Lithium Extraction from Geothermal Brine Solution · 2 Open slide master to edit List of estimated global Lithium end-use applications Source: L. Li, V. Deshmane, M. P. Paranthaman,

ORNL is managed by UT-Battelle, LLC for the US Department of Energy

Lithium Extraction from Geothermal Brine Solution

Parans ParanthamanChemical Sciences Division

Oak Ridge National LaboratoryOak Ridge, TN 37831-6100

Email: [email protected]. (865) 386-9030 (cell)

This research was supported by the Critical Materials Institute, an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Advanced Manufacturing Office. • Sam Evans, Ramesh Bhave, Ilja Popovs, Bruce Moyer (ORNL);

Stephen Harrison (All American Lithium); L. Wu, A. Navrotsky (UC, Davis)

mailto:[email protected]

22 Open slide master to edit

List of estimated global Lithium end-use applications

Source: L. Li, V. Deshmane, M. P. Paranthaman, R. Bhave, B. Moyer, S. Harrison, “Lithium recovery from aqueous resources and batteries – a brief review,” Johnson Matthey Technology Review, 2018, 62(2), 161-176. DOI: 10.1595/205651317X696676


Demand for Lithium is expected to increase drastically

Source: SQM

LCE: Lithium carbonate


Lithium: Market outlook

Source: Roskill, Benchmark Mineral Intelligence, UBS Estimates

Lithium hydroxide and Lithium carbonate cost are projected to go up


Lithium cost production


Lithium salts/compound conversion factors*Compound Formula Lithium

Content (%)Convert to Li

Convert to Li2O

Convert to Li2CO3

Convert to LiOH

Lithium Li 100 1.000 2.152 5.322 3.451Lithium Oxide

Li2O 46.46 0.465 1.000 2.473 1.603

Lithium Chloride

LiCl 16.37 0.164 0.705 1.743 0.565

Lithium Carbonate

Li2CO3 18.79 0.188 0.404 1.00 0.648

Lithium Hydroxide

LiOH 28.98 0.290 0.365 1.542 1.00

*Note: Assuming compounds with no water content

Battery grade (>99.5% Li, 0.50% H2O, 0.05% Na2O) - high end battery cathode materials

Source: LPI


Lithium Reserves and Lithium Resources (2016)

69 MMT of LCE (Estimated)LCE: Lithium carbonate

160 MMT of LCE (Estimated)

Source: SQM


Lithium production by country (2017)

Total production: 208 MT LCE (2017)

Source: SQM

(2-3%)


Lithium: Identified as near-critical

Medium Term: 2015 – 2025

Critical Materials Institute (CMI) Mission:To assure supply chains of materials critical to clean energy technologies,

enabling innovation in US manufacturing, and

enhancing US energy security.

https://cmi.ameslab.gov/

https://cmi.ameslab.gov/


Lithium sources Minerals (2,300 – 18,000 ppm)

• About 145 mineralogical species; few commercial sources (e.g. spodumene (lithium aluminosilicate), petalite (castorite) and lepidolite)

• Sedimentary clays (e.g. Hectories in USA y jaderites in Serbia) (2,000 – 3,000 ppm)

• Sea water (0.17 ppm)

Recycling lithium-ion batteries

Brines• Continental brines (100 – 2,700 ppm)• Geothermal brines (e.g. Imperial Valley, California, USA) (250 – 400 ppm)• Dried out “Salares” (e.g. Hombre Muerto in Argentina; Uyuni in Bolivia;

Atacama in Chile) (up to 1,800 ppm)• Salt lakes (e.g. Zhabuye and Qinghai in China)• Oil field brines (e.g. Smackover, Texas, USA) (60 – 500 ppm)• Clayton valley brines (Nevada, USA)


Recovery of lithium from spodumene (ORNL: 1959)

Differential thermal analysis

Source: N. P. Kotsupalo Theor. Found. Of Chem. Engg. 44 (4) 503(2010)


Foote lithium company status


Lithium recovery process from minerals, clay

Source: B. Swain, Separation and Purification Technology, 172, 388-403 (2017)

• Typical mine ore may contain 1-2% Li2O, however spodumene ore may contain 6-7% Li2O and higher grade may contain 7.6% Li2O.

• Issues: Too expensive; energy intensive process; secondary wastes.


