The high‐throughput scalable production of inexpensive and efficient electrode materials at high current densities demanded by industry is a huge challenge for large‐scale implementation of energy storage technologies. Here, inspired by theoretical calculations that a FeS2/TiO2 heterostructure with built‐in electric field (BEF) can reduce the reaction energy barrier and enhance charge transport, the scalable production of cheap FeS2/TiO2 heterostructure is fabricated by utilizing natural ilmenite as precursor, exhibiting excellent electrochemical performances for sodium‐ion capacitors (SICs) anode. Assembling it with activated carbon (AC) cathode for SICs delivers high energy density (73.7 Wh kg−1) and high power density (10 kW kg−1) as well as outstanding cycle lifespan. Impressively, the method breaks through the traditional preparation approach by using natural minerals instead of high‐purity chemical raw materials as precursors for constructing heterojunctions, and price of the mineral is nearly five orders of magnitude lower than that of commercial chemical raw materials with high‐purity, which greatly reduces raw materials cost and is available for mass production. Similarly, the method can be extended to utilize other minerals to construct heterostructures, thus achieving expanded electrochemical performance, which exhibits huge potentials in electrochemical energy storage.

Interfacial coupling strategy has allured extensive attention for the possibility to endow active electrode materials with superior performance. However, the design of strong coupling engineering with interfacial evolution during electrochemical processes is very challenging. Herein, inspired by the powerful robotic arms and density functional theory calculations, multiple functional groups identified with intense affinity to V atom are successfully grafted on carbon nanotubes (CNTs), thereby in situ building robust interfacial bonds (VOC and VC) to tightly anchor VS 4 particles. The largely decreased band gaps and energy barriers show the fortified conductivity of VS 4 -CNT heterostructure. Besides, the spacial confinement effect induced by interfacial linkages substantively enhances the mechanical properties to inhibit structural collapse, and restrains the dissolution of polysulfides as verified by molecular dynamics simulations, thus prolonging life span. Excellent energy density of 105.5 Wh kg -1 can be delivered after assembling full sodium-ion capacitors (activated carbon//VS 4 -CNT). Significantly, the reversible interfacial bonds confirmed by various ex situ characteristics during discharge/charge processes hold the key to remarkable sodium storage ability and prominent initial coulombic efficiency. More impressively, strong interfacial coupling effect can establish synergistic soft-rigid integrated solid-electrolyte interphase film, which is conducive to elevating the electrochemical performance of electrodes, convincingly constructing advanced sodium-ion capacitors.

The use of as acrificial cathode additive as ap remetallation method could ensure adequate metal sources for advanced energy storage devices.However,this pre-metallation technique suffers from the precise regulation of decomposition potential of additive.H erein, am olecularly compensated premetallation (Li/Na/K) strategy has been achieved through Kolbe electrolysis,i nw hicht he electrochemical oxidation potential of ametal carboxylate is manipulated by the bonding energy of the oxygen-metal (O-M) moiety.T he electrondonating effect of the substituent and the lowcharge density of the cation can dramatically weaken the O-M bond strength, further bringing out the reduced potential. Thus,s odium acetate exhibits asuperior pre-sodiation feature for sodium-ion battery accompanied with alarge irreversible specific capacity of 301.8 mAh g À1 ,r emarkably delivering 70.6 %e nhanced capacity retention in comparison to the additive-free system after 100 cycles.T his methodology has been extended to construct ah igh-performance lithium-ion battery and al ithium/sodium/potassium-ion capacitor.

Exploring new materials with high stability and capacity is full of challenges in sustainable energy conversion and storage systems. Metal–organic frameworks (MOFs), as a new type of porous material, show the advantages of large specific surface area, high porosity, low density, and adjustable pore size, exhibiting a broad application prospect in the field of electrocatalytic reactions, batteries, particularly in the field of supercapacitors. This comprehensive review outlines the recent progress in synthetic methods and electrochemical performances of MOF materials, as well as their applications in supercapacitors. Additionally, the superiorities of MOFs-related materials are highlighted, while major challenges or opportunities for future research on them for electrochemical supercapacitors have been discussed and displayed, along with extensive experimental experiences.

Highlights Interfacial bonding strategy has been successfully applied to address the high overpotential issue of sacrificial additives, which reduced the decompositon potential of Na2C2O4 from 4.50 to 3.95 V. Ultra-low-dose technique assisted commercial sodium ion capacitor (AC//HC) could deliver a remarkable energy density of 118.2 Wh kg−1 as well as excellent cycle stability. In-depth decomposition mechanism of sacrificial compound and the relative influence after pre-metallation were revealed by advanced in situ and ex situ characterization approaches. Abstract Sacrificial pre-metallation strategy could compensate for the irreversible consumption of metal ions and reduce the potential of anode, thereby elevating the cycle performance as well as open-circuit voltage for full metal ion capacitors (MICs). However, suffered from massive-dosage abuse, exorbitant decomposition potential, and side effects of decomposition residue, the wide application of sacrificial approach was restricted. Herein, assisted with density functional theory calculations, strongly coupled interface (M–O–C, M = Li/Na/K) and electron donating group have been put forward to regulate the band gap and highest occupied molecular orbital level of metal oxalate (M2C2O4), reducing polarization phenomenon and Gibbs free energy required for decomposition, which eventually decrease the practical decomposition potential from 4.50 to 3.95 V. Remarkably, full sodium ion capacitors constituted of commercial materials (activated carbon//hard carbon) could deliver a prominent energy density of 118.2 Wh kg−1 as well as excellent cycle stability under an ultra-low dosage pre-sodiation reagent of 15–30 wt% (far less than currently 100 wt%). Noteworthily, decomposition mechanism of sacrificial compound and the relative influence on the system of MICs after pre-metallation were initially revealed by in situ differential electrochemical mass spectrometry, offering in-depth insights for comprehending the function of cathode additives. In addition, this breakthrough has been successfully utilized in high performance lithium/potassium ion capacitors with Li2C2O4/K2C2O4 as pre-metallation reagent, which will convincingly promote the commercialization of MICs.