematic diagram of MG-Si production process.
obtained. The hydrometallurgical process is the only process that does
not require high temperatures (not higher than 100 ◦ C); thus, this pro­
cess consumes relatively little energy and has a low production cost.
Moreover, the hydrometallurgical process also has the advantages of
simple operation and easy large-scale production. It would be advan­
tageous for the PV industry if the impurities could be completely
removed using the hydrometallurgical process. Therefore, the purifica­
tion of MG-Si by the hydrometallurgical process has attracted significant
attention from many researchers in recent years. This article presents a
review of impurity removal from MG-Si using economical hydrometal­
lurgy techniques applicable to future MG-Si purification research.
2. Properties of the impurities in MG-Si
MG-Si is obtained from silica reduction processes, which require high
temperatures (usually higher than 1800 ◦ C). Thus, the production of
MG-Si has to be performed in a submerged electric arc furnace (SEAF)
system, which is shown in Fig. 3 (Könle, 2002). The carbothermic
reduction reaction of silicon dioxide (Eq. (1)) indicates that the raw
materials for the production of MG-Si include only silica and carbona­
ceous reducing agents (Takla et al., 2013; Børset et al., 2015). Therefore,
the impurities in these two raw materials are the main source of the
impurities in MG-Si. As shown in Table 1, the impurities in MG-Si mainly
include nonmetallic elements (B, P, C, and O) and metallic elements (Fe,
Al, Ca, Ti, Mn, V, Cu, Cr, and others); Fe, Al, and Ca are the dominant
impurities. Thus, according to the content of Fe, Al, and Ca, MG-Si
products are categorized as 553, 421, 3303, 2202, 1101, etc. in the in­
dustry. (Wu et al., 2020)
3
Hydrometallurgy 201 (2021) 105553
SiO2 + C = Si + CO2 (1)
The impurities in MG-Si can also be classified as segregation impu­
rities and insoluble impurities (Ohmi et al., 1992; Vick and Whittle,
1969). The segregated impurities refer to impurities that have small
segregation coefficients; these include metallic elements (e.g., Fe, Al, Ca,
Ti, V, Cu, and Cr) and nonmetallic elements (e.g., C, O). Due to the small
segregation coefficients of these impurities, their concentrations are
much higher than the maximum solid solubility (He et al., 2012). Thus,
co-precipitations are readily formed at the grain boundaries during MG-
Si melting and solidification (Trumbore, 1960). The morphologies and
components of these precipitates have been investigated by many re­
searches, and it was found that the precipitates primarily consisted of Si-
Fe, Si–Fe–Ti, Si–Fe–Al, Si–Fe–Al–Ca, Si–Fe–Al–Ti–V, Si–Ti–V, and
Si–Al–Cu phases (Gaffet et al., 1993; Li et al., 2020; Anglezio et al., 1990;
Franti and Koss, 1977; Anglezio et al., 1994). Due to the existence of
these impurity phases, the grain boundaries are more brittle than those
of the silicon substrate. Therefore, these impurities are easily fractured
and exposed on the surface of the silicon powder when the MG-Si bulk is
pulverized (Sun et al., 2013). Due to the substantially different sensi­
tivities of the exposed impurities and the silicon substrate to acid etch­
ants, the exposed impurities can be removed by suitable acid leaching
processes. However, the insoluble impurities typically have a larger
segregation coefficient than the segregated impurities and primarily
include nonmetallic impurities B and P, which cannot be precipitated at
the grain boundaries (Trumbore, 1960; Tang et al., 2009; Khattak et al.,
2002). Conversely, these impurities replace the silicon atoms and
occupy interstitial positions. For these reasons, the insoluble impurities
F. Xi et al. Hydrometallurgy 201 (2021) 105553

