Significant capacity losses are generally seen for batteries containing high-capacity lithium alloy forming anode materials such as silicon, tin and aluminium. These losses are generally ascribed to a combination of volume expansion effects and irreversible electrolyte reduction reactions. Here, it is shown, based on e.g. elemental analyses of cycled electrodes, that the capacity losses for tin nanorod and silicon composite electrodes in fact involve diffusion controlled trapping of lithium in the electrodes. While an analogous effect is also demonstrated for copper, nickel and titanium current collectors, boron-doped diamond is shown to function as an effective lithium diffusion barrier. The present findings indicate that the durability of lithium based batteries can be improved significantly via proper electrode design or regeneration of the used electrodes.

Rechargeable lithium‐based batteries generally exhibit gradual capacity losses resulting in decreasing energy and power densities. For negative electrode materials, the capacity losses are largely attributed to the formation of a solid electrolyte interphase layer and volume expansion effects. For positive electrode materials, the capacity losses are, instead, mainly ascribed to structural changes and metal ion dissolution. This review focuses on another, so far largely unrecognized, type of capacity loss stemming from diffusion of lithium atoms or ions as a result of concentration gradients present in the electrode. An incomplete delithiation step is then seen for a negative electrode material while an incomplete lithiation step is obtained for a positive electrode material. Evidence for diffusion‐controlled capacity losses is presented based on published experimental data and results obtained in recent studies focusing on this trapping effect. The implications of the diffusion‐controlled Li‐trapping induced capacity losses, which are discussed using a straightforward diffusion‐based model, are compared with those of other phenomena expected to give capacity losses. Approaches that can be used to identify and circumvent the diffusion‐controlled Li‐trapping problem (e.g., regeneration of cycled batteries) are discussed, in addition to remaining challenges and proposed future research directions within this important research area.

While the use of silicon‐based electrodes can increase the capacity of Li‐ion batteries considerably, their application is associated with significant capacity losses. In this work, the influences of solid electrolyte interphase (SEI) formation, volume expansion, and lithium trapping are evaluated for two different electrochemical cycling schemes using lithium‐metal half‐cells containing silicon nanoparticle–based composite electrodes. Lithium trapping, caused by incomplete delithiation, is demonstrated to be the main reason for the capacity loss while SEI formation and dissolution affect the accumulated capacity loss due to a decreased coulombic efficiency. The capacity losses can be explained by the increasing lithium concentration in the electrode causing a decreasing lithiation potential and the lithiation cut‐off limit being reached faster. A lithium‐to‐silicon atomic ratio of 3.28 is found for a silicon electrode after 650 cycles using 1200 mAhg⁻¹ capacity limited cycling. The results further show that the lithiation step is the capacity‐limiting step and that the capacity losses can be minimized by increasing the efficiency of the delithiation step via the inclusion of constant voltage delithiation steps. Lithium trapping due to incomplete delithiation consequently constitutes a very important capacity loss phenomenon for silicon composite electrodes.

The generation of a distribution of nanoparticles upon conversion reaction of thin Cu₂O layers is demonstrated to produce a wide electrochemical potential window, as well as a distinctive capacity increase in large area three-dimensional electrodes. Cu nanopillars with a 10–15 nm Cu₂O coating containing traces of nanocrystalline Fe₂O₃ yield capacities up to 0.265 mA h cm⁻² (at 61 mA g⁻¹), excellent cycling for more than 300 cycles and an electroactive potential window larger than 2 V, due to the size effects caused by the various Cu/Cu₂O nanoparticles formed during conversion/deconversion. These 3D Li-ion battery electrodes based on electrodeposited Cu nanopillars spontaneously coated with a Cu₂O layer are compatible with current densities of 16 A g⁻¹ (i.e. 61 C rates) after aerosol-assisted infiltration with an iron acetate solution followed by low-temperature pyrolysis. The capacity of the composite material increases by 67% during 390 cycles due to the growth of the electroactive area during the electrochemical milling of Cu₂O forced by its repeated conversion/de-conversion. The latter generates a distribution of nanoparticles with different sizes and redox potentials, which explains the broad potential window, as well as the significant capacity contribution from double layer charging. These 3D electrodes should be well-suited for Li-ion microbatteries and Li-ion batteries in general, since they combine high capacities per footprint area with excellent power capabilities. More importantly, such electrodes grant access to fundamental understanding of the electrochemical behaviour of these active materials providing new insights into both conversion mechanisms and nanostructured interfaces more in general.