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. 2026 Sep 16. Online ahead of print. doi: 10.1039/d6sc06091a

An orbital-coupling-driven bifunctional prelithiation additive for enhanced practical Li-ion full cells

Na Tian a, Xing Liu b, Kangyu Zhou c, Xiaolin Deng a, Shuting Kong b, Xiuli Jia b, Peixin Zhang a, Lipeng Zhang b,✉, Yanyi Wang a,✉, Dingtao Ma a,✉
PMCID: PMC13579521  PMID: 42751313

Abstract

Prelithiation has been widely recognized as an effective strategy to compensate for active lithium loss and enhance the energy density of lithium-ion batteries. This work develops a highly efficient Ti-doped cathode prelithiation additive, 2% Ti-doped Li2NiO2 (Ti 2-LNO). As demonstrated, such a prelithiation material delivers a lasting ion–electron bifunctional bridge: it efficiently replenishes the irreversible lithium loss of LiFePO4 during the initial cycle and transforms into Ti 2-LiNiO2 thereafter. Notably, the orbital coupling at the interface between Ti 2-LiNiO2 and LFP forms an efficient electron transport channel; meanwhile, the incorporation of Ti 2-LiNiO2 contributes to the formation of a stable, LiF-rich and low-impedance cathode/electrolyte interphase (CEI), thereby optimizing ion–electron synergistic transport, accelerating interfacial charge transfer, and alleviating both electrochemical and concentration polarization at high rates. Compared with the conventional Li‖LiFePO4 half-cell, enabled by the synergistic effect of efficient lithium compensation and capturing the sluggish electrons in LFP to achieve rapid electron transfer, the cell with a 10 wt% Ti 2-LNO additive exhibits significantly improved rate capability, delivering a high reversible capacity of 87.2 mA h g−1 at 5C after 1000 cycles. Furthermore, a practical graphite‖LiFePO4 with 10 wt% Ti 2-LNO full cell (N/P = 1.2) exhibits enhanced cycle stability, retaining 98.60% of its initial capacity after 200 cycles at 0.5C. This work presents a design concept for high-performance cathode prelithiation additives that synergistically couples efficient Li+ compensation with accelerated ion–electron transport kinetics, enabling high-power and long-life Li-ion full cells.

The interfacial orbital coupling between LFP and Ti-doped Li2NiO2 (Ti 2-LNO) captures sluggish electrons, boosting electronic conductivity. Besides, it facilitates the formation of a LiF-rich CEI and optimizes the interfacial kinetic properties.graphic file with name d6sc06091a-ga.webp

1. Introduction

Since the commercialization of lithium-ion batteries (LIBs), LIBs have gradually occupied a pivotal position in modern energy systems.1,2 As one of the most commercially successful cathode materials for LIBs, lithium iron phosphate (LFP) serves as the cornerstone of the industry and the mainstream power material by virtue of its superior thermal stability, high safety, and suitable operating voltage.3Howerver, the inevitable two-phase transition between LiFePO4 and FePO4 (ref. 4) as well as the irreversible lithium depletion5–7 caused by the formation of solid electrolyte interphase (SEI), lead to deterioration of the cycle lifespan in LFP batteries. These issues pose severe challenges to achieving high energy density and long-cycle-life LIBs.8 Prelithiation technologies9–11 have proven effective in addressing the above challenges, thus achieving an extended cycle life and breaking the energy limits of LFP based batteries.12,13 Notably, cathode prelithiation, a mainstream addictive, possesses prominent advantages such as favorable process compatibility, high operational safety, and superior cost-effectiveness. Typical cathode lithium supplement additives mainly include Li2O,14 Li2O2,15,16 Li3N,17,18 organic lithium salts, and lithium-rich oxides such as Li2NiO2 (LNO) and Li5FeO4 (LFO).19 Notably, Li2NiO2 exhibits a high lithium compensation capacity and excellent safety, free from adverse gas evolution.20 Benefiting from the variable valence of nickel, Li2NiO2 can still contribute to the reversible capacity after the initial charge–discharge activation, which distinguishes it fundamentally from conventional prelithiation agents.