Table 2 cannot be completely exposed during the grinding process. Therefore, it

Investigations for the purification of MG-Si by hydrometallurgical processes. is more difficult to remove insoluble impurities from MG-Si than
Materials (%) Acid etchants Purity of Silicon Ref. segregation impurities.
(%) and Residual
impurities 3. Impurity removal from MG-Si by traditional leaching
(ppmw)
techniques
MG-Si (~99.5), Fe Aqua regia, Si (<99.9), Fe Chu and Chu, 1983
(0.35), Al (0.15) HCl, H2SO4 + (350), Al (320) Generally, the leaching process should target as many elements as
HNO3
MG-Si (~99.0), Fe HCl, HF, H2SO4, Si (<99.98), Al Dietl, 1983
possible to ensure that the MG-Si hydrometallurgical purification
(~0.5), Al HNO3 (20), Ca (4), Fe method is cost-efficient. Additionally, silicon losses should be mini­
(~0.25), Ca (5) mized, and the environmental impact of the leaching treatment should
(~0.27) be as low as possible. Based on these factors, numerous researchers are
MG-Si (~98.0), Fe HCl, HF Si (<99.90), Fe Boulos and
investigating effective silicon purification methods using hydrometal­
(1.0) (95) Universite de
Sherbrooke, 1983 lurgy techniques. The most common acids used in the hydrometallur­
MG-Si (~97.0), Fe HCl, HF + Si (<99.90), Al Halvorsen and gical process to refine MG-Si include H2SO4, HCl, HNO3, HF, CH3COOH,
(3–5), Al (0.3), HNO3 (10), Fe (5) Elkem, 1985 and their mixtures. The purification of MG-Si by these traditional
Ca (0.2) leaching techniques are summarized in Table 2.
MG-Si (98.0), Fe HNO3, HCl, HF Si (<99.99), Al Bildl et al., 1986
(0.56), Al (0.3), (35), Ca (10), Fe
Ca (0.3) (10) 3.1. Single-acid leaching
MG-Si (98.0), Fe Aqua regia, HF Si (<99.95), Al Juneja and
(1.0), Al (0.25), (100), Ca (55), Mukherjee, 1986 H2SO4 is a highly corrosive acid but has been widely used in the
Ca (1.2) Fe (25)
industry. Since it is the most suitable acid for industrial use, H2SO4 has
MG-Si (98.0), Fe HNO3, H2SO4, Si (<99.90), Al Santos et al., 1990
(0.4), Al (0.81), HCl, HF, Aqua (800), Ca (70), been investigated in several studies for the purification of MG-Si.
Ca (0.088) regia Fe (180) However, the study demonstrated that H2SO4 only had a good perfor­
MG-Si (98.0), Fe HCl, H2SO4, Si (<99.98), Fe Lian et al., 1992 mance for reducing the C content but not for other impurities, and the
(0.73), Al HCl + HNO3 (17), Al (56), Ca impurity removal performance of H2SO4 was ~50% (Santos et al.,
(0.61), Ca (0.25) (88.4)
MG-Si (99.0), Fe Acids A, B, C Si (<99.80), Fe Yu et al., 2007
1990). Compared with H2SO4, HNO3 exhibited better performance for
(0.15), Ca (230), Al (140) impurity removal from MG-Si, reaching 55% ~ 75% (Santos et al., 1990;
(0.032), Al Ma et al., 2009). Nevertheless, studies have shown that Fe and Al could
(0.054) not be entirely removed by H2SO4 or HNO3 leaching. It was found that
MG-Si Aqua regia, HF Si (<99.80), Fe Lashgari and
HCl showed good performance for removing Al (Lian et al., 1992). Be­
(96.0–98.0), Fe (2174), Ca Yoozbashizadeh,
(0.315), Ca (20.4), Al (47.6) 2007 sides, the removal of other impurities (especially Ca) from MG-Si can
(0.007), Al also be enhanced. After leaching with HCl, the extraction yield of im­
(0.0.06) purities from MG-Si reached 70% ~ 85% (Dietl, 1983; Santos et al.,
MG-Si (99.0), Fe Aqua regia, HCl Si (<99.90), Fe Lee et al., 2009 1990). According to the sensitivity of different phases of impurities in
(0.06), Al + HF, HNO3 + (262), Al (224)
(0.20), Ca HF Ca (53.6)
HCl solutions, Margarido et al. (1994) determined the sensitivity order
(0.007) of the main impurity phases, which are CaSi, CaSi2, CaAl2Si1.5 > Calsifer
MG-Si (99.0), Al HF, HNO3, HCl Si (<99.90), Fe Ma et al., 2009 > Al–Fe–Si > > FeSi2. The study indicated that the FeSi2 phase was
(0.27), Fe (14.6), Al (461), insoluble in HCl solutions, and the Si–Fe–Ti phase was not sensitive to
(0.23), Ca Ca (3.6)
HCl (Santos et al., 1990). Thus, HCl solutions have poor removal per­
(0.058)
MG-Si (99.0), Fe HF Si (<99.98), Al Lu et al., 2011 formance for Fe impurities (Margarido et al., 1993). In addition, because
(0.43), Al (0.39) (720), Fe (460) SiO2 does not react with H2SO4, HNO3, and HCl, it is difficult to remove
MG-Si (99.0), Fe HF, HCl, HF + Si (<99.90), Fe Luo et al., 2012 impurities that are covered by a SiO2 film (Ebrahimfar and Ahmadian,
(0.234), Al HCl (121), Al (788), 2019). Due to the disadvantages of H2SO4, HNO3, and HCl leaching
(0.271), Ca Ca (99.5)
(0.058)
processes, HF was used to remove impurities from MG-Si and exhibited
MG-Si (98.0), Fe Aqua regia, Si (<99.98), Fe Zeng et al., 2012 an excellent impurity removal performance (>90%) (Lashgari and
(0.62), Al HCl, HF, HCl + (17), Al (2.6), Ca Yoozbashizadeh, 2007; Lee et al., 2009; Ma et al., 2009; Lu et al., 2011;
(0.008), Ca HF (170) Luo et al., 2012). Furthermore, HF has a high chemical reactivity with
(0.96)
SiO2; thus, the hidden impurities can also be removed. Lai et al. (2017)
MG-Si (99.5), Fe HNO3 + HF+ Si (99.99), Fe Kim and Osseo-
(0.127), Al CH3COOH (1.02), Al Asare, 2012 determined the sensitivity sequence of impurities to HF as Si–Al–Fe > >
(0.087) (0.173), Ti (<20) Si–Al–Fe–Ni, Si–V–Ti–(Mn) > Si–Ti–Fe > Si–Fe > > Si–Al–Ni–(Cu).
MG-Si (99.5), Fe Aqua regia Si (<99.90), Fe Zhang et al., 2013 However, it has been demonstrated that the insoluble salt hexa­
(0.142), Al (298.2), Al fluorosilicate (CaSiF6 and Al2(SiF6)3) was generated in MG-Si during the
(0.135), Ca (310.96), Ca
HF leaching process, indicating that the removal of some impurities (e.
(0.001) (55.55), Ti (81.4)
MG-Si (99.3), Fe HCl + HF, Si (<99.93), Fe Lu et al., 2017 g., Fe, Al, and Cu) by HF leaching still has limitations (Lai et al., 2016).
(0.419), Al HCl + HF + (351), Al (375),
(0.123), Ca CH3COOH Ca (33) 3.2. Successive acid leaching and mixed acid leaching
(0.028)
MG-Si (99.3), Fe HCl + HF + Si (<99.92), Fe Tian et al., 2018
(0.419), Al CH3COOH (339), Al (368), The acids H2SO4, HNO3, HCl, and HF have been used for impurity
(0.123), Ca Ca (27) removal from MG-Si, but they have inevitable. Successive acid leaching
(0.028) (Santos et al., 1990; Lian et al., 1992) and mixed acid leaching (Chu and
MG-Si (99.0), Fe HNO3, H2SO4, Si (<99.9), Fe Ebrahimfar and Chu, 1983; Halvorsen and Elkem, 1985; Lee et al., 2009; Luo et al., 2012;
(0.48), Al HCl + HNO3, (280), Al (330), Ahmadian, 2019
(0.386), Ca HCl + HF, HCl Ca (340)
Zeng et al., 2012; Kim and Osseo-Asare, 2012; Zhang et al., 2013; Lu
(0.197) + H2SO4 et al., 2017; Tian et al., 2018; Ebrahimfar and Ahmadian, 2019) were
proposed to combine the advantages of different acids and achieve high
impurity removal from MG-Si by hydrometallurgical processes. For

