Novel method of lithium production from brines combining battery material and

sodium sulphite as a cheap and environmentally friendly reducing agent

Sara Pérez-Rodrígueza, James Andy Miltonb, Nuria Garcia-Araeza,*

a: Chemistry, University of Southampton, Highfield Campus, SO17 1BJ Southampton, UK

b: Ocean and Earth Science, National Oceanography Centre, University of

Southampton, SO14 3ZH Southampton, UK

*Corresponding author: [email protected]

Abstract

The growing increase in the global demand for lithium for the production of lithium batteries

demands for the development of alternative, fast, environmental-friendly and cost-effective

technologies for lithium production. Most lithium resources are in the form of brines, which

are concentrated saline solutions containing lithium in the presence of an excess of other

cations (primarily, sodium, magnesium and potassium). The use of lithium battery materials

has been shown to be highly advantageous for the selective sequestration of lithium from

brines, thus achieving the efficient separation of lithium from other cations and, with this,

facilitating the production of the highly pure Li2CO3 required for the battery industry. The

sequestration of lithium by battery material can be driven by electricity or redox agents, and

the later has advantages in terms of the simplicity of the reactor design for large scale

production. A critical aspect in the use of redox agents is the cost and environmental

compatibility. Here we demonstrate the use of a novel redox reagent, sodium sulphite, that is

cheap, non-toxic and induces fast lithium sequestration reactions.

1
Key words: lithium production, sodium sulphite, chemical lithium extraction, brines, lithium-

ion batteries, lithium iron phosphate.

INTRODUCTION

The demand for lithium production worldwide has experienced a dramatic increase in recent

years, mainly due to the growth of the rechargeable lithium battery market, and an even

higher increase is expected in coming years due to the expansion of lithium battery

applications in electric vehicles, portable devices and grid storage.1–5 Consequently, the

development of alternative methods of lithium production is urgently needed to cope with the

increasing demands.6–9

Around 60% of the global lithium resources are in the form of highly saline solutions, called

lithium brines, which contain cations such as Na+, K+ and Mg2+ in much higher concentrations

than that of Li+.6,8 Unfortunately, current methods of lithium production can only be applied

to a narrow range of brine compositions,6 and hence, it is necessary to develop new methods

able to extract lithium ions selectively, in the presence of a vast excess of other cations, since

that would enable a massive increase in the lithium production. Several methods for lithium

sequestration from brines have been explored and the use of lithium battery materials to

enable the selective lithium extraction from brines appears particularly promising, as

illustrated in table 1.

2
 Table 1. Studies of lithium sequestration from brines using battery host materials.

Methodology for
Battery material Brine Quantification of lithium sequestration Experimental conditions Ref.
lithium recovery

10 cycles of lithium capture (from 1.0 to 0.2 V vs SCE e) and release

-1 a
Geothermal water Li uptake in solid = 11 mg g (from 0.2 to 1.0 V vs. SCEe) at 0.1 mV s-1 using a Pt/λ-MnO2 10

electrode and a Pt wire as counter electrode.

4 cycles of lithium capture from brine (reduction) and release in 1 st
recovery solution (oxidation) followed by 4 cycles of lithium capture
Salar de Atacama Δ[Li+]recovery solution = 18 mM b 11
from 1st recovery solution (reduction) and release in 2 nd recovery
solution (oxidation) in a λ-MnO2/Ag cell, ±0.5 mA cm-2, 30 min.
3 cycles of lithium capture from brine (reduction) and release in 1 st
recovery solution (oxidation) followed by 3 cycles of lithium capture
Salar de Atacama Δ[Li+]recovery solution = 60 mM b from 1st recovery solution (reduction) and release in 2 nd recovery 12

solution (oxidation) in a λ-MnO2/activated carbon cell, containing an

anion exchange membrane, ±0.5 mA cm-2, 30 min.
3 cycles of lithium capture (reduction, cut-off = 1.38 V) and release
Salar de Atacama Δ[Li+]recovery solution = 45 mM b (oxidation, cut-off = 1.93 V) in a λ-MnO2/Zn cell containing an anion 13

exchange membrane, ±0.5 mA cm-2.