Lithium-ion battery recycling


Lithium-ion batteries

C6 + LiCoO2 ↔ LixC6 + Li1-xCoO2

Anode: CarbonCathode: Lithium Cobalt Oxide, LiCoO2Electrolyte: 1 M Lithium hexafluoro-phosphate, LiPF6 in

Ethylene carbonate and Diethyl carbonate(EC/DEC)

During charging: C6 + x Li+ → LixC6 (anode)LiCoO2 → Li1-xCoO2 + x Li+ (cathode)

During discharging: Reverse reaction occurs

Critical elements: Li, Co, Graphite


Lithium-ion batteries with different cathode compositions

CathodeaAverage

Voltage vs. (Li/Li+)

Practical capacity (mAh/g)

AnodeAnode

capacity(mAh/g)

Cell specific energy (Wh/kg)

LiCoO2 3.8 140 graphite 350 185LiFePO4 3.45 150 graphite 350 176NMC-111 3.8 155 graphite 350 199NMC-424 3.85 155 graphite 350 201NMC-523 3.75 165 graphite 350 205

NCA 3.7 180 graphite 350 214HC-1 3.7 220 graphite 350 223HC-1 3.7 220 Si

composite1500 380

HC-2 3.7 250 graphite 350 263HC-2 3.7 250 Si

composite1500 425

a NMC-111: Li[Ni1/3Mn1/3Co1/3]O2; NMC-424: Li[Ni0.4Mn0.2Co0.4]O2; NMC-523: Li[Ni0.5Mn0.2Co0.3]O2; NCA: LiNi0.80Co0.15Al0.05O2; HC-1 and HC-2: xLi2MnO3∙(1-x)LiMO2.

Li-Sulfur batteries and Solid-state lithium ion batteries (Beyond Li-ion)


Recovery of carbon from recycled tires for clean energy applications (ORNL)

Electrodes for batteries and supercapacitors

Carbon catalyst for converting waste cooking

oils into biodiesel

Lithium-ionbatteries

Electrodes for cell phone and laptop batteries

Catalyst – Fuel cell; water desalination

(capacitive deionization) Se removal

• Journal Publications: 10• US Patents Issued: 3• Licensed the technology to

RJ Lee Group; FWD Energy

CMI FA1 Project: Sheng Dai (ORNL)


Lithium-ion battery cell composition

Christian Hanisch, Li-ion battery recycling webinar (2016)


Lithium-ion battery recycling processes



Lith O Rec II process


CMI FA3 Projects: T.J. McIntyre (ORNL) and T. Lister (INL)


Table of world brine compositions (Li and cations with higher concentrations)



Global comparison: Li grade in salt lakes

Estimates: 10.6 M MT of LCE at Salton Sea 100 km2 field; Mn, Zn and K can be recovered as well


Potential recovery of chemicals from brine solution

Current Market: $ 2.1 Billion Source: SQM


Li recovery process from Salar brines

Source: SQM Li recovery time: 18-24 months

Flow-chart


Salton sea brine

Brine compositionmg/kg mg/kg

Na 53,000 Li 250

K 20,000 Mn 1,500

Ca 33,000 Zn 500

SiO2 200 Cs 20

Fe 1,500 Rb 100

TDS 30wt% Cl 180,000

pH 5

• Geothermal Brines• Hutson Ranch II Geothermal Plant – 50 MW –

LCO capacity (15 MT/year)• Cal energy owns 13 geothermal power plants

with a capacity of ~ 375 MW – potential for 200 MT/year


To injection well

Brine

Silica mgmt. Lithium adsorption

By-products:Colloidal silica

Iron compounds

Mn / Zn precipitation

Manganesesulfate

Zinc sulfate Product

conversion

Lithium carbonate

(Li2CO3)

Lithium hydroxide

(LiOH)

Lithium chloride

Silica removal Improved Li sorbentsZn and MnO2

lab tests

Manufacture of cathode materials

K recovery

Lab tests and field demonstration

CMI Lithium project is focused on Li extraction from geothermal brine, purification, concentration and conversion (marked in a red box)

Lithium removal process flow from geothermal brine

Membrane: Forward osmosisSolvent Extraction: Li purificationNanoengineered sorbents: Ambient temp. brines

Source: S. Harrison, Simbol Final DOE GTO DE-EE0002790 Report (2014)


Three types of sorbents usedSpinel Lithium Manganese Oxide (Li-Mn-O)Spinel Lithium Titanium Oxide (Li-Ti-O)Lithium Aluminum Layered Double Hydroxide Chloride (LDH)

Recovery of lithium from brines by adsorption/ion-exchange



Li-Mn-O exhibited a high ion-exchange capacity and high selectivity for lithium ions from various aqueous resources.

