Reining in dissolved transition-metal ions

doi:10.1126/science.abc5454

GSTDTAP > 气候变化

DOI	10.1126/science.abc5454
	Reining in dissolved transition-metal ions
	Hooman Yaghoobnejad Asl; Arumugam Manthiram
	2020-07-10
发表期刊	Science
出版年	2020
英文摘要	With an increasing deployment of large-size lithium-ion batteries (LIBs) for applications beyond consumer electronics, critical questions surround their life span and safety. The LIB technology is based on oxide cathodes and graphite anodes developed in the 1980s ([ 1 ][1]). The current ∼350 cycle-life warranty (based on 100,000 miles and 300-mile range per full charge) ([ 2 ][2]) provided by major electric vehicle manufacturers falls short of the 1000 cycle-life target sought by the U.S. Department of Energy ([ 3 ][3]). As a result, a major focus has been to understand the fundamental factors that cause the degradation of LIBs. Among them, dissolution of transition-metal (TM) ions from the cathode into the liquid electrolyte has been recognized as a leading cause. We discuss the causes of the dissolution of certain metal ions from the cathode into the electrolyte, including the possible role of electronic structure. A typical commercial lithium-ion cell has a lithiated TM oxide (TMO) cathode (positive electrode), such as Li(Ni1/3Co1/3Mn1/3)O2. These cathodes are variants of the very stable but expensive LiCoO2 cathode in which some of the Co is replaced with less costly TMs. The challenge is that these replacement TM cations tend to dissolve into the liquid electrolyte and migrate and deposit on the graphite anode. Once there, they increase the solid-electrolyte interphase (SEI) layer thickness on graphite, trap cyclable lithium in the SEI, and raise the cell impedance, thereby limiting the cell cycle life ([ 4 ][4], [ 5 ][5]). The thicker SEI on the graphite anode also promotes lithium dendrites, which can result in fire and safety hazards. The problem of TM-ion dissolution is aggravated by the cathode chemistries that involve Jahn-Teller (J-T) distorted TM ions and can be attributed to trace amounts of hydrofluoric acid (HF) generated in the electrolyte. For example, metal dissolution is substantially higher for cathode compositions containing the J-T–active Mn3+ ions ([ 6 ][6], [ 7 ][7]). This finding raises the issue of delineating the complex chemistry involving the H+ acidic species, J-T distortion of TMOs, and the enhanced TM-ion dissolution observed. The electronic structure of TM cations is modified by J-T distortion. Most of the TM cations in TMOs adopt an aggregation of six oxide ligands arranged symmetrically along the Cartesian axes, giving rise to an octahedral (Oh) coordination (see the first figure, left). The Oh ligand electric field separates the d orbitals of the TM cation into triply degenerate t2g (d xy , d xz , and d yz ) and doubly degenerate eg (dz2 and dx2-y2) sets. This arrangement is preferred for TM cations that have a cubically symmetric electron density that is achieved when the eg orbital set is completely filled, half-filled, or empty (for example, t2g3 eg, t2g3 eg2, and t2g6 eg). ![Figure][8] Jahn-Teller (J-T) distortions The ligand field in manganese oxides used in lithium-ion battery cathodes distorts the six equivalent metal-oxygen bonds (left) into two longer axial bonds and four shorter equatorial bonds (right). Charge is transferred from the metal cation to the axial oxygens, which become more basic. GRAPHIC: A. KITTERMAN/ SCIENCE However, for certain TM cations, including high-spin Mn3+, high-spin Fe4+, and low-spin Ni3+, the electron density follows a noncubic distribution as a result of the single occupancy of the doubly degenerate eg set (for example, eg1). This unfavorable state is relaxed according to the J-T theorem by an elongation of two axial TM–O bonds and a shrinkage of the other four equatorial ones, which reduces the TMO6 symmetry from cubic to tetragonal (see the first figure, right). Note that the Co3+/4+ (high-spin or low-spin) ions in the commonly used LiCoO2 cathode (Co3+: t2g6 eg; Co4+: t2g5 eg) in LIBs avoid the problematic eg1 electronic state and resulting metal-ion dissolution and help account for their successful implementation in first-generation LIBs. The J-T effect can vary in strength with a global, macroscopic distortion of the crystal structure, as is the case often with Mn3+, or a local, microscopic distortion, as is usually observed with TMOs with Ni3+ and Fe4+. In the local distortion case, the individual TM–O bond lengths may vary without affecting the average macroscopic structure, which leads to a dynamic lattice instability. The strength of J-T distortion also correlates inversely with the covalency of TM–O bonds, which increases in the order Mn3+ < Ni3+ < Fe4+ because of an increase in the effective nuclear charge (Mn < Fe < Ni) combined with a higher formal charge on Fe4+. Thus, the local J-T distortion in TMOs with dynamic lattice instability also makes them reactive enough toward acidic species and susceptible to TM-ion dissolution. Understanding how J-T distortion, whether global or local, can cause TM-ion dissolution in acidic electrolytes can be addressed best through molecular orbital (MO) considerations. The axial-equatorial splitting of TM–O bonds alters the degree of overlap of the atomic orbitals of TM