Previous studies on Li2NiO2 have mainly focused on enhancing its initial charge–discharge capacity. For example, Cu2+ doping markedly elevates the initial charge capacity and prelithiation capacity of Li2NiO2.21 Han et al.22 calculated the effects of various dopants on the electronic conductivity of Li2NiO2, confirming that the band gap was significantly narrowed after Cr doping, which further affected the reactivity and average electrochemical voltage of the material. When utilized as a cathode prelithiation agent, tuning the ionic and electronic transport properties of the cathode driven by Li2NiO2 as well as compensating for lithium loss significantly determines the overall electrochemical performance of battery systems. Nevertheless, systematic investigations on coupling efficient Li+ compensation with accelerated ion–electron transport kinetics driven by Li2NiO2 remain insufficient to date.

Herein, trace doping of 3d0 transition metal Ti4+ is proposed to boost both prelithiation capacity and ionic/electronic transport ability (Fig. 1). On one hand, high valence Ti4+ introduces metallic vacancies and moderately expands the interlayer spacing, improving the initial charge–discharge specific capacity of Li2NiO2. On the other hand, Ti-doped Li2NiO2 acts as a critical ion–electron bifunctional bridge. Under high-rate charge–discharge conditions, the interfacial orbital coupling between Ti 2-LiNiO2 and LFP constructs rapid electron transport channels, which accelerate the migration of sluggish electrons. Meanwhile, it promotes the formation of LiF-rich CEI films, thereby facilitating Li+ diffusion kinetics. As a result, it constructs unimpeded electron transport pathways and significantly reduces charge-transfer resistance and electrochemical polarization. This synchronous and synergistic ion–electron transport effectively addresses the core issues of insufficient electronic conductivity and slow Li+ diffusion in LFP at high rates.23

Fig. 1. Schematic illustration of the ion–electron bifunctional bridge mechanism of LiFePO4.

Fig. 1

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2. Experimental

2.1. Materials

Li2O (99.99%, Aladdin), NiO (99.99%, Aladdin), TiO2 (99%, Aladdin), polyvinylidene fluoride (PVDF, Arkema), Super-p (Canrd), 1-methyl-2-pyrrolidinone (NMP, 99.5%, Innochem), lithium chips (Canrd), pristine LFP (Canrd) and commercial graphite anode (Canrd) were directly used without further purification. PP separators are punched into circular discs with a diameter of 17 mm. Pole pieces were cut into 12 mm diameter discs. The CR2032 coin cell housings and components (304 stainless steel) were ultrasonically cleaned prior to use.

2.2. Material synthesis

2.2.1. Synthesis of Li2NiO2

Li2O (99.99%, Aladdin) and NiO (Aladdin, 99.99%) with stoichiometric amounts were mixed in an agate mortar. Then, the mixture was calcined under an Ar atmosphere at 700 °C for 14 h with a ramping rate of 3 °C min−1. The final products were carefully collected after cooling to room temperature naturally and transferred into an Ar-filled glovebox.

2.2.2. Synthesis of Ti-doped Li2NiO2

Ti–Li2NiO2 was synthesized following the same approach as above with Li2O (99.99%, Aladdin), NiO (Aladdin, 99.99%) and TiO2 (99%, Aladdin).

2.3. Material characterization

Surface morphologies and element mapping images were examined using a field emission scanning electron microscope (FE-SEM) (JEOL, JSM-7800F) equipped with an energy dispersive X-ray spectrometer (EDS) (Ametek, TEAM Octane Plus) at an accelerating voltage of 15 kV. Transmission electron microscopy (TEM) was performed using a JEM-2100 & X-Max80 microscope at an accelerating voltage of 200 kV. X-ray diffraction (XRD) measurements were performed using a PANalytical Empyrean with Cu Kα radiation (λ = 1.54065 Å) at 45 KV and 40 mA. In situ XRD testing was conducted using a mold battery with an Al current collector and a testing window to monitor phase changes of the material during cycling, with a scanning range of 10–60°, and charge/discharge tests were conducted at a rate of 0.15C. During rate charge–discharge cycling, XRD patterns were collected at five-minute intervals. XPS measurements were performed using a Thermo Fisher Scientific K-Alpha spectrometer (Al Kα radiation) with a scanning rate of 0.05 eV per step.

