Lithium rich cathode/graphite anode combination for lithium ion cells with high tolerance to near zero volt storage

Crompton, K. R.; Staub, Jason W.; Hladky, Michael; Landi, Brian J.

doi:10.1016/j.jpowsour.2017.01.008

Cited by 12 publications

(15 citation statements)

References 43 publications

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“…Lithium-ion batteries continue to be the premier chemistry for electrochemical energy storage due to their increased specific energy and energy density compared to other chemistries . However, individual lithium-ion cells cannot be discharged to a voltage typically less than 2.0–3.0 V, a condition commonly referred to as overdischarge, without risking damage to the cell that can significantly decrease cell performance. − This risk of cell damage leads to lithium-ion batteries in an active-use state, requiring individual cell voltage monitoring and cell charge-state balancing systems to prevent individual cell overdischarge. Additionally, in an inactive state such as during storage or shipping, individual lithium-ion cells have to be voltage monitored and undergo maintenance charging to prevent the cell voltage from decreasing to less than 2.0–3.0 V. Altogether the overdischarge risk of the conventional lithium-ion cells leads to increased system complexity and maintenance logistics that can increase costs associated with lithium-ion battery systems.…”

Section: Introductionmentioning

confidence: 99%

“…The primary mode of damage to a conventional lithium-ion cell when it is overdischarged is widely attributed to oxidation and dissolution of the conventional copper foil current collector of the anode which can cause gas formation, internal short-circuiting, and other side reactions in the cell. − This oxidation and dissolution occurs due to lithium inventory (also referred to as reversible lithium, active lithium, or cycleable lithium) limitation that is present in conventional lithium-ion cells which leads to the anode potential increasing to the copper oxidation potential during overdischarge. ,,− Lithium inventory limitation is a result of passivation layer, or solid electrolyte interphase (SEI), formation on the anode during the initial cycling of a lithium-ion cell after fabrication. ,,− Lithium is irreversibly incorporated into the SEI layer, which leads to lithium-inventory depletion. ,,− …”

Section: Introductionmentioning

confidence: 99%

“…Given that oxidation and dissolution of the copper current collector of the anode is the primary source of lithium-ion cell performance fade from overdischarge, designs of nonconventional, overdischarge-tolerant lithium-ion cells have taken approaches to prevent or mitigate this process during overdischarge. These approaches have included using electrolyte additives like succinonitrile to passivate the copper foil in situ during overdischarge, passivating the copper during cell fabrication with nitrile compounds, or modifying the lithium inventory of the cell such that the anode does not increase to >3.2 V vs Li/Li + during overdischarge conditions that decrease the cell voltage to not less than 0.0 V. ,,,,− Other nonconventional cell designs have replaced the anode copper current collector altogether with materials that are more stable to potentials >3.2 V vs Li/Li + , such as titanium, stainless steel, or nickel. , These current collector replacements, particularly titanium, have proven to form a cell that is robustly tolerant to overdischarge . However, the substantially lower conductivity of these materials compared to copper can limit the power capability of the cell as well as necessitate thinner electrode architectures which will decrease the achievable cell level specific energy and energy density …”

Section: Introductionmentioning

confidence: 99%

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Analysis of Germanium Nanoparticle Composites with an Aluminum Current Collector toward Li-ion Battery Anodes with High Capacity and Broad Potential Stability Range

Crompton¹,

Hladky²

2021

ACS Appl. Energy Mater.

