Effects of soluble products decomposed from chelato-borate additives on formation of solid electrolyte interface layers

Wang, Peng; Cui, Xiaoling; Zhao, Dongni; Yan, Dingshun; Ding, Hao; Dong, Hong; Wang, Jie; Wu, Shumin; Li, Shiyou

doi:10.1016/j.jpowsour.2022.231451

Cited by 22 publications

(12 citation statements)

References 36 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The calculated radial distribution function g ( r ) clarifies that Li + comes in a variety of configurations in the electrolyte, involving coordination with solvents (Li–EC, Li–EMC, and Li–DEC) and additive (Li–TMB) with a prominent peak of TMB located at 2.75 Å (Figure c,d). Solvents such as EC, EMC, and DEC are reduced into unstable lithium ethylene dicarbonate and lithium ethylene monocarbonate, which finally reduce to a stable Li 2 CO 3 phase by a one-electron reduction process . TMB undergoes a similar process through which oligomeric borates are produced.…”

Section: Resultsmentioning

confidence: 99%

“…Solvents such as EC, EMC, and DEC are reduced into unstable lithium ethylene dicarbonate and lithium ethylene monocarbonate, which finally reduce to a stable Li 2 CO 3 phase by a oneelectron reduction process. 42 TMB undergoes a similar process through which oligomeric borates are produced. The strong interaction between Li + and TMB lowers the lowest unoccupied molecular orbital energy of TMB, and the preferential reduction of TMB occurs on the anode introducing the B−O oligomer to the as-formed SEI to boost the transport of Li + .…”

Section: Sei Characterization On LImentioning

confidence: 99%

See 1 more Smart Citation

Roles of Trimethyl Borate in Constructing an Interphase on Li Anode: Angel or Demon?

Ding

Wen

Lan

2023

ACS Appl. Mater. Interfaces

View full text Add to dashboard Cite

Although coupling a lithium metal anode with a Ni-rich layer cathode is a promising approach for high-energy lithium metal batteries, both electrodes are plagued by their intrinsic unstable interfaces which trigger electrolyte decomposition, lithium dendritic growth, and transition metal dissolution during cycling. Making use of electrolyte additives is one of the most effective solutions to address this issue. In this paper, we explore the roles of trimethyl borate (TMB)�a common film-forming additive to protect high-nickel-ratio ternary cathodes�in suppressing lithium dendrite growth. It is found that, on the one hand, the borate-containing solid electrolyte interphase (SEI) derived from the decomposition of TMB facilitates Li + transport, homogenizing the deposition of Li ions. On the other hand, TMB as an anion receptor provokes LiPF 6 decomposition, prompting the formation of SEI with superfluous LiF. As a result, it is imperative to raise awareness of this double-edge additive when using it to be immune to lithium dendrite and cathodic degradation.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Sei Characterization On LImentioning

confidence: 99%

Roles of Trimethyl Borate in Constructing an Interphase on Li Anode: Angel or Demon?

Ding

Wen

Lan

2023

ACS Appl. Mater. Interfaces

View full text Add to dashboard Cite

show abstract

“…As shown in Figure 4(a2–c2) and Figure 4(a3–c3), a trough represents a time constant, which means that the vertical view of the Nyquist plots will appear a semicircle [15] . From the comparison, we find that the initial voltage for LNMO‐LiF|1 M+LiDFP|Li cell to form the second time constant is at 4.52 V, whereas LNMO‐LiF|1 M|Li and LNMO|1 M+LiDFP|Li cells are at 4.48 and 4.43 V, respectively.…”

Section: Resultsmentioning

confidence: 99%

A Novel Scheme to Improve the Stability of Conventional‐Concentration Electrolyte at High Voltage