4
F. Xi et al. Hydrometallurgy 201 (2021) 105553

Table 3 removal from MG-Si; it was found that FeCl3 had a more positive effect
Studies on impurities removal by adding oxidizing agents during the hydro­ on the impurity removal than (NH4)2S2O8 during the leaching progress.
metallurgical process. In the presence of 0.1 M FeCl3, 66% Ca, 92% Cr, 27% Fe, 98% Cu, 98%
Oxidizing Acid leaching Results of main indicators Ref. Ni, and 89% Zn were removed from the MG-Si. Although some
agents treatments improvement in the impurity removal was achieved, the effects of the
(NH4)2S2O8 HCl RF: 40% Cr, 25% Fe, 98% Sahu and oxidizing agents (NH4)2S2O8 and FeCl3 are still limited because some
Cu, 93% Ni, 89% Zn Asselin, 2012 impurity phases (such as Si-Fe and Si–Fe–Ti) are not sensitive to HCl.
FeCl3 HCl RF: 66% Ca, 92% Cr, 27% Sahu and
Fe, 98% Cu, 98% Ni, 89% Asselin, 2012
Zn 4.2. H2O2
H2O2 H2O2; HF; RF: 90.5% Total, 98.8% Fe, Liu et al.,
NH4Cl: NH4F(w 98.0%Al, 80.1% Ca 2012 Liu et al. (2012) investigated the pretreatment of the oxidizing agent
%) = 30:5
H2O2 for enhancing impurity removal from MG-Si. In contrast to con­
H2O2 HF Si purity: 99.99% Lai et al.,
2016, 2017 ventional hydrometallurgical processes, the authors first immersed MG-
H2O2 HF + H2C2O2; Si purity: 99.99% Lai et al., Si into an H2O2 solution, followed by an HF leaching treatment and
HF + CH3COOH 2017 leaching in a mixture solution of NH4Cl-NH4F (NH4Cl:NH4F = 30 W%: 5
AgNO3 HF Si purity: 99.98% Xi et al., W%). The leaching results showed that the successive processes greatly
2018a
AgNO3 + HF Si purity: 99.99% Xi et al.,
facilitated the removal of both metallic and nonmetallic impurities from
H2O2 2018a, 2019a MG-Si. The optimized experimental conditions, i.e., H2O2 leaching for 5
Cu(NO3)2 + HF 6759 ppmw → 193.41 Xi et al., h, 4 M HF leaching for 22 h, and NH4Cl-NH4F mixture solution treatment
H2O2 ppmw 2018b for 5 h, resulted in removal efficiencies of the primary metal impurities
Fe, Al, and Ca of 98.8%, 98.0%, and 80.1%, respectively. It was notable
example, as shown in Table 2, Santos et al. (1990) obtained high-purity that the removal efficiency of the nonmetallic impurity B reached 90.5%
silicon (99.90%) by leaching in two successive steps with HCl and HF. under these experimental conditions.
Yu et al. (2007) obtained silicon with ~99.8% purity by successive Apart from the successive leaching processes, Lai et al. (2016, 2017)
leaching with acids A, B, and C. Although the high performance of studied the addition of H2O2 to HF mixture solutions to purify MG-Si.
successive acid leaching method has been demonstrated, the difficult The microstructural evolution of MG-Si after etching with/without
operation and long leaching time cannot be ignored. Thus, mixed acid H2O2 is shown in Fig. 4(a) and (b). It was found that the addition of H2O2
leaching methods were developed to achieve high-purity silicon. As affected the sensitivity sequence for removing impurities by HF. After
summarized in Table 2, examples of acid mixtures include H2SO4 + leaching with HF + H2O2, the typical impurity phases sensitivity
HNO3, HF + HNO3, aqua regia (HCl + HNO3), HCl + H2SO4, HCl + HF, sequence was changed to Si–Al–Fe > > Si–A–Fe–Ni, Si–V–Ti–(Mn) >
HNO3 + HF + CH3COOH, and HCl + HF + CH3COOH. Studies have Si–Ti–Fe, Si-Fe, Si–Al–Ni–(Cu). With the addition of H2O2, the overall
shown that aqua regia has a chemical cracking effect on MG-Si and can impurity removal efficiency was increased, and that of Cu significantly
be used to break silicon or expose impurities. Furthermore, HCl + HF increased from less than 10% to more than 95%. Under suitable
and their mixtures are widely considered the most effective acid com­ experimental conditions, the purity of MG-Si could be improved from
binations for impurity removal from MG-Si. 99.97% to 99.99%. In addition, the kinetics of the impurity removal
Moreover, the control of the experimental conditions during leach­ from MG-Si using HF + H2O2 also indicated that the leaching process
ing (e.g., the silicon particle size, leaching time, leaching temperature, was under chemical reaction control. The authors also found that the
acid concentration, and leaching agents) can influence the leaching addition of the oxidizing agent H2O2 resulted in the corrosion of the
dynamic conditions of traditional leaching techniques. Thus, many re­ silicon matrix due to the formation of micropores. Fig. 4(c) shows a
searches improved the MG-Si impurity removal performance by devel­ schematic diagram of the formation of porous silicon by a mixture of
oping appropriate experimental conditions for hydrometallurgy H2O2 and HF; the cathode, anode, and overall reactions are described in
techniques. However, due to insoluble impurities in MG-Si, traditional Eqs. (2)–(4) (Nahm et al., 1997; Chartier et al., 2008; Huang et al., 2011;
leaching techniques still face challenges in preparing high-purity silicon. Kolasinski, 2009). Moreover, to improve the removal efficiency of
nonmetallic impurities, Lai et al. (2017) also investigated the effect of
adding H2C2O2 and CH3COOH to mixture solutions of HF and H2O2.
4. Enhancing impurity removal by adding oxidizing agents
However, it is evident in Fig. 4(d) that the extraction efficiencies of the
other impurities and B, P are moderate, except for a slight increase in the
The oxidizing agents in the acid lixiviants can contribute to the
Cu removal fraction. Thus, it can be concluded that H2O2 plays a major
removal of impurities due to their positive valence state translation,
role in purifying MG-Si than H2C2O2 or CH3COOH in the HF + H2O2 +
which accelerates the impurity removal from MG-Si during the hydro­
H2C2O2 + CH3COOH mixture solutions. This result demonstrates the
metallurgical process. Thus, the addition of oxidizing agents during the
positive effect of adding the oxidizing agent H2O2 on improving impu­
hydrometallurgical process is considered an effective approach to
rity removal in hydrometallurgical processes.
enhance impurity removal from MG-Si. Table 3 summarizes studies on
enhancing impurity removal from MG-Si by adding oxidizing agents to Cathode : H2 O2 + 2H + →2H2 O + 2e+ (2)
hydrometallurgical processes.
Anode : Si + 2H2 O + 4e+ →SiO2 + 4H + ; SiO2 + 6HF→H2 SiF 6 + 2H2 O (3)
4.1. (NH4)2S2O8 and FeCl3
The overall reaction : 6HF + Si + 2H2 O2 →4H2 O + H2 SiF 6 (4)
Sahu and Asselin (2012) analyzed the effects of oxidizing agent
(NH4)2S2O8 on the purification of MG-Si during HCl acid leaching pro­ 4.3. AgNO3 and Cu(NO3)2
cesses. It was found that the addition of the oxidizing agent (NH4)2S2O8
had a negligible effect on improving the impurity removal from MG-Si. Xi et al. (2018a, 2019a) found that the oxidizing agent AgNO3 could
After adding 2% (NH4)2S2O8 to the HCl leaching lixiviants, the removal also enhance the removal of impurities from MG-Si during the hydro­
efficiency for removing Cr, Fe, Cu, Ni, and Zn impurities from MG-Si was metallurgical process. As shown in Table 3, after the addition of AgNO3
40%, 25%, 98%, 93%, and 89%, respectively. Furthermore, the authors to HF acid solutions, the purity of MG-Si was significantly increased to
also investigated the effects of the oxidizing agent FeCl3 on the impurity 99.98%. It is observed in Fig. 5(a) that the addition of AgNO3 caused the

5
F. Xi et al.
Fig. 4. Microstructural evolution of MG-Si after etching with (a) HF and (b) HF + H2O2, (c) Schematic illustration of chemical etching of silicon by HF + H2O2
mixture, (d) Effects of various lixiviants on the purification of MG-Si. (Lai et al., 2017).
formation of a porous structure on the silicon surface, thereby increasing
the contact area between the impurities and the acid etchants. In addi­
tion, the authors combined the oxidizing agents AgNO3 and H2O2; thus,
the AgNO3 + H2O2 + HF mixture solutions were used to improve the
impurity removal performance from MG-Si, and silicon with a purity of
99.99% was obtained. Compared with the AgNO3 + HF leaching treat­
ment, the addition of the oxidizing agent H2O2 increased the number
and depth of porous structures (Fig. 5(b)). The porous structures acted as
channels and provided better contact between the impurities and acid
etchants during the leaching process. It should be noted that the AgNO3
+ H2O2 + HF combination also resulted in good performance for the
removal of the nonmetallic impurities B (86.1%) and P (71.3%).
Furthermore, the authors demonstrated that the removal reaction of B
and P was in good agreement with the cracking shrinking kinetic model,
which was controlled by both of interfacial transfer and diffusion
through the product layer process.
Xi et al. (2018b) also investigated the removal of impurities from
large-sized MG-Si powders (150–180 μm) by an HF + H2O2 + Cu(NO3)2
6
Hydrometallurgy 201 (2021) 105553
leaching process, which has the advantage of low production cost of the
oxidizing agent Cu(NO3)2. As shown in Fig. 6(a), the HF + H2O2 + Cu
(NO3)2 leaching process exhibited better impurity removal performance
than HF leaching or HF + H2O2 leaching processes. The total removal
fraction of Fe, Al, Ca, Ti, Ni, V, and Cu increased from 89.31% to 97.14%
when compared to the leaching results without the oxidizing agent, and
the impurity content was significantly reduced from 6759 ppmw to
193.41 ppmw. Moreover, the study results showed that numerous ho­
mogeneous porous structures were formed (as shown in Fig. 6(b)) when
the oxidizing agent Cu(NO3)2 was added because channels were pro­
vided to increase the contact area between the impurities and acid
etchants. Thus, to some extent, the low-cost oxidizing agent Cu(NO3)2
has a significantly higher potential for impurity removal from MG-Si
than AgNO3 during the hydrometallurgical process.
5. Enhancing impurity removal by introducing external fields
The introduction of external fields in the hydrometallurgical process
F. Xi et al. Hydrometallurgy 201 (2021) 105553

Fig. 5. Surface SEM images of leached MG-Si: (a) HF + AgNO3; (b) HF + AgNO3 + H2O2. (Xi et al., 2018a).