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Reduction reactions with lithium at >0.3 V vs Li/Li + make germanium prospectively compatible with aluminum current collectors to form a copper-free lithium-ion cell anode that may enable lithium-ion cells that are more tolerant to overdischarge. Targeted 2.0 mAh/cm 2 germanium nanoparticle electrodes with an aluminum foil (Ge−Al electrode) current collector were fabricated and tested versus lithium from 0.3 to 1.5 V vs Li/Li + in 1.0 M LiPF 6 1:1 ethylene carbonate/diethyl carbonate (v/v) electrolyte and demonstrated a peak reversible capacity of 342 mAh/g Ge at a targeted C/10 rate. A targeted 2.0 mAh/cm 2 germanium nanoparticle electrode with a copper current collector (Ge−Cu electrode) was also tested from 0.005 to 1.5 V vs Li/Li + , the results of which are utilized as a representative comparison of germanium tested in a conventional lithium-ion anode potential range. Compared to the Ge−Cu electrode, after 50 cycles at a targeted C/10 rate the Ge−Al electrode showed 90% vs 18% capacity retention. Post-mortem analysis with XPS, SEM/EDS, Raman spectroscopy, and FTIR showed that compared to the Ge−Cu electrode the Ge−Al electrode had (1) less oxygen, fluorine, and carbon deposition, (2) less germanium amorphization, (3) formation of Li x C y and Ge−H, and (4) less Li 2 O formation. After 150 cycles at equivalent targeted rates, the Ge−Al electrode also had significantly less mid-frequency impedance growth than the Ge−Cu electrode. Modeling of 18650 format LiNiCoAlO 2 -cathode lithium-ion cells with a Ge−Al anode predicted an achievable energy density and specific energy of up to 491 Wh/L and 198 Wh/kg. A germanium dissolution potential of 4.2 V vs Li/Li + was assigned based on voltammetry and post-mortem SEM/EDS. Cycling of a Ge−Al electrode with an upper potential cutoff of 4.2 V vs Li/Li + every tenth cycle showed 30% capacity retention after 50 cycles, an increased capacity fade attributed to solid electrolyte interphase instability up to 4.2 V vs Li/Li + based on impedance and post-mortem analysis.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Analysis of Germanium Nanoparticle Composites with an Aluminum Current Collector toward Li-ion Battery Anodes with High Capacity and Broad Potential Stability Range

Crompton¹,

Hladky²

2021

ACS Appl. Energy Mater.

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“…Figure d displays that R values increase with MCMB anode potentials, which indicates that a higher APZBS brings more decomposition of SEI films on MCMB anodes, consequently leading to worse zero-charge storage performance. It has been reported that anode potential at the near-zero-charge state of a Li-ion battery can shift up from 1.9 to 2.9 V versus Li/Li + during zero-charge storage . More decomposition of the SEI film occurs when the APZBS shifts to a higher level.…”

Section: Results and Discussionmentioning

confidence: 99%

“…It has been reported that anode potential at the near-zero-charge state of a Li-ion battery can shift up from 1.9 to 2.9 V versus Li/Li + during zero-charge storage. 31 More decomposition of the SEI film occurs when the APZBS shifts to a higher level. Therefore, very less increase of the APZBS in zero-charge storage as an additional result of the Li 5 FeO 4 cathode additive also benefits high zero-charge storage performance.…”

Section: Resultsmentioning

confidence: 99%

Improved Zero-Charge Storage Performance of LiCoO₂/Mesocarbon Microbead Lithium-Ion Batteries by Li₅FeO₄ Cathode Additive

Liu

Xie

et al. 2022

ACS Appl. Mater. Interfaces

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Discharging lithium-ion batteries to zero-charge state is one of the most reliable ways to avoid the thermal runaway during their transportation and storage. However, the zero-charge state causes the degradation or even complete failure of lithium-ion batteries. Specialized solutions are required to endow lithium-ion batteries with improved zero-charge storage performance, namely, the ability to tolerate zero-charge state for a long time without unacceptable capacity loss. Here, we report that a Li5FeO4 cathode additive can improve the zero-charge storage performance of LiCoO2/mesocarbon microbead (MCMB) batteries. The irreversible charge capacity of the Li5FeO4 additive results in the downregulation of anode and cathode potentials when the battery is at zero-charge state. More importantly, the Li5FeO4 additive offers a small discharge plateau below 2.9 V versus Li/Li+, which can hold the anode potential at zero-charge battery state (APZBS) in a potential range of 2.4∼2.5 V versus Li/Li+ during storage for 10 days. Such a precise control on APZBS not only suppresses the decomposition of the solid electrolyte interface film on the MCMB anode and inhibits the dissolution of the copper current collector occurring at high potentials but also avoids the excessive decrease of the cathode potential at the zero-charge battery state and consequently protects the LiCoO2 cathode from overlithiation occurring at low potentials. As a result, the Li5FeO4 additive with a charge capacity percentage of 23% in the cathode increases the capacity recovery ratio of the LiCoO2/MCMB battery from 37.6 to 95.5% after being stored at the zero-charge state for 10 days.