1 cycle of lithium capture from brine (-0.01 mA cm-2) and release in
1st recovery solution (0.2 mA cm-2) followed by 1 cycle of lithium
LiMn2O4 Electrochemical
Desalination brine Li purity in recovery solution = 99% c capture from 1st recovery solution (-0.1 mA cm-2) and release in 2nd 14

recovery solution (0.1 mA cm-2) in a λ-MnO2/Ag cell. Reduction

current cut-off = 0.2 V. Oxidation current cut-off = 0.9.
1 cycle of lithium capture (reduction) and release (oxidation) in a λ-
Salar de Olaroz Δ[Li+]recovery solution = 16 mM b 15
MnO2/polypyrrole cell, ±2.5 mA cm-2, 16 h.
Li purity recovery solution = 61% (λ- 1 cycle of lithium capture (reduction) and release (oxidation) in a λ- 16
Salar de Atacama
MnO2/NiHCF), 96% (λ-MnO2/Ag) c MnO2/NiHCF or λ-MnO2/Ag cell, ±148 mA g-1, 60 min.
1 cycle of lithium capture (reduction, -0.2 V vs Ag/AgCl) and release
(oxidation, 1 V vs Ag/AgCl), each step for 2 h using a λ-
Salt lake brine Li uptake in solid = 35 mg g-1 a 17
MnO2/polypyrrole/polyninylsulfonate electrode and a Pt wire as
counter electrode.
1 cycle of lithium capture (reduction, at -0.6 V) and release
Simulated brine
Li uptake in solid = 21-22 mg g-1 a (oxidation, at 0.6 V), each step for 120 min, in a LiMn2O4/Li1-xMn2O4 18
concentrated seawater
cell containing an anion exchange membrane.
Δ[Li+]recovery solution = 18 mM (film electrode), 100 cycles of lithium capture (reduction) and release (oxidation) in a 19
Salt lake brine
25 mM (powder electrode) b λ-MnO2/Ag cell, ±50 mA g-1,30 min.
Taijinair lake Δ[Li+]recovery solution = 35 mM b 4 cycles of lithium capture (reduction, cut-off = 0.15 V) and release 20

3
 (oxidation, cut-off = 0.7 V) in a polyaniline/LixMn2O4 cell, ±0.5 mA
cm-2.
5 cycles of lithium capture (reduction) and release (oxidation) in a λ-
Salt lake brine Li uptake in solid = 14 mg g-1 a 21
MnO2/Ag cell, ±50 mA g-1, 30 min.
Li uptake in solid = 8 mg g-1 a 1 cycle of lithium capture (reduction) and release (oxidation) in a λ- 22
Sodium rich brine
Li purity in recovery solution = 85% c MnO2/Ag cell, ±0.5 mA cm-2, 120 min.
1 cycle of lithium capture (reduction) and release (oxidation) in a λ-
Salar de Atacama Li purity in recovery solution = 98% c 23
MnO2/Ag cell, ±0.5 mA cm-2, 60 min.
1 cycle of lithium capture (reduction) and release (oxidation) in a λ-
Salar de Atacama Li purity in recovery solution = 74% c 24
MnO2/NiHCF, ±108.5 mA g-1, 40 min.
1 cycle of lithium capture (reduction, at -1 V) and release (oxidation,
West Taijnar salt lake Li uptake in solid = 29-33 mg g-1 a at 1 V), each step for 10 h, in a LiFePO4/FePO4 cell containing an 25
LiFePO4
anion exchange membrane.
1 cycle of lithium capture (reduction, at -0.25 V) and release
Salt lake brine Li uptake in solid = 39 mg g-1 a (oxidation, at 0.25 V), each step for 10 h, in a LiFePO4/ FePO4 cell 26

containing an anion exchange membrane.

1 cycle of lithium capture (reduction, at -0.2 V) and release
(oxidation, at 0.2 V), each step limited to a current cut-off = 0.05 mA
West Taijnar salt lake Li uptake in solid = 25 mg g-1 a 27
cm-2, in a LiFePO4/FePO4 cell containing an anion exchange
membrane.
Li uptake in solid = 11 mg g-1 a 1 cycle of lithium capture (reduction) and release (oxidation) in a Li 1- 28
LiNi1/3Co1/3Mn1/3O2 Salar de Uyuni
Li purity in recovery solution = 97% c -2
x Ni1/3Co1/3Mn1/3O2/Ag cell, ±0.5 mA cm , 20 min.
Li uptake in solid = 9 mg g-1 a 1 cycle of lithium capture (reduction) and release (oxidation) in a Li 1- 29
LiNi0.5Co1.5Mn1.5O2 Salar de Uyuni
Li purity in recovery solution = 98% c -2
x Ni0.5Co1.5Mn1.5O2/Ag cell, ±0.44 mA cm , 20 min.
Central Altiplano Li uptake in solid = 46 mg g-1 a Na2S2O3 as reducing agent, [Na2S2O3] = 0.3 M, 24 h. 30