2.4. Electrochemical test

To evaluate the electrochemical performance of LFP half-cells and LiFePO4‖graphite full cells, an electrochemical test was performed using a coin-type cell (CR2032). All the coin cells were fabricated in an Ar-filled glove box with water and oxygen concentrations of less than 0.01 ppm. The cathode electrode preparation process is as follows: the active substance (LFP or LFP with a moderate amount of Ti 2-Li2NiO2 cathode prelithiation additive), conductive carbon black (Super P) and binder PVDF were evenly mixed at a mass ratio of 8 : 1 : 1, and N-methylpyrrolidone (NMP) solvent was added and continuously stirred to form a uniform slurry. The slurry was coated on aluminum foil, followed by drying in a vacuum oven for 12 h at 80 °C. The LFP electrode was cut into discs (Φ 12 mm) with a mass loading of 1.5–2 mg cm−2. For the anode fabrication, graphite, Super P, and poly(vinylidene fluoride) (PVDF) were mixed at a mass ratio of 8 : 1 : 1 to form a slurry. The resulting slurry was then cast onto a copper foil current collector and vacuum-dried at 80 °C for 12 h to obtain a graphite anode. The electrode was cut into discs (Φ 14 mm) with a mass loading of ∼1.4 mg cm−2.

The coin half cells (CR2032) were assembled with Li metal as the counter electrode and a Celgard 2325 polypropylene film as the separator and approximately 150 µL of the electrolyte (1 M LiPF6 in DMC : EC : EMC = 1 : 1 : 1 vol%) was injected into each half-cell. The LiFePO4‖graphite full cells were assembled with a negative-to-positive (N/P) capacity ratio of 1.2. A Celgard 2325 polypropylene film was used as the separator. Approximately 150 µL of electrolyte (1 M LiPF6 in DMC : EC : EMC = 1 : 1 : 1 vol%) was injected into each full cell. The CR2032 coin cells were assembled and aged for 12 h before the electrochemical measurements. The long cycling performance of the LFP coin cell was initially activated at 0.1C (1C = 170 mA h g−1) for three cycles at 2.5–4.3 V and then tested at other rates. Cyclic voltammetry (CV) measurement was performed using an electrochemical workstation (Solartron Analytical, Ametek, 1470E) at a scan rate from 0.1 to 1.5 mV s−1. The electrochemical performance of the LFP half cell was tested from 2.5 to 4.3 V on a LAND CT3001A. The electrochemical performance of the LFP full cell was tested from 2.5 to 3.8 V on a LAND CT3001A. The EIS spectra were measured after the cells had reached a stable open-circuit potential in the range of 100 kHz to 0.01 Hz.

2.5. DFT calculation

All the calculations are implemented using the VASP code.24 The GGA-PBE functional is selected for the exchange and correlation potentials.25 Weak van der Waals interaction is considered using the DFT-D3 functional.26 The cut-off energy for the plane wave is 500 eV. The Gamma point in the Brillouin zone is chosen for integration. The total energies of the systems converge to 10–5 eV in the iterative solution of the Kohn–Sham equation. The force on each atom reduces to 0.05 eV Å−1 after geometry optimization. The diffusion path and barrier are determined by the climbing image nudged elastic band method27

