ZnMnO 2 Batteries Timothy N Lambert SAND201911277 C DOEOE Peer Review Hotel Andaluz Albuquerque New Mexico September 24 2019 PROJECT OVERVIEW ZnMnO 2 Batteries 2 Need Safe reliable ID: 773434
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Zn/MnO2 Batteries Timothy N. Lambert SAND2019-11277 C DOE-OE Peer Review, Hotel Andaluz , Albuquerque, New Mexico, September 24, 2019
PROJECT OVERVIEW –Zn/MnO 2 Batteries 2 Need : Safe, reliable, low-cost electrochemical storage Cost Traditional alkaline primary batteries - $18-25 per kWhLow-cost materials and manufacturingEstablished supply chain Safety Aqueous chemistry Non-flammableEPA certified for landfill disposalReliabilityLong shelf-lifeLimited thermal management required Zn/MnO2 Batteries Reversibility and Cycle life are the Challenges Intermittent sources requires storage Wind/PV: ~ 30% of 43 GW new construction OE support of RESEARCH&DEVELOPMENT needs of battery chemistries that could impact Grid Storage: Reliable and resilient electricity system
PROJECT OVERVIEW 3 Technical Challenges Facing Zn/MnO 2 Cathode: Irreversibility of Cathode Susceptibility to Zinc poisoning Separator:Zincate crossoverAnode: Shape ChangeDendrite GrowthIrreversible ZnO Passivation820 mAh/g616 mAh/gMnO 2 Zn (Image adapted from CCNY) Full 2e - equivalent can be realized but is still susceptible to zinc poisoning G. G. Yadav, J. W. Gallaway , D. E. Turney , M. Nyce, J. Huang, X. Wei and S. Banerjee, Nat. Commun . , 8, 14424 (2017). Limiting Depth of Discharge has been shown to be a viable approach N. D. Ingale , J. W. Gallaway , M. Nyce, A. Couzis and S. Banerjee, J. Power Sources , 276, 7 (2015). Problem : Cycling Zn/MnO 2 (both electrodes) at high capacities for thousands of cycles - not realized Founded 2012
PROJECT TEAM 4 Dr. Jonathon Duay , Dr. Matthew Lim, Dr. Igor Kolesnichenko , Dr. Noah Schorr, David Arnot, Rachel Habing, Logan Ricketts, Rachel HabingAlkaline Batteries for Grid Storage ( FY19 Funding $700k )Dr. Timothy LambertProf. Sanjoy Banerjee Stable Zinc Anodes for High-Energy-Density Rechargeable Aqueous Batteries (FY19 $148k ) Theoretical Studies of the Electrochemical Behavior of g -MnO 2 Cathode Material in Rechargeable Zn/MnO 2 Batteries ( SNL-LDRD Leveraged Project, OE for FY20 ) Prof. Igor Vasiliev Birendra A. Magar Manufacturable Low-Cost MnO 2 Birnessite cathode ( FY19 $90k ) Dr. Damon Turney, Dr. Gautam Yadav, Michael Nyce , Brendan Hawkins, Jinchao Huang, Snehal Kolhekar Dr. Andrea Bruck, Matthew Kim Understanding Phase Change Processes of Energy Storage Materials ( FY19 $105k ) Prof. Joshua Gallaway Advanced Materials for Next Generation Batteries ( FY19 $120k ) Prof. Esther Takeuchi
PROJECT TEAM 5 OE support of RESEARCH & DEVELOPMENT, MANUFACTURING and DEMONSTRATION of Potentially Wide Impact, Low Cost Energy Storage Technologies Highlight of accomplishments $50/kWh (at scale) S. Banerjee Progress on Development of the Zn-MnO 2 rechargeable battery G. Yadav High Voltage Zn-MnO 2 Batteries: Making Zn the new Li I. Vasiliev Discharge Mechanism of MnO 2 in Deep-Cycle Rechargeable Zn/MnO 2 Batteries A. Marschilok Battery Systems Based on Naturally Abundant, Low Cost Materials Team Presentations Numerous Team Posters POSTER : S. Fleming et al. “Extreme Solar: Towards 24-7 Renewable Energy” DOE OE Energy Storage Peer Review 2019 (Albuquerque, New Mexico, September 23-26, 2019) POSTER: J. Huang et al. “Rechargeable Zinc Manganese Dioxide Batteries: From Concept to Product” DOE OE Energy Storage Peer Review 2019 (Albuquerque, New Mexico, September 23-26, 2019) RESULTS OE funded: 2 lab scale, 2 demo projects