LiFePO4 Redox agents Li uptake in solid = 44-45 mg g-1 a This

Central Altiplano Na2SO3 as reducing agent, [Na2SO3] = 0.3 M, 24 h.
Li purity in solid = 94-96%d work
a
The Li uptake is defined as the amount of recovered lithium per gram of solid (mg g-1). b Increase in lithium concentration in the recovery solution. C The lithium purity in the recovery solution defined as the relation between the lithium concentration in
solution and the total concentration of all cations in solution (including lithium).d The lithium purity in the solid is defined as the relation between the lithium uptake in the solid and the total uptake of all cations in the solid (including lithium). e SCE =
Saturated calomel Electrode.

4
Within the methods using battery materials, the use of redox agents to induce the reaction is

particularly well suited to be scaled-up for industrial lithium production. We first

demonstrated the suitability of the use of redox agents combined with battery materials by

employing sodium thiosulfate (Na2S2O3) to drive the lithium sequestration reaction into a

FePO4 host battery structure, thus producing LiFePO4 as the reaction product.30 As illustrated

in figure 1, once lithium is selectively sequestrated in the battery host structure (in the form of

LiFePO4), then the LiFePO4 powder is removed from the reaction mixture, and lithium is

released using an oxidising agent thus recovering the battery material (as FePO4) and

producing a lithium salt (e.g. Li2CO3) as the overall product of the whole process. Therefore,

the battery material can be used in many cycles of lithium sequestration and release, and only

the redox agents are consumed for the production of the lithium salt. In this work, we report

the use of an advantageous alternative redox agent, sodium sulfite (Na2SO3), which is

cheaper, induces a higher amount of lithium insertion per mole of reactant, is non-toxic and

the product of the reaction (Na2SO4) is completely inert. The reactions of lithium

sequestration are as follows:

Li+ + FePO4 + e- ⇌ LiFePO4 (E0 = 0.40 V vs. SHE)30 (1)

2S2O32-⇌ S4O62- + 2e- (E0 = 0.08 V vs. SHE)31 (2)

2Li+ + 2FePO4 + 2S2O32-⇌ 2LiFePO4 + S4O62- (G0 = -62 kJ/mol) (3)

SO32- + H2O ⇌ SO42- + 2H++ 2e- (E0 = -0.52 V vs. SHE, pH = 7)31 (4)

2Li+ + 2FePO4 + SO32- + H2O ⇌ 2LiFePO4 + SO42- + 2H+ (G0 = -178 kJ/mol) (5)

where E0 stands for the standard potentials and the driving force for the lithium sequestration

reactions are the lower values of standard potentials of the reducing agents (Na2S2O3 and

Na2SO3) compared to the LiFePO4/FePO4 redox potential.

Na2SO3 is a cheap and accessible reagent used in different applications, such as pulp and

paper industry,32 water treatment33 or in the textile industry.34 Additionally, it is also used in

5
chemical manufacturing as a sulfonation agent and in the production of Na2S2O3.35 Na2SO3

has also been proposed as a cost-effective alternative for battery recycling.36,37 On the other

hand, the use of Na2SO3 instead of Na2S2O3 seems to be favourable considering the

stoichiometry of the reactions (reactions 3 and 5). Indeed, reaction 5 has a stoichiometric

molar ratio Li+/Na2SO3 = 2/1, while the stoichiometric molar ratio of Li+/Na2S2O3 = 1/1

suggests that a higher amount of reducing agent would be required to induce the Li

intercalation using Na2S2O3 (reaction 3). Additionally, the reaction product of the

sequestration reaction induced by Na2SO3 is Na2SO4, which is inert and innocuous, and

Na2SO3 itself is also non-toxic.38 In this work, the use of Na2SO3 to induce the sequestration

of lithium into a FePO4 host structure is fully characterised and compared with the use of

Na2S2O3, concluding that the selectivity and kinetics of lithium sequestration reactions are

similar with both reagents, thus confirming the suitability of Na2SO3 as an advantageous

alternative reagent for the production of lithium from brines.

Figure 1. Methodology for the production of lithium using LiFePO4 battery material as

sequestering agent and redox reagents to drive the reactions.

6
MATERIALS AND METHODS

Chemical delithiation of lithium iron phospate

Commercial LiFePO4 (LFP, provided by Tatung, battery grade) was used for all the

experiments. LiFePO4 was chemically delithiated using K2S2O8 (Sigma Aldrich, ACS grade,

≥ 99%) as an oxidizing agent following the methodology reported previously.30,39 Briefly,

LiFePO4 (0.2 M) and K2S2O8 (0.1 M) were mixed in ultrapure water (18.2 M cm, Suez,

Select). The reaction was held for 24 hours at room temperature under continuous stirring.