3. Results and discussion

X-ray diffraction (XRD) was performed on the as-synthesized pristine Li2NiO2 and a series of Ti-doped samples with different doping levels (Ti 1-LNO, Ti 2-LNO, and Ti 3-LNO). All samples can be precisely indexed to Li2NiO2 with an Immm space group with the characteristic peaks at 19.6° and 25.7° corresponding to the (002) and (101) crystal planes of LNO (JCPDS no. 97-002-5000). As displayed in Fig. 2a, no impurity phases were observed in any of the Ti-doped samples, indicating that Ti4+ can be successfully incorporated into the host structure. This is attributed to the similar ionic radii of Ti4+ (0.605 pm) and Ni2+ (0.69 pm). Besides, as seen in Fig. 2a, the (101) diffraction peak gradually shifted toward lower Bragg angles with increasing Ti doping level. This is attributed to the introduction of high-valence Ti4+ inducing the formation of Ni2+ vacancies to maintain charge neutrality, which expands the interlayer spacing.28 Additionally, Rietveld refinement was performed on LNO and Ti 2-LNO using GSAS software (Fig. S1 and S2), and the obtained lattice parameters, cell volume, R factor (Rwp), χ2 and other data are listed in Table S1, in which Ti 2-LNO possesses larger lattice parameters (LNO: a = 3.7444 Å and c = 9.0217 Å; Ti 2-LNO: a = 3.7574 Å and c = 9.0370 Å). To further verify the enlarged interlayer spacing induced by Ti doping, transmission electron microscopy (TEM) was conducted on pristine LNO and Ti 2-LNO (Fig. 2c and d, respectively, and Fig. S3). Fast Fourier transform (FFT) and inverse fast Fourier transform (IFFT) were applied to selected regions, revealing distinct and uniform lattice fringes. The (103) crystal plane (Fig. c2 and d2) exhibited a lattice spacing of 0.204 nm for pristine LNO and a slightly increased value of 0.207 nm for Ti 2-LNO. By contrast, the lattice expansion along the (003) crystal plane (Fig. c1 and d1) was pronounced, with the spacing increasing from 0.236 nm (pristine LNO) to 0.248 nm (Ti 2-LNO). This variation exerts a positive and significant effect on the Li+ intercalation/deintercalation capability and ionic diffusion kinetics of the material. As shown by the X-ray photoelectron spectrometry (XPS) analyses29 in Fig. 2b, an intense and distinct Ti 2p signal appeared in Ti 2-LNO, whereas no Ti signal was detected in pure LNO, confirming the successful incorporation of Ti element. Meanwhile, the energy-dispersive spectroscopy (EDS) elemental mapping images of Ti 2-LNO (Fig. 2e) demonstrated the uniform distribution of Ti throughout the material. Additionally, field-emission scanning electron microscopy (FESEM) was carried out to investigate the effect of Ti doping on the morphology of LNO. Ti 2-LNO presented a relatively flat and smooth surface (Fig. 2e), in sharp contrast to the rough surface of pristine LNO shown in Fig. S4. This phenomenon arises because Ti doping suppresses the formation of impurities, which is consistent with the lower contents of the NiO impurity phase and Li2CO3 in Ti 2-LNO derived from Rietveld refinement of XRD patterns in Table S1. Besides, as shown in Fig. S5, Ti 2-LNO gradually transforms into the Ti–LiNiO2 structure during the charging process. The gradual disappearance of the (101) peak of LNO and the emergence of the (003) peak of Ti–LiNiO2 clearly identify the phase transition pathway.20

Fig. 2. (a) XRD patterns of pristine LNO and Ti-doped LNO. (b) XPS spectra of Ti 2P for pristine LNO and Ti 2-LNO. TEM images of pristine LNO (c) and Ti 2-LNO (d). (e) FESEM and EDS mapping images of Ti 2-LNO.

Fig. 2

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In order to evaluate the promotion effect of Ti doping on the lithium-supplementing performance of LNO, all samples were assembled into half-cells with metallic lithium as the counter electrode. As displayed in Fig. 3a, pristine LNO delivered initial charge and discharge specific capacities of 304.7 mA h g−1 and 109.1 mA h g−1, respectively, within a voltage window of 2.5–4.3 V at 0.1C (1C = 320 mA h g−1), possessing a contributing adscititious capacity of only 195.6 mA h g−1. Encouragingly, the initial charge and discharge specific capacities of all samples were improved thanks to Ti incorporation. Notably, the sample with 2% Ti doping showed the optimal performance, achieving an initial charge capacity of 367.7 mA h g−1 along with an initial discharge capacity of 131.2 mA h g−1, resulting in its obtainable irreversible capacity rising to 236.5 mA h g−1, an increase of 20.9% relative to pure LNO. These results reveal that Ti-modified materials, especially the 2% Ti-doped sample, possess enhanced lithium deintercalation capability. As intuitively displayed in Fig. 3b, the second-cycle charge/discharge capacities of Ti 2-LNO were significantly higher than those of pristine LNO. As presented in the cyclic voltammetry (CV) curves at a scan rate of 0.1 mV s−1 (Fig. 3c and S6), Ti 2-LNO exhibited a sharper and negatively shifted oxidation peak (Ti 2-LNO: 3.88 V vs. pristine LNO: 3.96 V) and a larger peak current density, confirming its more favorable reaction kinetics and higher lithium-supplementing capacity. Similarly, Fig. 3d revealed that Ti doping effectively reduced the diffusion resistance within LNO. These improvements can be attributed to the generation of vacancies, which provide more favorable pathways for Li+ migration.30 Meanwhile, vacancies act as “fast diffusion channels”, leading to higher ionic conductivity and faster Li+ diffusion.30 This conclusion is also consistent with the CV results at various scan rates (Fig. 3e and f). Ti 2-LNO showed a smaller peak potential difference (0.187 V) than pristine LNO (0.193 V), indicating lower polarization and more reversible electrochemical behavior. As illustrated in Fig. 3h, which showed the rate performance of all samples from 0.2C to 5C, Ti 2-LNO displayed remarkably superior rate capability. Furthermore, the modified materials maintained discharge capacities at the 100th cycle under 0.1C (Fig. 3g) of 45.6, 65.3, and 59.3 mA h g−1 for Ti 1-LNO, Ti 2-LNO, and Ti 3-LNO, respectively, all significantly exceeding the 36.8 mA h g−1 of pristine LNO. All Ti-modified samples exhibited more stable cycling performance, ascribed to the stronger bond energy of Ti–O compared with Ni–O, which stabilizes the lattice framework and prevents structural collapse during prolonged cycling.31,32