cations and O ligands. The eg1 electronic configuration (e.g., dz21 dx2-y2) allows the empty dx2-y2 orbital to overlap strongly with the four filled 2p orbitals of the oxide ligand-group in the equatorial x-y plane, yielding four s-bonding orbitals that are predominantly oxygen in character. However, the half-filled dz21 orbital, oriented along the z axis, overlaps weakly with the two filled 2p orbitals of the oxide ligand group along the same axis. This case leads to the formation of a low-energy axial σ-bonding orbital filled with oxide electrons and a high-energy axial s-antibonding orbital half-filled with the dz2 single electron. The longer axial TM–O bonds with a weaker overlap are more ionic compared to the shorter, more covalent equatorial TM–O bonds, resulting in a higher negative charge on the axial oxygen atoms with a more basic character from a Lewis acid-base perspective. Thus, J-T distortion induces higher reactivity with acid and increased TM-ion dissolution in LIBs in two ways: It places an electron into the dz21 orbital, and the electron is delocalized over the TM and O atoms; and it enhances the Lewis-base strength of the axial oxygens compared to the equatorial oxygens. Given this background, we can now address how the presence of acid leads to metal-ion dissolution in LIBs from TMOs with J-T ions. The hydrolysis of the LiPF6 salt in the electrolytes of LIBs by residual moisture generates the strong Lewis acid HF, whose H+ ions interact exclusively with the axial oxygens, which are the stronger Lewis bases, at the cathode-electrolyte interface (see the second figure, top). The acid-base interaction may lead to the formation of H2O, through oxide protonation. However, this cannot happen independently, as the oxygens in the TMO have less negative charge compared to the oxygen in H2O because of the higher covalency of TM–O bonds compared to the H–O bonds. The formation of H2O by the protonation of the TMO oxides requires a net electron transfer from the TMO to the axial oxide orbital. This charge transfer originates from the dz21 orbital of the TMO that contains the most reactive electron. Thus, protonation of the axial oxide ion and formation of H2O are accompanied by a simultaneous metal-to-ligand electron transfer that leaves the TM with a higher oxidation state (see the second figure, bottom). These as-formed TM cations (Mn4+, Fe5+, and Ni4+) are strong oxidizers that reduce back directly to the stable, J-T free state (Mn2+, Fe3+, and Ni2+) through a two-electron reduction pathway by oxidizing electrolyte solvent molecules into CO2 and other reactive protic species ([ 8 ][9], [ 9 ][10]). These stable, lower-valence TM oxides and fluorides tend to readily dissolve into the electrolyte. In turn, the as-formed water molecule can further react with the LiPF6 salt to generate more HF, creating a closed-loop cycle whose net effect is the destruction of the electrolyte salt and solvent, the cathode and the anode. The problem of proton-induced oxidation of TMOs extends to various degrees to other TMOs beyond Mn3+ that contain J-T–active ions. For example, the oxidation of TM to higher states under protic environments has been observed in LiMn3+Mn4+O2, LiNi3+O2, and Na4Fe4+O4 ([ 10 ][11]–[ 12 ][12]), where Mn3+, Ni3+, and Fe4+ are J-T–active ions. Despite the fundamental reactivity of J-T–active ions, oxides containing Ni, Fe, and Mn offer the advantage of abundance and low cost compared to Co, which is beneficial to the mass production of batteries. To reduce metal-ion dissolution, current research efforts are focused on two fronts. On an engineering level, surface coating of the electrodes by passive layers has been used to minimize direct electrode-electrolyte contact ([ 13 ][13]), but at the expense of increased cell resistance. On a chemistry level, the uneven electron density of the J-T–active TM ions has been diluted through ionic-doping and defect introduction strategies ([ 7 ][7]). For exmaple, the doping strategy can be executed by incorporating electrochemically inactive, J-T free Mn4+ in the LiNi1- x-y Co x MnyO2 series cathodes and a consequent reduction of an equivalent amount of Ni3+ to J-T free Ni2+ ([ 4 ][4]). ![Figure][8] How electrolytes affect cathodes The J-T distortion of Mn3+ cations makes it susceptible to dissolution from acid formed from the electrolyte attacking basic axial oxygens. GRAPHIC: A. KITTERMAN/ SCIENCE In parallel to the above cathode-level remedies, other cell-level measures can also be invoked to limit the extent of the acid-base reaction. For example, the electrolyte salt anion can be replaced with bis(trifluoromethane)sulfonimide [TFSI, (CF3SO2)2N−], in which the covalent C–F bonds are not prone to hydrolysis, unlike the highly polar P–F bonds as in the PF6− anion. 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领域	气候变化 ; 资源环境
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文献类型	期刊论文
条目标识符	http://119.78.100.173/C666/handle/2XK7JSWQ/283381
专题	气候变化资源环境科学
推荐引用方式 GB/T 7714	Hooman Yaghoobnejad Asl,Arumugam Manthiram. Reining in dissolved transition-metal ions[J]. Science,2020.
APA	Hooman Yaghoobnejad Asl,&Arumugam Manthiram.(2020).Reining in dissolved transition-metal ions.Science.
MLA	Hooman Yaghoobnejad Asl,et al."Reining in dissolved transition-metal ions".Science (2020).