Fig. 6. (a) Effects of various lixiviants on the purification of MG-Si and (b) SEM image of purified porous silicon after HF + Cu(NO3)2 + H2O2 treatment. (Xi
et al., 2018b).

is another suitable method to improve the impurity removal perfor­
mance from MG-Si. The external fields primarily include ultraviolet
radiation, an ultrasonic field, and oxygen pressure leaching treatment.
5.1. Ultraviolet radiation treatment
Li et al. (2009) incorporate ultraviolet radiation in the HCl, HF, and
HNO3 leaching processes. Compared to the hydrometallurgical pro­
cesses without ultraviolet radiation treatment, the proportion of the
remaining impurities Fe and Al was reduced by 41% and 16.4% when
the acids HCl and HF were used. In addition, it was found that the use of
the oxidizing acids HNO3 and H2O2 reduced the performance of the
ultraviolet radiation treatment. The authors believed that the increased
performance of impurity removal from MG-Si by the ultraviolet

Fig. 7. Effect of (a) ultrasonic and (b) oxygen pressure leaching on MG-Si particles.

7
F. Xi et al. Hydrometallurgy 201 (2021) 105553

radiation treatment during the hydrometallurgical process was attrib­ Table 4

utable to the oxidation effect. Concentration (ppma) of different elements in MG-Si as received and after
milling and sieving. (Santos et al., 1990).
5.2. Ultrasonic field treatment Elements MG-Si 120 μm 116 μm 75 μm 30 μm

Al 8100 8000 7700 8600 10,000

Ma et al., 2008, 2009) researched the effect of an ultrasonic field on Fe 4000 2700 3100 4400 4500
removing the impurities Al, Fe, Ca, Ti, and Cu from MG-Si during the HF, Ca 880 1400 900 1000 1400
HNO3, and HCl leaching processes. The experimental results showed Cu 110 30 60 110 170
Mn 100 70 40 80 80
that the removal fraction of the impurities increased by 16.2% (HF),
Cr 10 10 10 10 20
7.1% (HNO3), and 6.8% (HCl) when compared with a conventional Ni 30 20 30 40 40
mechanical stirring treatment. Jian et al. (2009) further demonstrated Zn 100 20 110 280 380
that acid leaching processes with an ultrasonic field treatment were Cd <2 0.6 0.3 0.7 0.9
more effective than with a magnetic stirring treatment, especially for
removing Fe, Al, and Ti impurities. In addition, Xi et al. (2019b) com­
by a wet-milling process to further expose the internal impurity pre­
bined an ultrasonic field treatment with metal-assisted chemical etching
cipitates of MG-Si. After leaching by mixture solutions of HF + HCl, most
(MACE), which proposed an effective method of ultrasonic-Cu catalyzed
of the impurities (except B and P) were removed, and high-purity silicon
chemical leaching (U-CuCCL) to enhance impurity removal from MG-Si.
(~99.98%) was obtained. Moreover, Zong et al. (2015) obtained
The incorporation of the ultrasonic field treatment further increased the
nanoscale silicon particles (<100 nm) using a high-energy ball milling
efficiency of impurity removal by the CuCCL method, resulting in silicon
(HEMM) process. When the nanoscale silicon particles were leached
purity of 99.995%. As shown in Fig. 7(a), the improvement in the per­
with a solution of HF, HCl, and HNO3, the purity of the silicon improved
formance of the impurity removal from MG-Si can be ascribed to the
considerably to 99.999%. However, studies also found that the con­
acoustic streaming and acoustic cavitation effects of the ultrasonic field.
centration of impurities in raw MG-Si material increased when the
Therefore, the exposure of impurities in MG-Si can be enhanced by the
material was crushed to a very small size (Zhang et al., 2013; Lai et al.,
ultrasonic field treatment, facilitating their removal during the hydro­
2016). For example, Santos et al. (1990) found that the concentrations of
metallurgical process.
impurities increased as the MG-Si particle size decreased (Table 4).
Similar results were also observed by many researchers and were
5.3. Oxygen pressure leaching treatment
ascribed to the aggregation of impurities in the finer fractions (Chan­
drasekhar and Ramaswamy, 2002; Thomas et al., 2016). Thus, although
In addition, the oxygen pressure leaching treatment can also improve
more impurities can be exposed by an ultrafine grinding process, the
the kinetic conditions of the hydrometallurgical process (Jan et al.,
difficulty of impurity removal was also increased. Moreover, fine silicon
1976; Filippou et al., 1997; Ruiz et al., 2007; Provis et al., 2003). As
powers require energy to create and cause dust pollution. Therefore, this
shown in Fig. 7(b), the device for the pressure leaching reaction con­
strategy may still need to be improved in the future.
sisted of a stainless-steel jacket and polytetrafluoroethylene (PTFE)
inner tank; the leaching process primarily occurred in the inner tank (Lin
et al., 2018). Xie et al. (2011) and Yu et al. (2011, 2012) conducted 6.2. Introduction of cracks or porous structures in MG-Si
extensive research on impurity removal from MG-Si using pressure
leaching and found that the removal of the primary impurities Fe and Al The creation of cracks or porous structures in silicon is another
was increased by using an HCl solution. The effects of the particle size, strategy to expose the internal impurities of silicon to the etchants
temperature, total pressure, and acid concentrations on the kinetics and during the hydrometallurgical process. Won et al. (2011) prepared
mechanism of Fe and Al removal were also investigated. The study porous combustion-synthesized silicon (CS-Si) via an Mg thermal
showed that the apparent activation energy of Fe (46.908 kJ/mol) was reduction process and obtained >99.99% purity silicon using a three-
higher than that of Al (4.067 kJ/mol), leading to a higher removal step successive acid leaching process of H2SO4, HCl + HNO3 +
fraction for Fe than Al. Furthermore, the authors also analyzed the C2H5OH, and HF + HNO3 + C2H5OH. As shown in Fig. 8(a), unique
performance of oxygen pressure leaching on the purification of MG-Si microporous network structures are formed in the CS-Si particles,
and found that the removal efficiencies of Fe, Al, Ca, and Ti were increasing the leaching efficiency of the subsequent acid leaching pro­
22.2%, 34.9%, 19.5%, and 0.6% higher than those of the low-pressure cess. It was confirmed that the leaching behavior of the impurities was
leaching process. much better for the porous CS-Si than for the non-porous MG-Si. Sun
et al. (2013) found that cracks and defects were formed on the surface of
6. Enhancing impurity removal by increasing the impurity the MG-Si powder (as shown in Fig. 8(b)) after calcination at 1000 ◦ C,
exposure to the etchants followed by quenching in cold water. The cracks and defects also
contributed to the exposure of the internal impurities on the MG-Si
As mentioned above, the hydrometallurgical process is an excellent surface. After the subsequent acid leaching, the removal of impurities
and economical method to separate impurities from MG-Si. However, was significantly enhanced compared with the leaching results of the
the internal impurities of MG-Si cannot be exposed on the silicon powder raw MG-Si.
surface to react with the acid lixiviums, increasing the difficulty of In addition to high-temperature treatments, porous silicon can also
removing them. Many methods for the exposure of the internal impu­ be obtained by a hydrometallurgical process. Chadwick et al. (2012)
rities have been developed to increase the contact area between the successfully prepared porous MG-Si using a chemical etching process
impurities and etchants. with a nitric-acid-based mixture (as shown in Fig. 8(c)). It was found
that the impurities (Fe, Al, Ca, C, and O) promoted the formation of
6.1. Ultra-fine MG-Si powder preparation holes and porous structures at the particle surfaces in the HNO3 + HF
acid mixture solutions. Basing on this process, Khalifa et al. (2012,
In 1976, Hunt et al. (1976) chose a fine MG-Si powder (<53 μm) as 2013a, 2013b) obtained porous silicon by exposing MG-Si powders to
the raw material and performed leaching in a mixture of HNO3 and HCl the vapor of an acid mixture of HF/HNO3 or HF/H2O/HNO3, improving
solutions for 12 h at 75 ◦ C; it was found that the removal efficiency of the the removal of impurities from MG-Si. In addition, Xi et al. (2018a)
primary impurities (including Fe, Al, Zn, and Cu) from MG-Si was combined MACE and hydrometallurgy and proposed a metal-assisted
approximately 90%. Dietl (1983) obtained ultra-fine powder (<20 μm) chemical leaching (MACL) process, creating porous structures to