Fig. 3. (a) Initial charge and discharge curves of pristine LNO and Ti-doped LNO. (b) The second charge and discharge specific capacity of LNO and Ti-doped LNO. (c) CV curves of the first cycle at 0.1 mV s−1 of pristine LNO and Ti 2-LNO. (d) EIS spectra and the equivalent circuit of samples. CV curves of pristine LNO (e) and Ti 2-LNO (f) at different scan rates. (g) Long-term cycling performance of LNO and Ti-doped LNO at 0.1C in the voltage range of 2.5–4.3 V. (h) Rate performance.

Fig. 3

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To elucidate the effect of Ti 2-LNO on the electrochemical performance of LiFePO4 (LFP), half-cells were fabricated using bare LFP and LFP with different Ti 2-LNO addition contents (6 wt%, 10 wt%, and 14 wt%). The initial charge–discharge profiles in Fig. 4b clearly demonstrated Li+ intercalation/deintercalation capability: the initial specific capacities increased gradually with increasing Ti 2-LNO content. The initial charge specific capacities of bare LFP and LFP with 6 wt%, 10 wt%, and 14 wt% Ti 2-LNO samples are 170.4, 179.5, 193.6, and 201.7 mA h g−1, respectively, with corresponding discharge specific capacities of 160.5, 172.3, 170.8, and 173 mA h g−1. An enlarged view of the selected region in Fig. 4b (Fig. 4c) showed that the electrode with 10 wt% Ti 2-LNO exhibited the lowest charge plateau and the highest discharge plateau, corresponding to the smallest voltage polarization. However, the cycling data at 1C after 500 cycles manifested in Fig. 4a indicated that although the LFP with 14 wt% Ti 2-LNO sample delivered a relatively high specific capacity in the early cycles, it suffered severe capacity fading during subsequent cycling, with a decay rate second only to that of bare LFP. This phenomenon can be attributed to the excessive lithium-supplement additive blocking Li+ diffusion pathways, leading to irreversible capacity loss during cycling. By comparison, the LFP with 6 wt% and 10 wt% Ti 2-LNO samples exhibited much better cycling stability, and the LFP with 10 wt% Ti 2-LNO electrode achieved the optimal balance between high specific capacity and superior cycling durability. The capacity retention of samples with different addition contents was more intuitively displayed by histograms and line graphs derived from the cycling data in Fig. S7. After 500 cycles at 1C, the discharge specific capacities and capacity retention ratios of bare LFP and LFP with 6 wt%, 10 wt%, and 14 wt% Ti 2-LNO electrodes were 108.9, 134.6, 142, and 123.8 mA h g−1, with capacity retention ratios of 77.5%, 91.2%, 94.8%, and 83.6%, respectively. Fig. 4d and S8 compare the cyclic voltammetry (CV) curves of the 10 wt% Ti 2-LNO cathode and bare LFP at a scan rate of 0.1 mV s−1. The LFP with 10 wt% Ti 2-LNO sample clearly showed a negatively shifted oxidation peak related to the Fe2+/Fe3+ redox couple33,34 (10 wt% Ti 2-LNO: 3.58 V vs. bare LFP: 3.63 V), indicating significantly improved electrochemical kinetics, and a new peak near 3.92 V, providing additional capacity contribution, which corresponded with Ti 2-LNO. Notably, the second and third CV curves overlap almost completely, demonstrating excellent reaction reversibility of the LFP with 10 wt% Ti 2-LNO electrode. The rate performance at different current densities ranging from 1C to 10C (Fig. 4e) and the galvanostatic charge–discharge (GCD) profiles (Fig. 4f and S10) further revealed the superior electron transport properties of the LFP with 10 wt% Ti 2-LNO electrode. At 10C, the 10 wt% sample delivers an average discharge capacity of 69.34 mA h g−1, much higher than the 24.67 mA h g−1 of bare LFP. After varying the current density from 1C to 10C and returning to 1C, the electrode with 10 wt% Ti 2-LNO recovered a discharge capacity of 148.1 mA h g−1, compared with 137.4 mA h g−1 for bare LFP. More impressively, long-term cycling at 5C (Fig. 4g) verified the outstanding high-rate capability: the cathode with 10 wt% Ti 2-LNO maintained a discharge capacity of 87.2 mA h g−1 after 1000 cycles, far exceeding the 48.9 mA h g−1 of bare LFP. This highlights the remarkable enhancement effect of Ti 2-LNO on the fast-charging performance of LFP.