Zhang

Wang

et al. 2022

Batteries & Supercaps

Self Cite

View full text Add to dashboard Cite

It is well-known that conventional-concentration electrolytes (CCEs) will undergo serious oxidative decomposition in highvoltage lithium-ion batteries, while high-concentration electrolytes (HCEs) have good oxidation stability. However, HCEs are difficult to scale-up for industrial applications due to their high viscosity and cost. Herein, based on the anti-oxidation mechanism of HCE, a novel scheme to improve the stability of CCE at high voltage was proposed. By means of magnetron sputtering LiF on LiNi 0.5 Mn 1.5 O 4 surface and introducing LiPO 2 F 2 additive, a stable cathode electrolyte interphase (CEI) film is constructed in CCE. AFM results show that the constructed CEI film in CCE has better mechanical strength and adhesion than that formed by HCE. Moreover, the battery performance with the constructed CEI film in CCE, which affords high stability at high voltage, fastcharging kinetics, and improved cycling stability (135 mAh g À 1 after 200 cycles), is comparable to that with HCE.

show abstract

“…A CHI660E electrochemical workstation (Chenhua, Shanghai, China) through a three-electrode system was used for the following tests, using a Si@Graphite@C electrode as the working electrode and lithium sheets as both the reference electrode as well as the counter electrode, respectively. Electrochemical impedance spectroscopy (EIS) measurements of cells with different electrolytes were tested after the fifth cycle and 100th cycle over the frequency range from 10 mHz to 100 kHz. − PRI-EIS was performed in the potential range of open circuit potential to 0.01 V, in the frequency range of 10 mHz–100 kHz.…”

Section: Methodsmentioning

confidence: 99%

Improving Toleration of Volume Expansion of Silicon-Based Anode by Constructing a Flexible Solid-Electrolyte Interface Film via Lithium Difluoro(bisoxalato) Phosphate Electrolyte Additive

Wang

Zhang

et al. 2022

ACS Sustainable Chem. Eng.

Self Cite

View full text Add to dashboard Cite

The silicon (Si) anode is considered one of the most promising candidates among many novel anode materials in lithium-ion batteries owing to its high theoretical capacity and earth abundancy. Nonetheless, a large volume expansion of Si particles appears with cycling, prompting unceasing breakage/reformation of the solid-electrolyte interface (SEI) and fast capacity degradation in traditional electrolytes. For the purpose of tolerating volume expansion for the Si anode, lithium difluoro(bisoxalato) phosphate (LiDFBOP) was adopted in the standard (STD) electrolyte based on LiPF6. Density functional theory (DFT) calculations, Young’s modulus from atomic force microscopy, potential-resolved in situ electrochemical impedance spectroscopy (PRI-EIS) measurement, and other characterizations proved that the formed SEI can inhibit volume expansion of a Si@Graphite@C anode. In the STD+2% LiDFBOP electrolyte, the solvation structure of Li(EC)2(PF6)1(DFBOP)1 is more likely to be produced, and this kind of solvation structure has stronger reducibility and easily participates in SEI formation. The 2% LiDFBOP additive increases the inorganic LiF component of SEI, which yields great advantages in regulating the uniform diffusion of Li+ ions passing through the SEI. Besides, the organics containing P and F atoms are also abundant in SEI, which has greater flexibility and can tolerate volume expansion of the Si@Graphite@C anode. Therefore, the STD+2% LiDFBOP electrolyte can improve the electrochemical performances of Si@Graphite@C/Li half-cells. This work has practical implications not only for the molecular design of novel lithium salt but also for the constructions of SEI and electrolyte systems compatible with the Si@Graphite@C anode.

show abstract

Effects of soluble products decomposed from chelato-borate additives on formation of solid electrolyte interface layers

Cited by 22 publications

References 36 publications

Roles of Trimethyl Borate in Constructing an Interphase on Li Anode: Angel or Demon?

Roles of Trimethyl Borate in Constructing an Interphase on Li Anode: Angel or Demon?

A Novel Scheme to Improve the Stability of Conventional‐Concentration Electrolyte at High Voltage

Improving Toleration of Volume Expansion of Silicon-Based Anode by Constructing a Flexible Solid-Electrolyte Interface Film via Lithium Difluoro(bisoxalato) Phosphate Electrolyte Additive

Contact Info

Product

Resources

About