8
F. Xi et al. Hydrometallurgy 201 (2021) 105553

Fig. 8. Introduction of cracks or porous structures: (a) Calcination and quenching treatment; (b) Mg-thermal reduction; (c) HF/HNO3; (d)1-AgACL; (e) 2-AgACL; (f)
CuCCL. (Won et al., 2011; Sun et al., 2013; Chadwick et al., 2012; Xi et al., 2018a; Xi et al., 2018b).

expose the internal impurities of MG-Si. As shown in Fig. 8(d) and (e),
porous structures were obtained, increasing the contact area between
the impurities and lixiviants during the leaching process. Furthermore,
Xi et al. (2018b, 2020) also investigated the performance of the low-cost
Cu-catalyzed chemical leaching (CuCCL) process to obtain porous sili­
con (as shown in Fig. 8(f)) and proved that the purification of large-sized
particle MG-Si powders could also be enhanced.
6.3. Enhancing impurity diffusion by thermal pretreatments
In addition, since most impurity separation coefficients are less than
1, thermal treatments can improve the impurity removal performance
by transferring impurities to the formed SiO2 layer (Kim et al., 2014; Ai-
suo et al., 2009). Because the SiO2 layer can be easily removed by HF
solutions, the exposure of impurities (especially the nonmetallic impu­
rities B and P) by a thermal pretreatment is combined with the hydro­
metallurgical process. Tian et al. (2019) achieved a 54.59% removal
fraction of B by combining a thermal oxidation pretreatment and HCl +
HF leaching; this proportion is higher than that of the raw MG-Si. Khalifa
et al. (2013a, 2013b) demonstrated that the thermal oxidation process
improved the removal efficiency of B and P from MG-Si. In addition,
thermal oxidation was used to treat the porous silicon samples to ensure
that the impurities diffused from the inside to the surface layer of the
silicon grains. Because the thermal oxidation pretreatment weakened

Fig. 9. Reaction mechanism of boron removal using Cao-SiO2 slag. (Chen et al., 2019).

9
F. Xi et al. Hydrometallurgy 201 (2021) 105553

Table 5 impurity removal from MG-Si, but the removal of nonmetallic impurities
Reported results for MG-Si purification by combining slag refining and acid B and P remains very difficult. Furthermore, some metallic impurities,
leaching. such as Fe, Al, and Ca, cannot be entirely removed by hydrometallur­
Slag systems Acid leaching Results of main indicators Ref. gical processes. Thus, the combination of a secondary refining process
treatments and hydrometallurgical processes was proposed to further enhance im­
CaO–SiO2–Na2O HCl + HF RF: 100% Fe, 95% Ti, Meteleva- purity removal from MG-Si. Although many types of secondary refining
94.9% Al, 97.9% C, Fischer et al., processes (such as gas blowing (Wu et al., 2014a, 2014b; Xia et al.,
97.9% B, 82.1% P a 2012 2017), slag treatment (Teixeira and Morita, 2009; Cai et al., 2011; Wu
CaO–SiO2–CaF2 HCl RF: 96% Fe, 98% Al, Fang et al.,
et al., 2014a, 2014b), plasma refining (Lee et al., 2011; Tsao and Lian,
99.1% Ca 2014a
CaO–SiO2–CaCl2 HCl P: 0.43 ppmw Huang et al., 2005), and solvent refining (Yoshikawa and Morita, 2012; Ma et al.,
2016a 2014)) have been used in metallurgical treatments, the most suitable
CaO–SiO2–CaCl2 HF + HCl B: 0.81 ppmw Zhou et al., secondary refining methods with hydrometallurgical processes are slag
2019 refining and solvent refining.
CaO–SiO2–CaCl2 HNO3; HNO3 RF: B: 71.5% → 88.7% Huang et al.,
+ HF; HNO3 P: 32.7% → 57.6% 2016b

7.1. Combination of slag refining and hydrometallurgical processes

the bonds between the impurities and Si, 99.996% purity silicon was
successfully obtained following the HF leaching treatment (Khalifa
et al., 2012). Xi et al. (2019b) combined ultrasonic and rapid thermal
treatments with the CuCCL process and obtained silicon with a purity of
99.995%.
7. Enhancing impurity removal by combining secondary
refining process
Hydrometallurgy techniques have resulted in significant progress in
Slag refining methods are typically used in the steel industry to
remove sulfur and phosphorus; the method is based on the principle of
liquid–liquid extraction (Inoue and Suito, 1982; Basu et al., 2010). In
various slag systems, the oxides in the slags play an important role in the
absorption and separation of impurities from the molten MG-Si. There­
fore, the slag refining method is regarded as a promising purification
method to eliminate impurities from MG-Si via an oxidation reaction
(Wu et al., 2020). Fig. 9 shows a typical B impurity removal process
using the CaO–SiO2 slag treatment (Chen et al., 2019). This process has 5
steps: (a) the dissolved B in the silicon solution diffuses toward the

Fig. 10. Impurities precipitations in the source MG-Si (a) and CaO–SiO2–Na2O slag treated MG-Si(b), concentrations of Al, Ca, Mg, and Na in MG-Si treated by
CaO–SiO2–Na2O slag with different Na2O contents (c). (Meteleva-Fischer et al., 2012).