Fig. 4. (a) Long-term cycle performance of bare LFP and LFP with 6% Ti 2-LNO additive, with 10% Ti 2-LNO additive and with 14% Ti 2-LNO additive electrodes at 1C after 3 cycles of 0.1C activation. The first cycle of GCD curves of bare LFP and LFP with 6% Ti 2-LNO additive, with 10% Ti 2-LNO additive and with 14% Ti 2-LNO additive electrodes (b) and the selected region enlarged profile (c). (d) CV curves of the initial three cycles at 0.1 mV s−1 of the LFP with 10% Ti 2-LNO additive electrode. (e) Rate performance. (f) GCD curves of the LFP with 10% Ti 2-LNO additive electrode at different current densities. (g) Long-term cycle performance of bare LFP and LFP with 10% Ti 2-LNO additive electrodes at 5C after 3 cycles of 0.1C activation.

Fig. 4

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To investigate the mechanism of Ti 2-LNO, a series of in situ, ex situ, and post-cycling characterization studies were performed, as presented in Fig. 5a–d. In situ XRD tests were conducted on bare LFP and LFP with 10 wt% Ti 2-LNO (Fig. 5a and b) to monitor the structural evolution of LFP during charge–discharge cycling. As shown in Fig. 5b, during the charge/discharge process, the two-phase reaction region is shortened,23,35 probably benefiting from the construction of a stable interface to impede parasitic reactions, in which Ti 2-LNO plays a crucial role in making up for lithium loss. Besides, the cathode with 10% Ti 2-LNO displayed weaker peak attenuation, which proves that LFP with 10 wt% Ti 2-LNO possesses enhanced lattice stability. Fig. S11 shows the SEM and EDS characterization results of LFP with 10 wt% Ti 2-LNO before cycling. We can see blocky Ti 2-LNO and spherical LFP scattered around. Fig. 5c and d show FESEM, TEM, and XPS characterization results of LFP electrodes with and without the lithium-supplement additive after 100 cycles, respectively. In contrast to the severe cracking of bare LFP particles (Fig. 5c1), the electrode modified with the lithium-supplement additive (Fig. 5c2) exhibited significantly less surface deposition and a much more intact and smooth morphology, which benefit long-term stability.36Fig. 5c3 and c4 illustrate the morphology of the CEI layer. The CEI layer on the electrode with 10 wt% Ti 2-LNO was notably thinner and more uniform, forming a CEI layer with a thickness of approximately 6.13 nm, whereas that on the bare LFP electrode was thicker and unevenly distributed, varying from 18.81 nm to 40.83 nm. Such an interfacial structure increases the diffusion resistance of Li+, resulting in degraded cycling stability and capacity fading.37,38 In C 1s XPS spectra (Fig. S12 and S13), the relative intensity of the main organic by-product peaks (C–F) originating from solvent decomposition decays as the etching depth increases for both LFP with 10 wt% Ti 2-LNO and bare LFP, which confirms a reduction in the inner organic components.20 It is worth noting that LFP with 10 wt% Ti 2-LNO (7.71% and 6.29%) has a lower proportion of organic components at different etching times compared to bare LFP (8.09% and 7.64%). As shown in Fig. 5d, analyzing the F 1s spectra, we can see two obvious peaks: the peak near 688 eV represents organic fluorides, while the peak near 685.5 eV represents LiF species. Fitting results of the F 1s XPS spectra (Fig. S14) revealed that the electrode with 10 wt% additive possessed a higher abundance of LiF species, which can effectively suppress side reactions at the electrode interface and inhibit the dissolution of metal ions.39,40

Fig. 5. In situ XRD patterns of evolution of the main characteristic diffraction peaks during the initial charge and discharge at 0.15C of (a) the LFP cathode and (b) the LFP with 10% Ti 2-LNO additive cathode. (c) FESEM and TEM images of bare LFP and the LFP with 10% Ti 2-LNO additive cathode after 100 cycles. (d) XPS spectra of the F 1s region of CEI formed on bare LFP and the LFP with 10% Ti 2-LNO additive cathode after 100 cycles.