The resultant solid was filtered, washed and dried overnight at 80 ºC. These conditions led to

the complete delithiation of LiFePO4 (LFP), obtaining FePO4 (FP) as the reaction product.30,39

Chemical lithiation of iron phospate

Delithiated LiFePO4 (FePO4 or FP, obtained as described above) was chemically lithiated

using Na2S2O3 (Na2S2O3·5H2O, Sigma Aldrich, ACS grade, ≥ 99.5 %) or Na2SO3 (Sigma

Aldrich, ACS grade, ≥ 98%) as reducing agents and Li2SO4 (Li2SO4·H2O, Sigma Aldrich,

ACS grade, ≥ 99 %) as the lithium source. In a typical experiment, a known amount of FePO 4

(around 1 g), the reducing agent (Na2S2O3 or Na2SO3) and Li2SO4 were dissolved in 35 mL of

ultrapure water under continuous stirring at room temperature. The initial molar

concentrations of the reagents in the mixture were 0.375 M FePO4, 0.75 M Li2SO4 and 1.5 M

Na2S2O3 or Na2SO3. Thus, the molar ratio of FePO4 : Li+ : reducing agent in the initial mixture

was 1:4:4. The reaction was stopped after 20 min, 1 hour or 24 hours. The resultant solid was

filtered, washed and dried overnight at 80 ºC. The solid reaction product was characterized by

XRD, galvanostatic cycling in Li-half cells, and ICP measurements of the digested solid.

Chemical extraction of lithium from artificial brines

Chemical extraction of lithium was also performed in two different artificial brines. The

molar compositions are listed in Table 2. These experiments were carried out in the presence

of 0.3 M Na2SO3. For brine 1, 0.03 M FePO4 was employed, and for brine 2, 0.1 M FePO4.

7
Therefore, the molar ratio of FePO4 : Li+ : reducing agent in the initial mixture was 1:2:10 for

brine 1 and 1:2:3 for brine 2. These initial compositions were selected so that, throughout the

process of lithium sequestration, lithium ions and the reducing agent are both in excess with

respect to FePO4 for both brine compositions. The reactions were carried out at room

temperature for 24 h. The solid reaction product was characterized by XRD, galvanostatic

cycling in Li-half cells, and ICP measurements of the digested solid.

Chloride salts, LiCl, NaCl, KCl and MgCl2·6H2O (Sigma Aldrich, ACS grade, ≥ 99%), were

used for the preparation of the brines with the exception of the potassium source in brine 2,

where K2SO4 (Sigma Aldrich, 99%) was used. These artificial brines represent two typical

compositions in the lithium reserves in Central Altiplano (Bolivia),40 and they were used in

our previous study using Na2S2O3 as reducing agent.30

Table 2. Molar compositions of the artificial brines studied in this work.

Brine LiCl NaCl KCl K2SO4 MgCl2

1 0.06 M 4.0 M 0.2 M - 0.3 M
2 0.2 M 2.4 M - 0. 3 M 1.3 M

X-ray diffraction characterization

X-ray diffraction (XRD) patterns of the materials were recorded using a Bruker D2 Phaser

diffractometer equipped with a 300 W (30 kV-10 mA) Cu Kα radiation source with a Bragg-

Brentano configuration. Scans were done at 5.3 ° min−1 for 2θ values from 10° to 50°.

Electrochemical characterisation in Li-half cells

LixFePO4 electrodes were prepared by mixing the active material (LiFePO4 as received or as

obtained from the lithiation reaction of FePO4), carbon black (Timcal SUPER C65) and

polyvinylidene fluoride (PVDF, Solef® 5130) in a weight ratio of 80:10:10. Slurry inks were

prepared using N-methyl-2-pyrrolidone (NMP) as solvent. The slurry was mixed under 2000

rpm for 5 minutes with a planetary mixer (THINKY ARE-250). This last process (2000 rpm

8
for 5 minutes) was repeated three times to obtain a homogeneous mixture. Subsequently, the

resultant slurry was hand coated on an aluminum foil (Advent Research Materials, thickness =

0.125 mm, 99%) with a K-bar to a wet thickness of 200 µm. Prior to the coating, the

aluminum foil was roughened with a P1200 sandpaper to improve adhesion. The electrodes

were dried in a vacuum oven at 80 ºC overnight and then, punched (precision punch, Nogami)

with a 11 mm diameter die and calendaring to 10 tonnes (Specac). The active material mass

loading was ≈ 3-4 mg cm-2.