10
F. Xi et al.
Fig. 11. Schematic purification process of (a) MG-Si alloyed with Cu, (b) treatment using CaO–SiO2–CaCl2 slag, and (c) acid leaching. (Huang et al., 2016b).
silicon boundary layer; (b) diffusion from the silicon boundary layer to
the silicon/slag interface; (c) chemical reaction between B and the slag
at the interface; (d) diffusion from the interface to the slag boundary
layer; (e) calcium borate diffusion to the slag bulk phase from the slag
boundary layer. Similar to B, the impurities Al, Ca, Ti, and P can also be
oxidized and absorbed during the formation of calcium borate. How­
ever, other impurities may be introduced to the purified silicon, which
cannot be ignored. Typically, the induced impurities in the slag-refined
MG-Si (S-MG-Si) are easier to remove by the hydrometallurgical process
than the original impurities in MG-Si. Therefore, the combination of slag
refining and hydrometallurgy techniques was proposed for enhancing
the removal of impurities from MG-Si. Important research studies that
used this combination are summarized in Table 5.
7.1.1. CaO–SiO2–Na2O slag systems
Meteleva-Fischer et al. (2012) used the slag systems of
CaO–SiO2–Na2O to refine MG-Si. It was found that the concentrations of
B and P were significantly reduced, but the contents of Fe, Ti, Cu, V, and
Zr were not changed substantially by the slag treatment. As shown in
Fig. 10(a) and (b), the components and structures of the impurity pre­
cipitations changed after the slag refining process, and small calcium
phase particles were observed. Apart from Ca and Na, the concentrations
of Al and Mg also increased after the slag treatment. Although the
concentrations of the impurities Al, Ca, Mg, and Na in the S-MG-Si were
reduced for different Na2O contents, the contents were still very high (as
shown in Fig. 10(c)). In addition, due to the sensitivity between the Si-Ca
intermetallics and HCl acid, the subsequent acid leaching treatments are
very important. After the pretreated MG-Si was leached with 20% HCl
and HF mixture acids, the removal efficiency of impurities Fe, Ti, B, P,
Al, and Ca was 100%, 95%, 97.9%, 82.1%, 94.9%, and 97.9%,
respectively.
7.1.2. CaO–SiO2–CaF2 slag systems
Fang et al. (2014a, 2014b) proposed purification of MG-Si by pre­
treating MG-Si with the CaO–SiO2–CaF2 slag refining process, followed
by an HCl acid leaching treatment. Similar to the results of Meteleva-
Fischer et al. (2012), Si − Ca silicide phases, such as Si − Ca − M (Al/Ti)
11
Hydrometallurgy 201 (2021) 105553
and Si − Ca − Fe − M (Al/Ti/Mn) were also found in the S-MG-Si. Be­
sides, the contents of the main impurities Mn, Al, B, and P were signif­
icantly decreased after the CaO–SiO2–CaF2 slag pretreatment.
Furthermore, the study proved that the subsequent HCl acid leaching
was highly efficient and provided better performance for S-MG-Si than
for the MG-Si for the removal of the main impurities Fe, Al, Ca, Ti, Mn, B,
and P.
7.1.3. CaO–SiO2–CaCl2 slag systems
Huang et al. (2016a) investigated the combination of
CaO–SiO2–CaCl2 slag refining and HCl acid leaching to remove the
nonmetallic impurity P from MG-Si. It was found that P in S-MG-Si
primarily occurred as Ca3(PO4)2 and Ca3P2, which could be easily
leached out by HCl; the chemical reactions are described in Eqs. (5) and
(6). After the combined processes, the concentration of P in silicon had
significantly decreased to 0.43 ppmw. Zhou et al. (2019) further com­
bined the CaO–SiO2–CaCl2 slag treatment and acid leaching process to
remove the nonmetallic impurity B from MG-Si. The study results
showed that most of the B was removed due to the conversion into
gaseous boride BOCl after the CaO–SiO2–CaCl2 slag refining process, and
only 1.37 ppm B remained in the silicon. To determine the details of the
B removal process, 3 wt% B-doped silicon alloy was used as a raw ma­
terial for purification. A high B removal efficiency was also observed in
the combined processes. After leaching with an HCl + HF acid mixture,
the content of B in MG-Si had decreased to 0.81 ppmw.
Ca3 (PO4 )2 (s) + 6HCl(aq.)→3CaCl2 (l) + 2H3 PO4 (l) (5)
Ca3 P2 (s) + 12HCl(aq.)→3CaCl2 (l) + 2PCl3 (l) + 6H2 (g) (6)
Moreover, Huang et al. (2016b) also used the CaO–SiO2–CaCl2 slag
treatment to remove B and P from Cu-alloyed MG-Si. As shown in
Fig. 11, low-purity MG-Si was first alloyed with Cu to form a Si-Cu alloy
phase and underwent CaO–SiO2–CaCl2 slag refining. The high-purity
silicon was obtained using a selective acid leaching treatment. After
alloying with MG-Si and Cu, the P, Fe, Al, and Ca impurities coexisted
with the precipitates, and B was concentrated in the Si-Cu alloy phase.
The Si-Cu alloy phase further attracted abundant B, P, Fe, and Ca to form
F. Xi et al.
Fig. 12. (a) Si-based binary phase diagram (b) schematic diagram of the solvent refining process.
precipitates during the slag refining process. Thus, B and P were effec­
tively aggregated in the Si-Cu alloy phase. In addition, the selective acid
leaching procedure (Step 1: 2 M HNO3, 5 h; Step 2: 2 M HNO3 + 1 M HF,
2 h; Step 3: 1 M HNO3, 1 h) played a unique role in the separation of the
Si-Cu alloy phase and the removal of impurities. After the successive
treatments, the removal efficiency of B and P from MG-Si was increased
from 71.5% to 88.7% and 32.7% to 57.6%.
7.2. Combination of solvent refining and hydrometallurgical processes
The solvent refining process, which is also known as alloying
refining, is based on the principle of fractional crystallization (Li and
Zhang, 2019). Fig. 12(a) and (b) show the Si-based binary phase dia­
gram and schematic diagram of the solvent refining process. During the
solvent refining process, the metals are dissolved in molten silicon to
form an alloy. Due to the low thermodynamic stability of some impu­
rities in MG-Si, their segregation coefficients are low in MG-Si-based
alloys (A-MG-Si) (Hopkins and Rohatgi, 1986; Hu et al., 2013). Thus,
the removal of impurities from MG-Si can be enhanced by the solvent
refining process. However, the stripping of the alloy phases and silicon
after the solvent refining processes is a key issue. Due to the advantages
of hydrometallurgy techniques, their use in combination with solvent
refining is considered a promising approach to obtain high-purity silicon
from MG-Si. A summary of the combination studies is provided in
Table 6.
12
Hydrometallurgy 201 (2021) 105553
7.2.1. Si-Fe alloy systems
Esfahani and Barati (2011) reported on the use of low-cost Fe as an
impurity getter in the solvent refining process; it was found that the
impurities did not diffuse into the silicon phase when the quenching
temperature was above the eutectic temperature. When the obtained A-
MG-Si was immersed into the HF + CH3COOH mixture, the Si-Fe phases
were dissolved from the A-MG-Si. Nearly all impurities were eliminated
after treatment with the HF + HNO3 + H2O mixture leaching process, as
shown in Table 6. Khajavi et al. (2015) investigated the removal of B
from silicon in Si-Fe alloy systems using a combination of acid leaching
processes. The authors found that a strong affinity was formed between
B and Fe after the Fe alloying process. After leaching with an HF +
CH3COOH mixture, the removal efficiency of B was significantly
increased to 70%.
7.2.2. Si-Ca alloy systems
As mentioned above, some impurities can be dissolved into the Si-Ca
alloy phases during the Ca–slag treatment, indicating that Si-Ca alloys
may be potential alloy systems for solvent refining of MG-Si. Shimpo
et al. (2004) investigated the interaction between Ca and P in molten
silicon and found that the segregation of P was enhanced by alloying Ca.
Thus, the addition of Ca is an effective P getter in the molten MG-Si.
These results indicate that the combination of Ca alloying refining and
an aqua regia acid leaching treatment resulted in high removal effi­
ciencies of P and Ca. He et al. (2012) studied the removal of metallic
impurities from MG-Si using these combination treatments. After the Ca
F. Xi et al. Hydrometallurgy 201 (2021) 105553

