Science - USA (2020-07-10)

the electrodes by passive layers has been

used to minimize direct electrode-electrolyte

contact ( 13 ), but at the expense of increased

cell resistance. On a chemistry level, the un-

even electron density of the J-T–active TM

ions has been diluted through ionic-doping

and defect introduction strategies ( 7 ). For ex-

maple, the doping strategy can be executed

by incorporating electrochemically inactive,

J-T free Mn4+ in the LiNi1-x-yCoxMnyO 2 series

cathodes and a consequent reduction of an

equivalent amount of Ni3+ to J-T free Ni2+ ( 4 ).

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 elec-

trolyte salt anion can be replaced with

bis(trifluoromethane)sulfonimide [TFSI,

(CF 3 SO 2 ) 2 N–], in which the covalent C–F

bonds are not prone to hydrolysis, unlike

the highly polar P–F bonds as in the PF 6 –

anion. Also, apart from the native moisture

present, the anodic decomposition of elec-

trolyte solvents on the cathode at the high

applied charging potentials serves as

a second source of protic species ( 14 ).

Thus, limiting the charging potential,

introduction of additives that can

scavenge the H+ byproduct, increas-

ing the solvent-system anodic decom-

position potential threshold, or de-

creasing the kinetics of such reactions

may all be pursued to achieve the

promise of long–cycle-life recharge-

able batteries.j

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GRAPHIC: A. KITTERMAN/

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bital to overlap strongly with the four filled

2 p orbitals of the oxide ligand-group in the

equatorial x-y plane, yielding four s-bond-

ing orbitals that are predominantly oxygen

in character. However, the half-filled dz 21

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 s-bonding orbital filled with oxide elec-

trons and a high-energy axial s-antibonding

orbital half-filled with the dz 2 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 perspec-

tive. 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 dz 21 orbital, and the

electron is delocalized over the TM and

O atoms; and it enhances the Lewis-base

strength of the axial oxygens com-

pared 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 LiPF 6 salt in the electrolytes

of LIBs by residual moisture gener-

ates 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 H 2 O, through ox-

ide protonation. However, this cannot

happen independently, as the oxygens

in the TMO have less negative charge

compared to the oxygen in H 2 O be-

cause of the higher covalency of TM–O

bonds compared to the H–O bonds.

The formation of H 2 O by the proton-

ation of the TMO oxides requires a net

electron transfer from the TMO to the

axial oxide orbital. This charge trans-

fer originates from the dz 21 orbital of

the TMO that contains the most reac-

tive electron. Thus, protonation of the

axial oxide ion and formation of H 2 O

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 CO 2 and other reactive protic spe-

cies ( 8 , 9 ). 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

LiPF 6 salt to generate more HF, creating a

closed-loop cycle whose net effect is the de-

struction 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+O 2 , LiNi3+O 2 ,

and Na 4 Fe4+O 4 (10–12), 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 com-

pared 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

Acid generation

The hydrolysis of the LiPF 6 salt and generation of HF with the electrolyte

solvent releases Mn2+ ions into the electrolyte.

Nucleophilic attack by the axial oxide on two protons (H+) in the electrolyte

transfers electrons from the dz 21 orbital of the manganese to oxygen. This

process forms water and causes oxidation of the Mn3+ to Mn4+.

Ion dissolution

The partial structure of a J-T–active Mn3+ oxide at the solid surface,

with the highest occupied molecular orbital with appreciable dz 2

character, is shown for one of the TMO 6 units superimposed.

Solvent

oxidation

Solvated

Mn2+

+ + +

PF 6 – H 2 O Li+ H+F– PF 5 LiOH

+2e–

H+

REFERENCES AND NOTES

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ACKNOWLEDGMENTS

This work was supported by the Welch Foundation

(grant F-1254).

10.1126/science.abc5454

10 JULY 2020 • VOL 369 ISSUE 6500 141

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.