The electrochemical tests were performed in PFA Swagellok® type cells, previously dried at

80 ºC overnight. The cells were assembled in an argon glove box (≤ 0.1 ppm H2O; ≤ 0.1 ppm

O2), using the LixFePO4 electrodes as working electrodes and a lithium foil (Rockwood

Lithium, 100 µm thickness, cut in 12 mm diameter discs) as both counter and reference

electrode. The electrolyte was 150 µL of 1.0 M lithium hexafluorophosphate solution (LiPF6)

in ethylene carbonate (EC) and dimethyl carbonate DMC with a volume ratio EC/DMC =1/1

(LP57, PuriEL). Two glass fibers (Whatman®, grade GF-F, 12 mm diameter) were used as

separators. Aluminium current collectors were used for the LixFePO4 electrodes, whereas

copper collectors were used on the lithium side. LixFePO4 electrodes and GF-F separators

were dried under vacuum at 120 ºC for 48 hours in a Büchi tube oven before being introduced

in the glovebox.

The cells were placed in a Memmert climatic chamber set to 25 °C and electrochemical

measurements were done with a VMP2 multichannel potentiostat (BioLogic). Galvanostatic

cycling with potential limitations (GCPL) between 2.7 and 4.1 V vs Li+/Li were performed at

a C-rate of C/10 corresponding to a specific current (normalized by the mass of Li xFePO4

active material) of 17 mAh g-1.

9
Inductively coupled plasma mass spectrometry (ICP-MS)

ICP-MS analysis were performed on a Thermo Scientific X-Series II spectrometer to

determine the amounts of Li+, Na+, K+ and Mg2+ present in the LixFePO4 solids. Samples were

digested in 2 ml of a solution of 20 wt.% of HCl (Sigma Aldrich, ACS grade, 37%) and 20

wt.% HNO3 (Sigma Aldrich, ACS grade, 70%) in ultrapure water (18.2 M cm, Suez,

Select). The mixture was stirred at 60 °C for 2 hours. PFA volumetric flasks with screw caps

were used for the digestions. The flask and stirrer were washed with ultrapure water

previously to each experiment.

RESULTS AND DISCUSSION

Kinetics of lithium sequestration by FePO4 induced by Na2SO3 or Na2S2O4

The reaction of sequestration of lithium onto a FePO4 battery host driven by Na2SO3 (reaction

5) or Na2S2O3 (reaction 3) produces LiFePO4 as a reaction product. The reaction was

characterised by mixing FePO4 power (FP, as obtained after de-lithiation of LiFePO4, LFP),

the reducing agent (Na2SO3 or Na2S2O3) and a lithium salt (Li2SO4), with initial

concentrations of 0.375 M FePO4, 1.5 M Na2SO3 or Na2S2O3 and 0.75 M Li2SO4. Under these

conditions, the initial concentration of reducing agent and Li+ are 4 times higher than that of

FePO4, thus ensuring that the reaction of lithium sequestration does not produce a significant

change in the concentrations of reducing agent and Li+, while enabling the full conversion of

FePO4 into LiFePO4. The reaction was stopped after 20 minutes, 1 hour or 24 hours, and the

solid powder reaction product was filtered, dried and characterised by XRD, electrochemical

measurements in Li-half cells and ICP measurements of the digested solid. Table 3 shows the

result of the evaluation of the lithium molar content on the LixFePO4 powder sample using

these three techniques. The kinetics of the lithium sequestration reaction are fast, since almost

full lithiation is achieved in one hour for both reducing agents.

10
Table 3. Lithium molar content, x, of LixFePO4 samples obtained by lithiation of FePO4 from

the reaction product of 0.375 M FePO4 + 0.75 M Li2SO4 + 1.5 M Na2S2O3 or Na2SO3 after

different reaction times, as indicated, as estimated from ICP (a), electrochemical (b) and XRD

(c) measurements.