Fig. 5

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To clarify the electron/ion transport bridging effect of Ti 2-LiNiO2, theoretical calculations were conducted. Density of states (DOS) calculations illustrated the mechanism by which Ti 2-LiNiO2 modifies the electrical conductivity of LFP. As shown in Fig. 6a and b, LFP with Ti 2-LiNiO2 possesses a higher electron density near the Fermi level (Ef), indicating enhanced electronic conductivity of LFP, which benefits the battery's cycling and rate capabilities.41 Notably, the unoccupied 3d orbitals of Ti overlap significantly with the 3d orbitals of Fe. The orbital coupling forms rapid electron transfer channels at the interface, facilitating faster electron transport in LFP with Ti 2-LiNiO2 and avoiding phase separation and structural degradation caused by slow electron transport during cycling. Fig. 6c shows the Fe 3d orbital centers of bare LFP and LFP with Ti 2-LiNiO2, in which the Fe 3d orbital center was elevated after Ti 2-LiNiO2 introduction (−1.74 eV → −1.68 eV), indicating strengthened Fe–O bonding, which contributes to a longer battery cycling lifespan.41 Structural models of bare LFP and LFP with Ti 2-LiNiO2 are presented in Fig. 6d and e. As shown in Fig. 6f, the Li+ migration energy barriers of LFP with Ti 2-LiNiO2 (0.2162 eV) are much lower than those of bare LFP (1.8702 eV), demonstrating reduced Li+ migration barriers and accelerated Li+ diffusion kinetics.42 It should be noted that the unusually high migration barrier of 1.8702 eV obtained in this work arises from a different surface termination.

Fig. 6. Analysis of the density of states (DOS) for bare LFP (a) and LFP with Ti 2-LiNiO2 (b). (c) Schematic of the rise of the d-band center in LFP with Ti 2-LiNiO2 based on calculation data of (pDOS) of Fe 3d. The corresponding overall schematic diagram of the Li+ diffusion path. (d) Bare LFP and (e) LFP with Ti 2-LiNiO2. (f) The calculated diffusion energy barrier profiles of bare LFP and LFP with Ti 2-LiNiO2.

Fig. 6

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To further explore the improved Li+ transport kinetics in LFP batteries enabled by Ti 2-LNO, multiple kinetic analyses were carried out, including galvanostatic intermittent titration technique (GITT), CV, and in situ EIS. The Li+ diffusion coefficients (DLi+) calculated from GITT measurements (Fig. 7a) are plotted in Fig. 7b. During both charge and discharge processes, the Li+ diffusion coefficient of LFP is notably enhanced after introducing 10 wt% Ti 2-LNO, confirming smoother Li+ diffusion and superior electrochemical kinetics. This is attributed to the fact that Ti 2-LNO promotes the formation of a thin and uniform LiF-rich CEI layer on LFP as well as the fast and homogeneous phase transition reaction, facilitating the rapid completion of Li+ intercalation and deintercalation processes, thus enhancing its lithium ion diffusion and transport capability.39 More importantly, Ti-doped Li2NiO2 acts as a critical ion–electron bifunctional bridge between LFP and the electrolyte. Under high-rate charge–discharge conditions, the empty 3d orbitals of Ti4+ couple with Fe 3d orbitals, rapidly capturing electrons accumulated at the LFP interface, constructing unimpeded electron transport pathways, and significantly reducing charge-transfer resistance and electrochemical polarization. Fig. 7c and d display the CV curves of bare LFP and 10 wt% Ti 2-LNO-modified LFP at various scan rates. The modified sample exhibited a significantly reduced potential difference of 0.242 V, compared with 0.349 V for bare LFP, indicating a weaker electrochemical polarization. Besides, Fig. S9 shows that peak currents (Peak A and B) for both electrodes have linear relationships with the square root of scan rates. In situ EIS tests were performed on both electrodes (Nyquist plots are shown in Fig. 7e and f). The semicircle in the medium–high frequency region corresponds to the charge-transfer resistance (Rct) at the electrode/electrolyte interface, while the linear slope in the low-frequency region represents the Warburg impedance (Zw).43,44Fig. 7g intuitively presents the fitted Rct values derived from Fig. 7c and d. For bare LFP, Rct initially decreases, likely due to the formation of the CEI layer, but gradually increases after the 20th cycle, which can be attributed to continuous side reactions and structural degradation during cycling.41 In comparison, the Rct value of the modified electrode remains considerably lower after CEI formation and shows no obvious increase over 50 cycles. This demonstrates that the CEI layer stabilized by the lithium-supplement additive effectively shields the electrode surface from electrolyte erosion. The remarkably reduced Rct facilitates fast Li+ transport and contributes to significantly improved electrochemical kinetics.