PROJECT OBJECTIVES 6 SNL FY Objective 1 - INCREASE UNDERSTANDING and the DEPTH OF DISCHARGE (CAPACITY) OF Zn ELECTRODE PROBLEM: Zn Capacity has not be realized for thousands of cycles Shape change Dendrite formation Passivation H2 evolutionJ. Fu et al., Adv. Mater. 29, 1604685 (2017)Anode Issues to AddressPOSTER: B. Hawkins et al. “Real-Time Identification and Understanding of Zinc Compounds in Rechargeable Zinc Electrodes” DOE OE Energy Storage Peer Review 2019 (Albuquerque, New Mexico, September 23-26, 2019)POSTER: S. Kolhekar et al. “Electrochemically Produced Zinc Oxide Electrode in Rechargeable Alkaline Batteries” DOE OE Energy Storage Peer Review 2019 (Albuquerque, New Mexico, September 23-26, 2019)RESULTS
PROJECT RESULTS 7 Minimized Shape Change and Mass Loss POSTER : M. Lim et al. “Effect of ZnO-Saturated Electrolyte on Rechargeable Alkaline Zinc Batteries at High Depth-of-Discharge” DOE OE Energy Storage Peer Review 2019 (Albuquerque, New Mexico, September 23-26, 2019)Pre-saturating electrolyte with ZnO increases lifetime of Zn up to 200% Increased cycle Life with ZnO electrolytew/ No loss in voltage or efficiency 110% 191% 235% RESULTS
PROJECT OBJECTIVES 8 Properties of an Effective Separator: Stability in alkaline electrolyte (pH >14) High ionic conductivity High hydroxide permeability Low zincate permeability Ease of Fabrication/ProcessingSNL FY Objective 2 – DEVELOP NEW ZINCATE BLOCKING SEPARATORPROBLEM: Bi/Cu-MnO2 only cycles well in absence of Zn – Need to prevent Zincate [Zn(OH)42-] Crossover to MnO2 Cathode HO- Charge screening, size screening, and/or chelation results in a hydroxide selective membrane. HO - Zn(OH) 4 2- J. Duay et al. “Evaluation of a Ceramic Separator for Use in Rechargeable Alkaline Zn/MnO 2 Batteries” J. Power Sources 2018 , 395 , 430–438. 10.1016/j.jpowsour.2018.05.072. (Previous work with NaSICON )
PROJECT RESULTS 9 POSTER : I. Kolesnichenko et al. “Zincate-Blocking Polymeric Separators for Zn/MnO2 Batteries”DOE OE Energy Storage Peer Review 2019 (Albuquerque, New Mexico, September 23-26, 2019)Ex Situ – Hydroxide Selective Separator Successfully Developed Polymer 4CellophaneCelgardZincate DiffusionRESULTSASV Analysis of Zn performed for the first time in alkaline conditions J. Duay, T.N. Lambert, R. Aidun, Electroanalysis, 29 (2017) 1-8. Cellophane Celgard Hydroxide Diffusion Polymer 4 D HO -/ DZn (OH)4 2- = > 10,000
PROJECT RESULTS 10 POSTER : I. Kolesnichenko et al. “Zincate-Blocking Polymeric Separators for Zn/MnO2 Batteries”DOE OE Energy Storage Peer Review 2019 (Albuquerque, New Mexico, September 23-26, 2019) In Situ – Separator effective at blocking zincate crossover in Zn/MnO2 BatteryDischarge of Zn / MnO2 Primary Cells confirms Zn(OH)42- blockingCycling with (CCNY/UEP) Bi/Cu-MnO2 in progressRESULTS1st e- regime2nd e- regimew/ Separatorvs Nivs Zn vs Zn w/Sandia Separator
PROJECT OBJECTIVES 11 SNL FY Objective 3 – USE AB INITIO DFT TO UNDERSTAND CATHODE MECHANISMS PROBLEM: Cathode cycling mechanism are not well understood Prof. Igor Vasiliev RESULTS Work also supported by SNL-LDRD Program POSTER : B. Ale Magar et al. “Theoretical Studies of the Electrochemical Properties of Bi- and Cu-Modified d -MnO 2 Electrodes in Rechargeable Zn/MnO 2 Batteries” DOE OE Energy Storage Peer Review 2019 (Albuquerque, New Mexico, September 23-26, 2019)