The acid generated during lithium uptake needs to be recycled for regenerating the sorbents. This could potentially reduce the cost of the acid consumption itself.

Some of the common issues with the Li-Mn-O sorbents are the dissolution of Mn2+ in the acid during the regeneration process, causing a decrease in the ion-exchange capacity and a poor cycling stability.

Further studies are needed to improve the stability during cycling to realize a stable ion-exchange capacity.

Li-Mn-O based sorbents - Summary



H2TiO3 is an attractive sorbent for selective lithium extraction with superior advantages including high ion-exchange capacity, high selectivity, high stability, environmentally-friendliness, and economic-efficiency.

There are no issues with Ti dissolution in acid solutions.However, it is still at the laboratory scale, partly due to the acid

requirement during the regeneration process, which produces secondary wastes.

Li-Ti-O based sorbents - Summary



Lithium layered double aluminum hydroxide chloride (LDH) is an attractive candidate for application in large-scale industrial plants due to its various advantages, including low cost, environmental-friendliness, easy regeneration.

LDH has a general formula [LiAl2(OH)6]+Cl-·nH2O. Crystallized in the hexagonal symmetry with the Li+

located in the vacant octahedral sites within the Al(OH)3layer.

[LiAl2(OH)6]+ layers are separated by water molecules and hydroxide ions.

Li/Al LDHs can be synthesized by intercalating LiCl into gibbsite (α-Al(OH)3)

LDH based sorbents - Summary

Source: M. P. Paranthaman, L. Li, J. Luo, T. Hoke, H. Ucar, B. A. Moyer, S. Harrison, “Recovery of lithium from geothermal brine with lithium aluminum layered double hydroxide chloride sorbents,” Environmental Science and Tech. 2017, 51, 13481. DOI: 10.1021/acs.est.7b03464.


Li/Al layered double hydroxide chloride (LDH) sorbents• Lithium chloride is intercalated into interlayers of hexagonal gibbsite.

Source: C.J. Wang and D. O’Hare, Topotactic synthesis of layered double hydroxide nanorods, J. Mater. Chem. 22, 23064-23070 (2012). DOI: 10.1039/C2JM34670B


• The XRD peaks of the sorbent synthesized at 90°C are sharper, which is indicative a better crystallinity.

• Scaled up this process to prepare 2 kg quantities

Optimizing the reaction temperature for LDH sorbents



(d) 90°C

(a) 18°C

(b) 30°C

(c) 40°CMicrostructure of the LDHs with Al/Li = 2:1 synthesized at various temperatures

Optimizing the reaction temperature for LDH sorbents



Bench-scale selective column extraction of LiCl from simulated geothermal brine using LDH sorbents

Load Wash StripSource: M. P. Paranthaman, L. Li, J. Luo, T. Hoke, H. Ucar, B. A. Moyer, S. Harrison, “Recovery of lithium from geothermal brine with lithium aluminum layered double hydroxide chloride sorbents,” Environmental Science and Tech. 2017, 51, 13481. DOI: 10.1021/acs.est.7b03464.

Operation at 95°C


Summary: LDH is effective in extracting Li from geothermal brine. However, ~ 180 ppm of K and ~ 520 ppm of Na are still present in the strip eluate solution. Further purification process is needed to selectively remove Li from K and Na.• Alternate methods are being explored in CMI to address this

issue

ICP data on the strip eluate solution with LDH sorbents



C&E News cited ORNL research



Achievement:Successfully demonstrated the continuous bench-scale extraction of nearly 100% LiCl recovery from simulated brine for nearly 500 hours of operation using newly developed sorbents.

Significance and ImpactLong-term stability of the sorbent and separation performance is prerequisite to industry acceptance, potentially leading to a major, expandable domestic supply of lithium

Research Details Prepared newly developed sorbents and scaled up to 200 g batches

using a low-pressure reactor Successfully conducted semi-automatic bench-scale extraction of

LiCl for up to 500 hours through 100 cycles of load, wash, and strip Eluants were collected manually at various strip cycles for ICP

analysis >95% recovery of LiCl from simulated geothermal brine achieved

under process conditions XRD analysis of sorbents after 500 hours of operation indicated no

major change except some minor phases present

Successfully demonstrated the continuous operation of bench scale column extraction for 500 hours using sorbents


Lithium and Sodium Extraction w HDBM and TOPO

Method

• Extraction using Dibenzoylmethane (HDBM) and Trioctylphosphine oxide (TOPO).