Reducing
20 min 1h 24 h
agent
0.29a
Na2S2O3
0.25b 0.86b 1.02b
ref.30
0.22c 1.00c 1.00c
0.78a 0.92a 0.98a
Na2SO3 0.74b 0.90b 1.00b
1.00c 1.00c

Figure 2 shows some examples of the XRD characterisation, illustrating that nearly full

conversion to LiFePO4 is obtained with both reducing reagents after 1 hour of reaction time,

since the characteristic diffraction peaks associated to FePO4 have fully disappeared and the

diffraction peaks associated to LiFePO4 have appeared after the reaction.30

11
 ¨ Olivine LFP structure
§ Heterosite FP structure
§ § §
§
§
FP § §
§
K2S2O8 § § §§§
§ §

Intensity (a.u.)
¨ ¨ ¨ ¨
LFP
¨ ¨
Na2SO3 ¨¨ ¨
¨ ¨¨ ¨ ¨
¨ ¨
¨ ¨
LFP
¨ ¨ ¨
Na2S2O3 ¨ ¨ ¨¨ ¨
¨ ¨
¨ ¨ ¨ ¨
As received
¨
LFP ¨ ¨ ¨ ¨
¨ ¨¨ ¨ ¨

10 15 20 25 30 35 40 45
2q (°)

Figure 2. XRD patterns of the LixFePO4 solid powders obtained from the reaction product of

0.375 M FePO4 + 0.75 M Li2SO4 + 1.5M Na2S2O3 or Na2SO3 after 1 hour of reaction time.

The diffractograms of the as received LiFePO4 (LFP) powder and of FePO4 (FP) obtained

from chemical delithiation of LFP using K2S2O8 are also shown for comparison.

Electrochemical testing in Li-half cell cells was also performed to quantify the extent of

lithium insertion into the FePO4 host. For that purpose, the LixFePO4 reaction product powder

was dried and mixed with carbon and binder to produce composite electrodes that were cycled

against a lithium metal electrode in Swagelok cells in an organic carbonate electrolyte (LP57).

Figure 3 illustrates an example of the galvanostatic removal of lithium from the electrodes

prepared with the LixFePO4 reaction product obtained using Na2SO3 as the reducing agent at

different reaction times. The capacity associated with the first electrochemical extraction of

lithium from the LixFePO4 electrode is proportional to the amount of lithium present initially

in the electrode, according to the Faradays’s law. The lithium content in Li xFePO4 was

obtained taking into account that the as received, fully lithiated LiFePO4 produces an

experimental capacity of 160 mA h g-1.

12
 4.2
20 min
1hA
24 h
4.0

E (V vs Li+/Li)
3.8

3.6

3.4

0 20 40 60 80 100 120 140 160

-1
Capacity (mA h g )

Figure 3. First charge (delithiation) curves of LixFePO4 electrodes obtained from the reaction

product of 0.375 M FePO4 mixed with 0.75 M Li2SO4 and 1.5 M Na2SO3 with different

reaction times. Specific current: 17 mA g-1 (C-rate of C/10).

Figure 4 shows examples of the galvanostatic cycling done with electrodes made with the

LixFePO4 obtained from the chemical insertion driven by Na2S2O3 or Na2SO3 after 24 hours

of reaction time. The electrochemical data in figure 4a shows that full lithiation of FePO4 was

obtained with both reducing agents after 24 hours of reaction time, since the first lithium

extraction capacities were the same as in the as received LiFePO4. Further cycling of the

samples is shown in figure 4b, showing good cycling stability, in good agreement with the

measurements with the as received LiFePO4. The good electrochemical performance of the

samples obtained after the lithium sequestration reaction indicates that the present approach

could also be applied for the direct recycling of battery electrodes.41,42 For example, the

addition of a reducing agent could be used to recover fully lithiated LiFePO4 from a battery

containing used LixFePO4 electrodes that could have inhomogeneities in the lithium content

13
(or state of charge), due to, for example, the presence of regions of the electrode with poor or

no contact with the current collector as a result of electrode structural degradation.

a 4.2 b 4.2
As received LFP
LFP-Na2S2O3 4.0

4.0
LFP-Na2SO3 3.8
E (V vs Li+/Li)

E (V vs Li+/Li)
3.6

3.8 3.4

3.2

3.6 3.0

2.8

3.4 2.6

2.4
0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160

Capacity (mA h g-1) Capacity (mA h g-1)

Figure 4. First charge (a) and first discharge and second charge (b) curves of LixFePO4

electrodes obtained from the reaction product of 0.375 M FePO4 mixed with 0.75 M Li2SO4

and 1.5 M Na2S2O3 or Na2SO3 with 24 hours of reaction time. The curve of the as received

LiFePO4 (LFP) is also shown for comparison. Specific current: 17 mA g-1 (C-rate of C/10).

Selectivity of lithium sequestration from brines induced by Na2SO3 or Na2S2O3

Critical for the success in the implementation of the novel method of lithium production

proposed here is a high selectivity for lithium sequestration from solutions containing other

ions. Therefore, the selectivity was studied by performing the lithium extraction experiments

in solutions mimicking the composition of natural lithium brines, which typically contain

sodium, magnesium and potassium in much higher concentration than lithium, see table 2.