PROJECT OBJECTIVES 12 SNL FY Objective 3 – USE AB INITIO DFT TO UNDERSTAND CATHODE MECHANISMS PROBLEM: Cathode cycling mechanism are not well understood Prof. Igor Vasiliev POSTER : J. Duay et al. “Rechargeable Solid-State Copper Sulfide Cathodes for Alkaline Batteries: Importance of the Copper Valence State,” DOE OE Energy Storage Peer Review 2019 (Albuquerque, New Mexico, September 23-26, 2019) RESULTS Work also supported by SNL-LDRD Program SNL FY Objective 4 – DEVELOPMENT OF NEW LOW COST HIGH CAPACITY BATTERY CHEMISTRIES POSTER : B. Ale Magar et al. “Theoretical Studies of the Electrochemical Properties of Bi- and Cu-Modified d -MnO 2 Electrodes in Rechargeable Zn/MnO 2 Batteries,” DOE OE Energy Storage Peer Review 2019 (Albuquerque, New Mexico, September 23-26, 2019) RESULTS Highly Soluble Highly Soluble Insoluble Precipitate S Cu Cu&S ~1500 mAh g -1 (S) ~300 mAh g -1 (Cu 2 S) ~ 23 mAh cm -2 >135 Wh L -1 ~ 250 cycles Sulfur is known to have a high theoretical specific capacity: 1650 mA h g -1 Work also supported by SNL-LDRD Program Zn/Cu 2 S
PROJECT RESULTS 13 FY 19 Accomplishments – Highlights Conducted study into effect of zincate on Zn DOD and battery life in a model system 100-200% cycle life improvement, lower mass loss with more compact morphologies Performed in operando Raman characterization of Zn anode in Zn/MnO2 – ongoingDemonstrated several selective separators (hydroxide > zincate) – currently undergoing battery evaluation with 2e- cathodes from CCNY/UEPDiscovery of new rechargeable energy dense solid-state copper-sulfide cathode for alkalineConstructed a theoretical phase diagram outlining possible redox reaction pathways in the Bi/Cu-d-MnO2 electrode. = I. Vasiliev et al.First demonstration of > 2 V Zn/MnO2 battery concept = G. Yadav et al.
PROJECT RESULTS 14 FY 19 Manuscripts ( 3 published, 2 in peer review, 3 in preparation ) J. Duay et al. “Rechargeable Solid-State Copper Sulphide Cathodes for Alkaline Batteries: Importance of the Copper Valence State” J. Electrochem. Soc. 2019 166 (4), A687-A694. DOI: 10.1149/2.0261904jes.I. Vasiliev et al. “Ab Initio Studies of Hydrogen Ion Insertion into pyrolusite, ramsdellite and nsutite MnO2 polymorphs and implications for shallow cycled Rechargeable Zn/MnO2 batteries” J. Electrochem. Soc. 2018 165 (14), A3517-A3524. DOI: 10.1149/2.1161814jes.G. G. Yadav et al. “Breaking the 2 V Barrier in Aqueous Zinc Chemistry: Creating 2.45 and 2.8 V MnO2-Zn Aqueous Batteries” ACS Energy Lett. 2019, 4, 9, 2144-2146.DOI: 10.1021/acsenergylett.9b01643G. G. Gadav et al. "Going Beyond Intercalation Capacity of Aqueous Batteries By Exploiting Conversion Reactions of Mn and Zn electrodes For Energy-Dense Applications", Advanced Energy Materials 2019 in peer review.L. Wang et al. “Silver-Containing α-MnO2 Nanorods: Electrochemistry in Rechargeable Aqueous Zn-MnO2 Batteries” in peer review.B. A. Magar et al. “Ab Initio Studies of Discharge Mechanism of MnO2 in Deep-Cycled Rechargeable Zn/MnO2 Batteries” manuscript in preparation.M. B. Lim et al. “Effect of ZnO-Saturated Electrolyte on Rechargeable Alkaline Zinc Batteries at High Depth-of-Discharge” manuscript in preparation.I. V. Kolesnichenko et al. “Zincate blocking polymers for Zn/MnO2 alkaline batteries” manuscript in preparation.
