DDifferent Production Routes

i to Lithium Hydroxide

Introduction

Standard Lithium Hydroxide Production

Principle of Membrane Electrolysis

Impurity Removal

Alternative Lithium Sources

Membrane Electrolysis from Li 2SO4 Liquor

Crystallization Subsequent to Electrolysis

Introduction
Lithium carbonate is at least partially replaced as final product of lithi-
um extraction. Battery manufacturers, a major consumer of lithium
compounds with strongly growing demands, show an increasing inter-
est in employing lithium hydroxide instead of lithium carbonate, since it
presents a number of advantages in the production of high capacity
electrode materials.

Standard lithium hydroxide production

by lithium carbonate conversion
Classically LiOH is produced from Li2CO3 by reaction with Ca(OH)2 ac-
cording to equation 1.

Li2CO3 + Ca(OH)2 → 2LiOH + CaCO3 (1)

The process yields a LiOH liquor with lithium concentrations of approx.

3 wt.-%. At higher concentrations Li losses in the solid side product
CaCO3 would be obtained. By evaporation of the liquor, LiOH is ob-
tained as monohydrate.

Currently the classical process is more and more challenged by a pro-

cess called membrane electrolysis.

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Principle of Membrane electrolysis
In membrane-electrolysis an aqueous lithium bearing solution is elec-
trolyzed and lithium forms at the cathode. Since it is highly reactive,
lithium instantly forms LiOH and hydrogen in the aqueous medium
(equations 2 & 3).

Li+ + e- → Li (2)
2Li + 2H2O → 2LiOH + H2 (3)

This process can yield LiOH liquors of much higher concentration

(approx. 2 times higher) compared to the standard process, thus less
energy is required for subsequent crystallization.

If the lithium liquor is sufficiently pure it can directly employed for

electrolysis and no intermediate carbonate precipitation step is re-
quired.

LiOH liquor also allows for the production of lithium carbonate by intro-
ducing carbon dioxide (equation 4).

2LiOH + CO2 → Li2CO3 + H2O (4)

Impurity levels of individual elements have to be minimized by an ap-

propriate treatment in order to enable the direct production of lithium
hydroxide from the liquor via membrane electrolysis. Initial impurity
levels are of course depending on the source material.

Brines are in general not suitable for direct electrolysis, since they con-
tain high concentrations of alkali metals such as sodium or potassium.
These impurities can hardly be removed from the liquor, thus one has
to follow the standard route and lithium has to be precipitated as car-
bonate for purification. Nevertheless it is possible to transform purified
Li2CO3 to LiOH by electrolysis instead of using the precipitation process.

Spodumene or petalite mineral concentrates obtained from hard rock

sources are favorable for direct production of LiOH.

They are commonly processed by roasting with sulfuric acid followed by

a water leach. These minerals also release impurities to the leach.
While brines contain mainly other alkali metals, a hard rock leach con-
tains impurities like aluminum, iron or manganese. Adjusting the pH to
9 - 10 these impurities precipitate as hardly soluble hydroxides which
can then be easily removed by filtration.

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The selection of an appropriate reagent for pH adjustment of the liquor
is extremely important to condition it in the ideal way for use as feed in
electrolysis. The standard spodumene processing as e.g. applied by
Talison Lithium uses sodium hydroxide for impurity removal. By reac-
tion with sulfuric acid soluble sodium sulfate is formed. This leads to
high sodium content in the liquor. While the Na content can be sepa-
rated easily in lithium carbonate precipitation, in electrolysis a mixture
of NaOH and LiOH would be obtained.

Impurity Removal
As discussed above application of an appropriate pH adjustment agent
will yield a hardly soluble product which can be readily separated from
the liquor by filtration.

Calcium oxide or hydroxide is an example of suitable reagents for pre-

cipitation of impurities. Both are relatively inexpensive and form hardly
soluble gypsum upon reaction with the sulfuric acid as displayed in
equation 5.

H2SO4 + Ca(OH)2 → 2 H2O + CaSO4 (5)

Applying these reagents very pure liquor at only slightly increased cal-
cium concentrations is obtained. While sodium can hardly be removed
from the liquor, calcium can be easily separated by carbonate precipi-
tation (e.g. by addition of Li2CO3 or CO2) and by ion exchange. Alterna-
tively LiOH could be the applied for pH adjustment. But since the re-
quired amounts are very high, the required amount of LiOH for neutral-
ization significantly reduces the product yield; this alternative is com-
monly not applied.