Table 6 Moreover, Lai et al. (2015) compared the leaching efficiency of

Reported results for MG-Si purification by combining solvent refining and acid Ca–alloyed MG-Si by analyzing the precipitate evolution before and
leaching. after the addition of HCl, aqua regia, and an HCl + HF mixture, con­
Alloy Acid leaching Results of main indicators Ref. firming that the HF + HCl mixture was the optimal lixiviant to purify
systems treatments MG-Si and A-MG-Si.
Si–Fe HF + CH3COOH; Residual impurities Esfahani and
HF + HNO3 + H2O (ppmw): Barati, 2011 7.2.3. Si-Cu alloy systems
Al (10), Mn (3), Ni (3), Cr Cu can also be chosen as the impurity getter of MG-Si in the solvent
(1), Fe (1), B (2), P (29); V,
refining field because of the following advantages: (1) Cu has low sol­
Ba, Li, Be, Mg (<0.5)
Si–Fe HF + CH3COOH RF: 70% B Khajavi et al., ubility in silicon, and there are large differences in their densities
2015 (Olesinski and Abbaschian, 1986). (2) The impurities in the Cu–Si-alloy
Si–Ca Aqua regia RF: 80.4% P, 99.3% Ca Shimpo et al., have low segregation coefficients between the solid silicon and alloy
2004 melt. (3) Cu–Si–alloy has a relatively low melting point and a high af­
Si–Ca HCl; Aqua regia; Residual impurities He et al., 2012
HF (ppmw):
finity for a wide range of elements (Mitrašinović and Utigard, 2009).
Fe, Al, Ti, Ni:<5; Ca: 110 However, the highly efficient separation of the primary silicon and
Si–Ca HCl; HF; HCl + HF Si purity: 99.995% Meteleva- Cu–Si-alloy is difficult. Conventional separation methods include elec­
Residual impurities Fischer et al., trolysis (Santos et al., 1990) and gravity sedimentation (Visnovec et al.,
(ppmw): 2013
2013), but both methods have to be performed in large-scale equipment
Al (10–25), Ca (15–35), B
(10–15), Ti (1–2) at high temperatures, limiting the development of Cu alloying refining
Si–Ca HCl; HCl + HNO3; Residual impurities Lai et al., 2015 to purify MG-Si. Mitrašinović and Utigard (2009) reported the successful
HCl + HF (ppmw): separation of primary silicon from 50 wt% Cu–50 wt% Si alloy by HNO3
P (~5), Fe (~4), Ni (~4), or mixed HCl + HNO3 solutions. It was found that the total impurities in
Cu (~4)
Si–Cu HCl; HNO3 5277 ppmw → 225.5 ppmw Visnovec et al.,
the separated silicon decreased after the treatment. Subsequently, many
(Total) 2013 studies were conducted on the combination of Cu alloying refining and
Si–Cu HCl/HNO3/Aqua RF: B: 21.0% → 58.7% Huang et al., acid leaching to purify MG-Si. Huang et al. (2016c) used the Cu alloying
regia; HNO3 + HF; P: 23.2% → 42.2% 2016c refining process to remover B and P and determined that B and P could
HNO3
be absorbed into the Si-Cu alloy phase. The authors designed a three-
Si–Cu HNO3; HNO3 + HF; Fe: 816.94 ppmw → 1.44 Huang et al.,
HNO3 ppmw 2016d step acid leaching procedure (Step 1: 2 M HCl/HNO3/aqua regia, Step
Si–Cu–Ca HCl/HNO3/Aqua RF: ~82% P Huang et al., 2: 2 M HNO3 + trace HF, Step 3: 1 M HNO3) to separate the Si-Cu alloy
regia; HNO3 + HF; 2018 phase and purify silicon. In the first step, aqua regia not only exhibited
HNO3 good performance for separating the purified silicon and Si-Cu alloy
Si–Al Aqua regia + RF: 99.2% Fe, 99.2% Ti, Yoshikawa and
phase but also removed B and P from the formed metal phases by the
H2SO4 64.5% Al, 98.2% B, 98.2% Morita, 2005
P proposed Eqs. (7) and (8). Subsequently, the second step (HNO3 + HF
Si–Al Aqua regia Si purity: 99.92% Li et al., 2012 mixture) was performed to dissolve the residual Cu3Si obtained in the
B: 5.25 ppmw, P 13.5 first step; the reactions are defined in Eqs. (9), (10), and (11). The last
ppmw,
step (HNO3) desorbed SiF4 and nitrogen oxide gases. After the successive
Si–Al–Sn Aqua regia; HF RF: 97.7% B, 99.8% P, Hu et al., 2013
>99.9% Metallic leaching processes, 58.7% B and 42.2% P were leached out. Further­
impurities more, the authors also investigated the performance of Fe removal from
Si–Al–Ti Aqua regia + B: 1.2 ppmw Lei et al., 2016a MG-Si using the combination processes (Huang et al., 2016d). During
H2SO4 the Cu alloying refining process, the Fe impurities were transferred into
Si–Mg HCl (Twice) Residual impurities Safarian and
the Si-Cu alloy phase in the form of Si–Fe–Mn and Fe–Mn–Ti phases, and
(ppmw): Tranell, 2016
B: ~28, P: ~7 then were eliminated by the subsequent acid leaching steps. Huang et al.
Si–Mg HCl Si purity: 99.92% Espelien et al., (2018) also found that P could be homogeneously adsorbed in the
2017 formed secondary phase CaCu2Si2 after Ca was added to the Si-Cu
Si–Mg HCl P: 15.1 ppmw → 0.2 ppmw Zhu et al., 2020
refining system. Therefore, a high removal efficiency of P can be ob­
Si–Mg HCl + HF Si purity: 99.995% Mei et al., 2020
Aqua regia B: 36.3% → 94.0%,
tained when the Si–Cu–Ca alloying refining process is combined with
P: 22.6% → 98.9% acid leaching.
Si–Zr HCl + HF RF: 97.5% Total, 99.9% Zr Lei et al., 2017a ( )
Si–Hf HCl + HF; Aqua 6126 ppmw → 94 ppmw Lei et al., 2017b xy + 3y 2
Mx By (s) + HNO3 (aq.) +xyHCl(aq.)+ y − xy H2 O(l)→xMCly (aq.)
regia (Total) 3 3
xy + 3y
+yB(OH)3 (aq.) + NO(g) (7)
3
alloying refining process, Ca as the main impurity formed precipitates in
the Si-Ca alloy or Si–Ca-based alloys. A comparison of the leaching effect xy + 5y 2y − 2xy
of HCl, aqua regia, and HF indicated that HCl exhibited the best per­ Mx Py (s) +
3
HNO3 (aq.) + xyHCl(aq.) +
3
H2 O(l)→xMCly (aq.)
formance for the metal impurity removal from A-MG-Si. After the suc­ xy + 5y
cessive processes, the contents of the main metallic impurities Fe, Al, Ti, + yH3 PO4 (aq.) + NO(g) (8)
3
and Ni decreased to<5 ppmw. Based on these results, Meteleva-Fischer
et al. (2013) systematically summarized the influences of different pa­ 3Cu3 Si(s) + 16HNO3 (aq.) + 6HF(aq.)→3Cu(NO3 )2 (aq.) + H2 SiF6 (aq.)
rameters on the microstructure and impurity removal performance of + 10H2 O(l) + 10NO2 (g) (9)
Ca–alloyed MG-Si, which found that different Ca additions and cooling
rates influenced the silicon microstructure and impurity removal per­ 3Cu3 Si(s) + 28HNO3 (aq.) + 18HF(aq.)→9Cu(NO3 )2 (aq.) + 3H2 SiF6 (aq.)
formance. Although HCl was the most efficient acid for the removal of + 20H2 O(l) + 10NO(g) (10)
Al, Ca, Cu, Mn, and Ni, it was inefficient for the removal of Cr, Ti, V, C,
Mo, and Zr. Therefore, HCl + HF mixture solutions were chosen as the 4Cu3 Si(s) + 34HNO3 (aq.) + 24HF(aq.)→12Cu(NO3 )2 (aq.) + 4H2 SiF6 (aq.)
most suitable etchants to enhance the impurity removal from A-MG-Si. + 25H2 O(l) + 5N2 O(g) (11)

13
F. Xi et al. Hydrometallurgy 201 (2021) 105553

Fig. 13. Combinations of the (a)Sn/Al and (b) Mg alloying and acid leaching processes. (Hu et al., 2013; Zhu et al., 2020).