PROJECT RESULTS 15 FY 19 Presentations ( 17 Presentations ) M. B. Lim, I, Kolesnichenko, D. Arnot and T. N. Lambert “Effect of ZnO -Saturated electrolyte on Rechargeable Alkaline Zinc Batteries at High Depth-of-Discharge” 2019 Postdoc Research Symposium and Career Fair, Los Alamos, NM, August 27th, 2019.Invited Talk: T. N. Lambert, J. Duay, M. Kelly, B. A. Magar, I. Vasiliev, M. B. Lim, D. Arnot, I. V. Kolesnichenko, B. R. Chalamala “Advances in Alkaline Storage Batteries and their Potential Impact for Society” 9th WMRIF Symposium and General Assembly, Budapest, Hungary, June 17-20, 2019.Invited Talk: T. N. Lambert “Effect of Additives and Selective Separators on Alkaline Zn-based Batteries” NAATBatt International Workshop on Zinc Battery Technology, New York, New York, November 16, 2018.D. J. Arnot, I. Kolesnichenko, J. Duay, and T.N. Lambert “Ion Selective Separators for Rechargeable Alkaline Zn/MnO2 Batteries” Annual AIChE Student Conference, Pittsburg, PA, October 26-29, 2018.M. B. Lim. M. Kelly, J. Duay, I. V. Kolesnichenko, T. N. Lambert “Improving Cycle Life and Active Materials Utilization for Rechargeable Alkaline Zn–MnO2 Batteries” 235th ECS Meeting, Dallas, TX, May 26-30, 2018.B. Ale Magar, T. N. Lambert, J. Duay, B. Chalamala, and I. Vasiliev “Discharge Mechanism of the gamma-MnO2 Electrode in Shallow-Cycled Zn/MnO2 Batteries: An Ab Initio Study”, 2018 APS March Meeting, Los Angeles, California, March 5-9th, 2018.MRS Spring 2019: Brendan E. Hawkins, Damon Turney, Gautam Ganapati Yadav, Sanjoy Banerjee and Robert J. Messinger, "Real-Time Identification and Understanding of Zinc Compounds in Rechargeable Zinc-Alkaline Electrodes”MRS Fall 2019: Brendan E. Hawkins, Damon Turney, Ankur Jadhav, Gautam Ganapati Yadav, Robert J. Messinger and Sanjoy Banerjee, "Investigating the Dynamic Behavior of Zinc Oxide Discharge Product in Rechargeable Zinc Electrodes”ECS 2019: Brendan E. Hawkins, Damon Turney, Ankur Jadhav, Gautam Ganapati Yadav, Robert J. Messinger and Sanjoy Banerjee, "Investigating the Dynamic Behavior of Zinc Oxide Discharge Product in Rechargeable Zinc Electrodes”
PROJECT RESULTS 16 FY 19 Presentations continued… ECS 2019: Michael D'Ambrose , Gautam Ganapati Yadav, Damon Turney, Joshua W Gallaway, Michael Nyce , Robert J. Messinger and Sanjoy Banerjee, "Failure Analysis of the Rechargeable Porous Zinc Electrode in Alkaline Electrolyte"Gautam Yadav, Presentation at the Institute of Chemical Technology, Mumbai, India and Chemical Engineering, Purdue University, "Engineering an energy dense aqueous MnO2|Zn Battery to challenge Li-ions dominance"Valerio De Angelis Urban Electric Power, "The role of storage in replenishing energy supply on a human time scale: potential and challenges", Energy Storage Session, Techconnect World Innovation Conference, and Expo, Boston, 17-19 of June 2019. Sanjoy Banerjee, City College of New York, "Alkaline zinc manganese dioxide batteries for grid-scale energy storage: potential and challenges", ICESI - PPSS 2019, Hawaii, January 5 – 10, 2019.Sanjoy Banerjee, Panel on Long-Duration Storage Solutions, NY-BEST Annual Meeting and Conference: Capture the Energy, Albany, NY, March 13-14Gabriel Cowles, Urban Electric Power, "Urban Electric Power Company Overview", NaatBatt Zinc Workshop, New York, November 16, 2018. Gabriel Cowles, Urban Electric Power, "Member Update Presentation", NaatBatt 2019 Annual Meeting & Conference, Arizona, March 11 – 14, 2019.Esther, Takeuchi “Synthesizing Low Cost Materials for Zinc Batteries: Zn Battery Technology Workshop, NAATBATT, New York, November 16, 2018. FY 19 Patent Applications(SNL) T. N. Lambert and J. Duay, United States of America Patent Application, 16/054,114, 2018 -PCT/US18/45187, 2018.
LOOKING FORWARD 17 NEXT STEPS Incorporate Zincate, Effect of 3D Architecture and Cell Builds on Zn cycling Continued Development of Zincate Blocking Separators – Increased Conductivity and Demonstration with High capacity Zn/MnO 2 electrodesFurther Development and Understanding of High Capacity CathodesCo-develop UEP Roadmap to $50/kWh for Zn/MnO2 Batteries
PROJECT CONTACTS 18 Imre Gyuk Babu ChalamalaTimothy N. Lamberttnlambe@sandia.govBabu Chalamalabchalam@sandia.gov Tim Lambert And COLLABORATORS! ACKNOWLEDGEMENTS THIS WORK WAS SUPPORTED THROUGH THE ENERGY STORAGE PROGRAM, MANAGED BY DR. IMRE GYUK , WITHIN THE U.S.DEPARTMENT OF ENERGY’S OFFICE OF ELECTRICITY Ivan Pineda-Dominguez Logan Ricketts Rachel Habing Maria Kelly Ruby Aidun David Arnot Kristen Maus Elijah Ruiz Jonathon Duay Matthew Lim Igor Kolesnichenko Noah Schorr ADDITIONAL SUPPORT PROVIDED BY the Laboratory Directed Research and Development program at Sandia National Laboratories. Howard Passell Sandia Team