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The Potential Regulation of Working Anode for Long‐Term Zero‐Volt Storage at 37 °C in Li‐Ion Batteries

Wang,

Liu,

Jiang

et al. 2024

Advanced Materials

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The advanced lithium‐ion batteries (LIBs) that can tolerate over‐discharge to 0 V and zero‐volt storage (ZVS) are highly desired for active implantable medical devices and spacecraft. However, ZVS can raise the anode potential and lead to continuous oxidation of the Cu current collectors and SEI degradation, which significantly reduces battery capacity and causes safety issues, especially at 37°C. In this contribution, a stable anti‐fluorite structured compound, Li6CoO4, is proposed as a cathode additive for zero‐volt storage of LIBs. By quantitatively regulating the dosage of Li6CoO4 additives, controllable potential of the working anode under abusive‐discharge conditions has been demonstrated. The addition of Li6CoO4 keeps ZCP (zero‐crossing potential) and the potential of ZVS less than 2.0 V (versus Li/Li+) for LiCoO2|mesocarbon microbead cells at 37°C. The capacity retention ratio (CRR) increases from 69.1% and 35.9% to 98.6% and 90.8% after 10 and 20 days of ZVS, respectively. The dissolution of the Cu and degradation of SEI have been effectively suppressed, while the over‐lithiated cathode exhibits high reversible capacity in working ZVS batteries. The limiting conditions of long‐term ZVS has been explored and a corresponding guide map is designed. When quantitatively regulating ZCP and the potential in ZVS, special attention should be paid to avoid the threshold of Cu dissolution, the rate of SEI degradation as potential rises, the time and potential window for irreversible conversion of the cathode. This contribution designs the most reasonable potential range for ZVS protection at 37°C, and realizes the best CRR record through precise potential regulation for the first time.This article is protected by copyright. All rights reserved

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Lithium rich cathode/graphite anode combination for lithium ion cells with high tolerance to near zero volt storage

Cited by 12 publications

References 43 publications

Analysis of Germanium Nanoparticle Composites with an Aluminum Current Collector toward Li-ion Battery Anodes with High Capacity and Broad Potential Stability Range

Analysis of Germanium Nanoparticle Composites with an Aluminum Current Collector toward Li-ion Battery Anodes with High Capacity and Broad Potential Stability Range

Improved Zero-Charge Storage Performance of LiCoO₂/Mesocarbon Microbead Lithium-Ion Batteries by Li₅FeO₄ Cathode Additive

The Potential Regulation of Working Anode for Long‐Term Zero‐Volt Storage at 37 °C in Li‐Ion Batteries

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Lithium rich cathode/graphite anode combination for lithium ion cells with high tolerance to near zero volt storage

Cited by 12 publications

References 43 publications

Analysis of Germanium Nanoparticle Composites with an Aluminum Current Collector toward Li-ion Battery Anodes with High Capacity and Broad Potential Stability Range

Analysis of Germanium Nanoparticle Composites with an Aluminum Current Collector toward Li-ion Battery Anodes with High Capacity and Broad Potential Stability Range

Improved Zero-Charge Storage Performance of LiCoO2/Mesocarbon Microbead Lithium-Ion Batteries by Li5FeO4 Cathode Additive

The Potential Regulation of Working Anode for Long‐Term Zero‐Volt Storage at 37 °C in Li‐Ion Batteries

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Improved Zero-Charge Storage Performance of LiCoO₂/Mesocarbon Microbead Lithium-Ion Batteries by Li₅FeO₄ Cathode Additive