Although the electrochemical insertion of sodium into the FePO4 structure obtaining

NaFePO4 has been reported by several authors,43–48 it is kinetically slower than the formation

of LiFePO4, 27,48–50 and it has been suggested that the introduction of small amounts of lithium

14
in the FePO4 structure could block the insertion of sodium ions.51 On the other hand, the

insertion of magnesium or potassium into FePO4 seems to be prevented.27 In order to assess

the applicability of the new reducing agent proposed here for commercial applications, two

artificial brines were used with similar compositions to those found in lithium reserves in

Central Altiplano (Bolivia).40

Figure 5 shows the XRD patterns of the solids obtained by reaction of FePO4 in brines in the

presence of 0.3 M Na2SO3 after 24 hours of reaction. The characteristic peaks of the olivine

LiFePO4 structure were the only peaks observed for both artificial brine compositions,

indicative of the complete chemical insertion of lithium ions forming LiFePO4 only. The

insertion of Na+ into FePO4 would produce characteristic diffraction peaks associated to

olivine NaFePO4,44 which are not observed experimentally. The insertion of any other cation

in the FePO4 structure, including the insertion of protons, would also produce the appearance

of diffraction peaks at different reflection positions,52 and therefore, it can be excluded too.

Figure 6 shows the results of the electrochemical characterisation, showing the same behavior

as the as-received LiFePO4 sample, which again confirms the formation of fully lithiated

LiFePO4 as the reaction product. Similar results were previously reported using the same

experimental conditions but with Na2S2O3 as reducing agent.30

15
 ¨ Olivine LFP structure
¨ ¨ ¨
¨
LFP-Brine 2
¨
¨ ¨
¨ ¨ ¨¨
¨ ¨
¨¨ ¨
Intensity (a.u.) ¨ ¨ ¨
¨

¨ ¨ LFP-Brine 1
¨ ¨ ¨ ¨¨ ¨
¨ ¨¨ ¨

¨ ¨ ¨
¨

¨ ¨ As received LFP
¨ ¨
¨ ¨ ¨¨ ¨
¨¨ ¨

10 15 20 25 30 35 40 45 50

2q (°)

Figure 5. XRD patterns of the LixFePO4 solid powder obtained from the reaction of FePO4 in

brines with 0.3 M Na2SO3 after 24 hours of reaction. The diffractograms of the as received

LiFePO4 (LFP) powder is also shown for comparison.

a b 4.2
4.2
As-received LFP
4.1 LFP-Brine1 4.0
LFP-Brine2
4.0 3.8
E (V vs Li+/Li)
E (V vs Li+/Li)

3.9 3.6

3.8 3.4

3.7
3.2

3.6
3.0
3.5
2.8
3.4
2.6
0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160

Capacity (mA h g-1) Capacity (mA h g-1)

Figure 6. First charge (a) and first discharge and second charge (b) curves of Li xFePO4

electrodes obtained from the reaction of FePO4 in brines with 0.3 M Na2SO3 after 24 hours of

reaction. Curves of the as received LiFePO4 (LFP) are also shown for comparison. Specific

current: 17 mA g-1 (C-rate of C/10).

16
Table 4 compares the results of ICP elemental analysis of the digested LixFePO4 obtained

with the two different brines using Na2SO3 as reducing agent; the results using Na2S2O3 are

also included for comparison purposes. The values of Li, Na, K and Mg uptake reported here

have been defined as the amount of ion, in mg, normalized to the mass, in g, of the absorbing

material (FePO4). For full lithiation of FePO4, forming LiFePO4, the Li uptake is expected to

be 46 mg g-1. Table 4 shows that, for both reducing agents (Na2SO3 and Na2S2O3), the Li

update is indeed close to 46 mg g-1. Furthermore, it is observed that the uptake of other

cations is very small, thus demonstrating the high selectivity for lithium.