By appropriate processing with suitable reagents liquor containing

mainly Li2SO4 with only minor impurities can be obtained. Processing
routes based on lithium chloride play a very subordinate role and are
not in the scope of this article.

Lab tests at ANZAPLAN have shown that by causticizing of an acidic

spodumene leach with Ca(OH)2 a liquor having a Li/Na ratio of 26.5
was obtained. When NaOH was applied for causticizing, the liquor the
Li/Na ratio was 0.065. Residual Calcium content in the liquor was
approx. 50 times higher when calcium was applied. But by precipitation
with a carbonate (preferably Li2CO3) followed by ion exchange this
content could be easily reduced below the detection limit. Since ion
exchange was applied that removes most polyvalent ions, also trace of
many other nuisance elements could be removed. Thus electrolysis can
be fed with liquor containing only alkali metals.

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Alternative Lithium Sources
If Li micas (e.g. zinnwaldite or lepidolite) are applied as lithium source
minerals, processing is different from the above discussed processing.
Though the number of Li mica deposits significantly exceeds the num-
ber of spodumene or petalite deposits these minerals are seldomly
applied for Li extraction. Main reason for this being that most micas
have lower lithium contents than spodumene or petalite.

Additionally, the composition of micas differs significantly from those of

spodumene or petalite resulting in a leach that commonly contains
several elements (especially alkali metals) that can be hardly removed
from the liquor. Thus the lithium liquor obtained from a mica leach
cannot be directly used in electrolysis but has to be pretreated.
Figure 1: Three chamber-setup for an
electrolysis of lithium sulfate
All existing Li mica projects producing lithium hydroxide follow the
classical production route via conversion of lithium carbonate.

Membrane Electrolysis from Li2SO4

Liquor
During electrolysis of a Li2SO4 liquor at the anode sulfuric acid is
formed (equation 6).

2 SO42- + 2 H2O → 2 H2SO4 + O2 + 4 e- (6)

LiOH formed at the cathode immediately reacts to lithium sulfate, re-

sulting only in the electrolysis of water. Therefore it is necessary to
physically separate anode and cathode by a membrane. Those mem-
branes have to be ion selective, so that only cations can move towards
the cathode and no back diffusion towards the anode is possible.

The common setup for this process consists of three chambers (Fig.1).

Li2SO4 liquor is fed to the central chamber which is separated from the
outer electrode containing chambers by membranes. During electroly-
sis the cathode chamber is enriched with LiOH while the anode cham-
ber is enriched in sulfuric acid.

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Crystallization Subsequent to
Electrolysis
Electrolysis cannot separate lithium from other alkali metals occurring
in solution. The main focus of electrolysis is to enrich the solution in
the cathode chamber and to separate lithium from its anion (commonly
sulfate).

Sodium and potassium occurring in solution will also be enriched in the

cathode chamber.

Thus it is crucial to carefully control crystallization subsequent to elec-

trolysis. Since solubility of LiOH in water is approximately ten times
lower compared to NaOH and KOH as stated in Table 1, it is possible to
crystallize the major part of LiOH without co-precipitation of NaOH and
KOH.

Table 1: Solubilities of alkali hydroxides at 20 °C in water

Compound Solubility [g/l]

LiOH 128
NaOH 1,090
KOH 1,120

Electrolysis results only in the separation of the metal from the anion
(i.e. sulfate in hard rock leaches and chloride in brines). There is no
separation between different alkali metals during electrolysis. Thus,
due to lack of alkali elements other than lithium, both petalite and
spodumene are ideal sources for direct production of LiOH without in-
termediate precipitation of Li2CO3 whereas brines or liquors from mica
leaching contain significantly higher amounts of sodium and potassium.
The resulting liquor from mica leaching is a mixture of LiOH, NaOH and
KOH making a separation of pure LiOH by fractional crystallization at
satisfactory recoveries impossible.

To prove the amount of purification crystallization tests at ANZAPLAN

with liquor containing LiOH and NaOH has provided results showing the
Li/Na ratio of the sample could be increased by a factor of 15.

For recovery of residual lithium contained in the remaining liquor, it is

possible to saturate the solution with carbon dioxide, to form hardly
soluble lithium carbonate.

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Analysenzentrum
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gesellschaft mbH
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