• Aqueous Phases: 1. 0.02 M LiCl, 0.1 M KOH and

0.88 M KCl (total metal conc: 1M)

2. 0.02 M LiCl, 0.1 M KOH (total metal (0.12 M)

3. 0.02 M NaCl, 0.1 M KOH and 0.88 M KCl (total metal conc: 1M)

• Organic Phase: 0.1 M HDBM and 0.1 M TOPO in Toluene

Lithium and Sodium Extraction

Observations and Future Work• Extraction of Li > Na

• Calculated SF = 324.

• Without KCl in solution 2 a white precipitate formed at the interface but Li detected in the organic phase very similar to solution1.

To do:

• Mary Healy, Ilja Popovs are working to develop alternate ligands.

Confirmation of literature/method: J. Inorg. Nucl. Chem 1968, Vol 30, pp 2807 - 2821

31.90

0.100.00

5.00

10.00

15.00

20.00

25.00

30.00

35.00

Li Na


LDH sorbents: Formation enthalpies and energetics for lithium ion capture

Source: L. Wu, S. F. Evans, T. A. Eskander, B. A. Moyer, Z. Hu, P. J. Antonick, S. Harrison, M. P. Paranthaman, R. Riman, A. Navrotsky, “Lithium Aluminum Layered Double Hydroxide Chlorides (LDH): Formation Enthalpies and Energetics of Lithium Ion Capture”, Journal of the American Ceramic Society (2018) DOI: 10.1111/jace.16150


Enthalpy of formation of LDH with various LiCl ratios and Fe doping levels

Source: L. Wu, S. F. Evans, T. A. Eskander, B. A. Moyer, Z. Hu, P. J. Antonick, S. Harrison, M. P. Paranthaman, R. Riman, A. Navrotsky, “Lithium Aluminum Layered Double Hydroxide Chlorides (LDH): Formation Enthalpies and Energetics of Lithium Ion Capture”, Journal of the American Ceramic Society (2018) DOI: 10.1111/jace.16150


LDH or Fe-LDH sorbent is mixed with DI water in order to “unload” Li from the structure in a well sealed container at 95°C.

This unloaded LDH is used in trials to load Li from the brine solution Sorbent structure studied using X-Ray Diffraction

Trials 0.5 g sorbent, 10 mL brine at different concentrations placed in a well sealed vial Agitated and kept at room temperature for 24 hours Filtered, Diluted, Run with Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-

OES)

Loading and unloading trails (batch process)


0 100 200 300 400 500 600 700 800 900 1000

16

18

20

22

24

26

28

30

Li in aqueous phase (mg/L)

Li in

sor

bent

(mg/

g)

Fe-LDH LDH

• Lithium in geothermal brine is ~ 250 ppm

• Absorption capacity in LDH and Fe-LDH is similar : 6 mg/g

• Also determined the stability of LDH phase of up to 125 °C

95 °C; stirred conditions; 1h;0.125 mg sorbent/5 ml brine

Developed isotherms of Li absorption for LDH sorbents


Brines to Batteries

Geothermal Zone

Brine

LiExtraction

Plant

Flash SteamPower Plant

Source: Y. Li, G. Fu, M. Watson, S. Harrison, and M. P. Paranthaman, “Monodispersed Li4Ti5O12 with controlled morphology as high-power lithium ion battery anodes,” ChemNanoMat 2, 642-646 (2016); DOI: 10.1002/cnma.201600106.

Achievement:Successfully demonstrated the continuous cycling of lithium ion batteries with a stable performance of up to 300 cycles at one charge-discharge rate.


Recent workshop on Lithium Recovery from Geothermal Brine


Summary and outlook

• Extraction of lithium from geothermal brine seems to be economically and environmentally attractive

• LDH and modified LDH sorbents; other compositions are promising – high selectivity; high capacity

• Membrane and solvent extraction are good for further purifying the eluate downstream solution for achieving high purity LiCl

• Recycling of lithium-ion batteries

Documents

Lithium Extraction from Geothermal Brine Solution · 2 Open slide master to edit List of estimated global Lithium end-use applications Source: L. Li, V. Deshmane, M. P. Paranthaman,