(Fig. 13(b)). It was found that Mg2Si and Fe–Al–Si–Ca were the major
7.2.4. Si-Al alloy systems
intermetallic phases in the solidified A-MG-Si after the alloying refining
The Si-Al alloy system is another suitable solvent for refining MG-Si.
process. Because of the high reactivity of HCl and the Si-Mg alloy, HCl
However, the similar densities of the primary silicon and Si-Al melt
was chosen as the optimal acid to remove impurities from the formed A-
result in difficulties separating them (Hu et al., 2013; Li et al., 2012). A
MG-Si. Their research group further conducted a study on P removal
combination of acid leaching with Si-Al alloying refining processed is
from MG-Si using these combinations, verifying the attraction of P in the
considered an economical and effective method to collect primary sili­
Mg alloying refining process (Zhu et al., 2020). After two successive Si-
con from the Si-Al melt and purify silicon. Yoshikawa and Morita (2005)
Mg alloying refining processes and acid leaching processes, a SOG-Si P
separated solidified silicon grains from the Si-Al melt under a fixed
concentration of 0.2 ppmw was obtained. Furthermore, Mei et al. (2020)
alternating magnetic field, followed by leaching with aqua regia and
prepared a Si-Mg alloy by controlling the ratios of MG-Si and Mg during
H2SO4 mixtures. After successive treatments, the removal efficiencies of
the Mg alloying process. Many porous structures at the nanometer-scale
Fe, Ti, B, P, and Al were 99.2%, 99.2%, 98.2%, 98.2%, and 64.5%,
to micrometer-scale were formed. After successive leaching treatments
respectively. Li et al. (2012) used a combination of supergravity and acid
with HCl + HF and aqua regia, the high-purity silicon (~99.995%) was
leaching to produce high-purity silicon. It was found that supergravity
obtained.
successfully separated silicon from the Si-Al melt, and the aqua regia
leaching process resulted in further silicon and impurity separation. In
7.2.6. Transition metal alloy systems
addition, Hu et al. (2013) combined a Si-Al alloy system with an Sn-Si
It was found that some transition metals not only showed a strong
alloy system to form a Si–Al–Sn ternary alloying refining process
affinity for the impurities in MG-Si but also had very small segregation
(Fig. 13(a)), which significantly reduced the segregation coefficients of
coefficients in A–MG–Si (Trumbore, 1960; Lei et al., 2016b; Hopkins and
the main impurities. After the A-MG-Si were successively leached by
Rohatgi, 1986; Sachdeva et al., 2006; Schlesinger et al., 1993). There­
aqua regia and HF, the main impurities in the high-purity silicon product
fore, the combination of transition metal alloying refining and acid
were significantly reduced to below 1 ppmw, which met the re­
leaching processes was proposed to enhance the performance of impu­
quirements for manufacturing SOG-Si. Lei et al. (2016a) studied the
rity removal from MG-Si. Lei et al. (2017a) tested Zr as an impurity
addition of Ti to Si-Al alloy and proved that the removal of B from MG-Si
getter to form Zr–alloyed MG-Si and found that the Fe and Al impurities
was enhanced. After the following mixed acid (HCl: HNO3:H2SO4 =
were adsorbed as Si–Zr–Fe and Si–Zr–Fe–Al phases (as shown in Fig. 14
3:1:1) leaching treatment, the residual B was significantly reduced to 1.2
(a)) after the Zr alloying refining process. As shown in Fig. 14 (c-1), the
ppma.
authors further proved that the Si–Zr–Fe and Si–Zr–Fe–Al phases were
more soluble in the acid etchants than the impurity phases in the MG-Si,
7.2.5. Si-Mg alloy systems
and the order of leaching efficiency was HCl + HF > HF > aqua regia.
As a light metal, Mg has the potential to refine silicon due to the low
After the combination of Zr alloying refining and the HCl + HF leaching
reaction temperature during the alloying refining process. Besides, Mg
processes, the final removal fraction of all impurities (Fe, Al, Ca, B, P, Zr,
can react with most impurities to form stable compounds. Safarian and
Ti, V, Mn, Cu, and Ni) significantly increased to 97.5%. Lei et al. (2017b)
Tranell (2016); Espelien et al., 2017) investigated the combination of
also used the transition metal Hf as an impurity getter to purify MG-Si.
Mg alloying refining and acid leaching to remove impurities from MG-Si
Similar to the Zr–alloyed MG-Si, Fig. 14 (d) shows that the Hf–alloyed

14
F. Xi et al.
Fig. 14. Precipitate in MG-Si alloyed with 5 wt% Zr (a), 5 wt% Hf (d) and their EDS mapping analysis; SEM images of MG-Si with 5 wt% Zr before leaching(b, c) and
after leaching with aqua regia (b-1) and HF (c-1); SEM images of MG-Si with 5 wt% Hf before leaching(e, f) and after leaching with aqua regia(e-1) and HF (f-1). (Lei
et al., 2017a, 2017b). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
MG-Si also absorbed large amounts of the impurities Fe and Al and co-
precipitated as Si–Hf–Fe and Si–Zr–Fe–Al phases. Different from the
results of the Zr–alloyed MG-Si, it can be seen from Fig. 14 (d) that P
coexisted with Ca in the Hf–alloyed MG-Si, indicating that P can be
removed in the Zr alloying refining process. An analysis of the leaching
behavior of Hf–alloyed MG-Si demonstrated that Hf could be success­
fully removed by HF-containing lixiviants (as shown in Fig. 14 (f–1)).
After treatments with successive HCl + HF and aqua regia leaching, the
total concentration of impurities was reduced from 6126 ppmw to 94
ppmw.
The combination of secondary refining and hydrometallurgical
processes provide excellent performance for enhancing impurity
removal from MG-Si, especially for the nonmetallic impurities B and P.
However, since the slag/alloy systems contain many impurities, addi­
tional impurities are easily introduced into the purified silicon. There­
fore, the selection of the slag system and alloyed metals are very
important. Unlike the common hydrometallurgical processes, the
leached slag/solvent/waste acid contains many valuable metal ions.
Thus, the recycling of the slag/solvent/waste acid is also a crucial
problem requiring further research.
8. Conclusions
The present work provides an extensive review of studies focused on
the principle and development of impurity removal from MG-Si by
15
Hydrometallurgy 201 (2021) 105553
hydrometallurgy techniques. The general conclusions and perspectives
are as follows:
• The impurities in MG-Si can be classified as segregation impurities
and insoluble impurities. The segregation impurities are easily
exposed, but the insoluble impurities cannot be entirely exposed
when the MG-Si bulk is pulverized. Thus, the insoluble impurities
should be considered to obtain the requested high-purity silicon from
a hydrometallurgical treatment.
• Single-acid leaching (e.g., H2SO4, HNO3, HCl, and HF) only removes
specific impurities; thus, successive or mixture acid leaching (e.g.,
H2SO4 + HNO3, HF + HNO3, aqua regia, HCl + H2SO4, HCl + HF,
HNO3 + HF + CH3COOH, and HCl + HF + CH3COOH) are now
widely used in practice. The addition of oxidizing agents (e.g.,
(NH4)2S2O8, FeCl3, H2O2, AgNO3, and Cu(NO3)2) to the acid lixi­
viums also increases the impurity removal efficiency, especially for
H2O2 or its combinations with AgNO3 and Cu(NO3)2. Thus, it is
predicted that the use of hybrid processes and the development of
novel processes will be a future trend.
• The removal of impurities from MG-Si by hydrometallurgical pro­
cesses depends on the sensitivities of the silicon substrate and the
exposure of the impurities to the acid etchants. Thus, intensive
measures, such as introducing external fields (e.g., ultraviolet radi­
ation, ultrasonic field, and oxygen pressure leaching treatment) or
increasing the impurity exposure to the etchants (e.g., ultra-fine MG-
F. Xi et al.
Si, introducing cracks/porous structures, and thermal pretreatments)
could contribute to enhance impurity removal. Due to complex op­
erations, the simplification of the purification process should be
considered.
• Combinations of secondary refining (slag refining and solvent
refining) processes and hydrometallurgical processes are the most
effective methods to remove insoluble impurities from MG-Si. Slag
refining systems (e.g., CaO–SiO2–Na2O, CaO–SiO2–CaF2, and
CaO–SiO2–CaCl2) are usually combined with HCl or HCl-contained
acid mixtures in acid leaching, and various metals (e.g., Ca, Cu, Al,
Sn, Fe, Mg, Ti, Zr, and Hf) are used as solvents for solvent refining
requiring different acid leaching conditions. Since slag/alloy systems
introduce additional impurities into the purified silicon, new slag/
alloy systems containing few impurities that are easily removed by
the subsequent acid leaching treatments have to be developed.
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.
Acknowledgment
Financial support of this work from the National Natural Science
Foundation of China (Grant No. 61764009, 51762043, 51974143);
Chinese Scholarship Council (CSC201808740003); National Key R&D
Program of China (No. 2018YFC1901801, No. 2018YFC1901805);
Major Science and Technology Projects in Yunnan Province (No.
2019ZE007); Key Project of Yunnan Province Natural Science Fund (No.
2018FA027); Yunan Ten Thousand Talents Plan Young & Elite Talents
Project and the Program for Innovative Research Team in University of
Ministry of Education of China (No. IRT_17R48).
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