From the ICP results, it is useful to calculate the molar ratio of lithium ion and other cations

(M = Na+, K+ or Mg2+) in the solid ([Li+] solid:[M]solid, see values in table 4). This can, then, be

compared to the molar ratio of lithium and other cations in solution ([Li+]solution:[M]solution, see

table 4). Clearly, lithium is a minority component in solution (that is, in the artificial brines),

because the values of [Li+]solution:[M]solution are very small. But then lithium becomes the

majority component in the solid (that is, in LixFePO4) because the values of [Li+]solid:[M]solid

are very high. In order to quantify this change in relative abundance of Li with respect to

other cations in the solid with respect to the solution, and following our previous work,30 we

have defined the lithium selectivity as the enhancement of the lithium concentration over that

of other cations in the solid with respect to the solution:

[Li  ] solid :[M]solid

Lithium selectivity = (6)
[Li  ] solution :[M]solution

Table 4 shows that the use of Na2SO3 produces very high values of lithium selectivity, similar

to that with Na2S2O3. While the present ICP measurements were done in aqueous solutions,

which prevents the evaluation of proton insertion into FePO4, previous experimental and

17
 theoretical studies have shown that the insertion of protons or hydrogen into FePO4 is

negligible.52,53

The ICP results can also be used to calculate the lithium purity in the solid, which equals the

uptake of lithium by the solid divided by the sum of the uptakes of all cations. With Na 2SO3,

the lithium purity in the solid equals 94% and 96% for brines 1 and 2, whereas for Na2S2O3, it

is 90% and 96%. Thus, it is concluded that very high lithium purities in the solid can be

achieved by this method: the values of lithium purity compare well with the lithium purity in

the recovery solution reported in previous studies (see table 1). Further improvements in

lithium purity could be achieved via the optimization of the process and materials. For

instance, the LiFePO4 used in this work has been optimized for battery performance in terms

of particle size, carbon coating etc., but the properties required are different for lithium

production/recycling applications.

Table 4. Li, Na, K and Mg uptakes and lithium selectivity of samples obtained by the reaction

of FePO4 with Na2S2O3 or Na2SO3 in artificial brines 1 or 2 (see table 2) for 24 hours of

reaction time.

Reducing Uptake [Li+]solution: Lithium

Brine M [Li+] solid:[M]solid
agent (mg g-1) [M]solution selectivity
Li+ 45.7
Na+ 2.5 1:77 61:1 4700
Brine 1
K+ 1.5 1:3 170:1 510
Na2S2O3 Mg2+ 0.8 1:5 200:1 1000
ref.30 Li+ 46.4
Na+ 0.4 1:15 370:1 5550
Brine 2
K+ 1.4 1:3 180:1 540
Mg2+ 0.2 1:6.5 870:1 5600
Li+ 45.5
Na+ 0.9 1:77 164:1 12560
Brine 1
K+ 0.3 1:3 782:1 2608
Mg2+ 1.9 1:5 84:1 422
Na2SO3
Li+ 44.1
Na+ 0.2 1:15 585:1 8773
Brine 2
K+ 0.2 1:3 1060:1 3181
Mg2+ 1.3 1:6.5 118:1 765

18
CONCLUSIONS

Na2SO3 is shown to be an advantageous reducing reagent to drive the selective sequestration

of lithium from natural brines into a FePO4 host battery material, for applications in an

alternative and sustainable method of lithium production, as illustrated in figure 1. The

kinetics of the lithium sequestration reaction are found to be fast, since full lithiation is

achieved in one hour in 1.5 M Na2SO3 solutions. The selectivity of the lithium sequestration

reaction is found to be outstanding, since in natural brine solutions containing up to 60-fold

excess of sodium, 6-fold excess of magnesium and 3-fold excess of potassium, the amount of

lithium inserted per gram of solid absorbant is ca. 45 mg/g whereas the uptakes of sodium,

potassium and magnesium were below 0.9, 0.3 and 1.9 mg/g, respectively. Consequently, the

kinetics and selectivity of the lithium sequestration reactions are comparable to those

previously reported using Na2S2O3 as reducing agent.30 However, Na2SO3 has advantages in

terms of lower cost, reaction stoichiometry that involves less consumption of reagent, non-

toxicity and formation of an innocuous reaction product (Na2SO4).

Acknowledgments

Profs. John R. Owen, Phil N. Bartlett, Derek Pletcher, Andrew L. Hector, Ernesto Calvo and

Victoria Flexer are gratefully acknowledged for fruitful scientific discussions and Prof.

Andrew L. Hector is also acknowledged for his help in the preparation of Figure 1. Financial

support given to the project "A highly versatile selective approach for lithium production" by

the Royal Society (IC170232) is also acknowledged, and NGA thanks the EPSRC for an early

career fellowship (EP/N024303/1). The data for this article are available from the University

of Southampton at https://doi.org/10.5258/SOTON/D1235.

19
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Synopsis: Selective lithium sequestration

from natural brines with a battery
material using a novel reducing agent,
sodium sulphite, as a sustainable new
approach for lithium production.

24