Fig. 7. (a) GITT curves of the LFP cathode and LFP with 10% Ti 2-LNO additive cathode. (b) The calculated diffusion coefficient values. CV curves of bare LFP (c) and the LFP with 10% Ti 2-LNO additive cathode (d) at different scan rates. In situ EIS Nyquist plots of bare LFP (e) and the LFP with 10% Ti 2-LNO additive cathode (f) at different cycles. (g) The impedance of bare LFP and the LFP with 10% Ti 2-LNO additive cathode at different cycles.

Fig. 7

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To better understand the practical application of the prelithiation effect of Ti 2-LNO, we assembled LFP‖graphite full cells and tested them within a voltage range of 2.5–3.8 V (Fig. 8a). Graphite half-cell performance is provided in Fig. S15. As shown in Fig. 8b, the pristine LFP‖graphite cell delivers initial charge and discharge capacities of 160.74 and 149.58 mA h g−1, respectively. In contrast, the full cell with 10 wt% Ti 2-LNO exhibits significantly enhanced initial charge and discharge capacities of 170.80 and 157.57 mA h g−1, which can be attributed to the extra lithium contribution from the Ti 2-LNO prelithiation additive. These beneficial effects persist stably in full cells. On one hand, the introduction of Ti 2-LNO induces a thinner and more uniform CEI layer, which helps maintain the structural stability of LFP during cycling. On the other hand, Ti 2-LNO retains a robust structure after the first discharge and continues to provide a certain capacity contribution. More importantly, the orbital coupling at the interface between Ti 2-LiNiO2 and LFP forms an efficient electron transport channel, promoting the elimination of hard-to-transfer electrons. Through these dual effects, the full cell with 10 wt% Ti 2-LNO maintains a discharge capacity of 145.98 mA h g−1 after 200 cycles at 0.5C (Fig. 8c), corresponding to an ultra-high capacity retention of 98.60%. In comparison, the bare LFP cell only delivers 76.05 mA h g−1 after 200 cycles, representing a severe capacity drop of 47.15% from its initial capacity. Additionally, the cycling performance comparison of this work and the previously reported work45–50 is displayed in Table S2. Obviously, the cathode with the Ti 2-LNO additive shows superlative capacity retention with the highest specific capacity after cycling in a LFP‖graphite full cell. Such nearly lossless and ultra-stable cycling performance strongly demonstrates the promising commercialization potential of Ti 2-LNO. Fig. 8d and S16 further compare the rate performance of the two cells from 0.1C to 1C. The discharge specific capacities of LFP with 10 wt% Ti 2-LNO at 0.1/0.2/0.5/1C are 177.72/166.85/152.90/133.24 mA h g−1, respectively, whereas those of pristine LFP are only 152.63/144.42/133.72/121.06 mA h g−1. It can be seen that Ti 2-LNO significantly improves the rate performance of LFP. Overall, Ti 2-LNO exhibits a favorable enhancement effect on the full-cell performance of LFP‖graphite, which is attributed to the interfacial optimization and pre-lithiation effect of Ti 2-LNO. This work provides a meaningful reference for its practical commercial application.

Fig. 8. (a) Schematic of a lithium-ion full-cell with a graphite anode and LiFePO4 cathode. (b) The initial charge and discharge curves of bare LFP and LFP with 10% Ti 2-LNO‖graphite in the potential range of 2.5–3.8 V at 0.1C. (c) Long-term cycle performance of bare LFP and LFP with 10% Ti 2-LNO‖graphite at 0.5C. (d) Rate performance.

Fig. 8

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4. Conclusion

This study designed Ti 2-LNO as a pre-lithiation additive for LFP-based batteries. The results show that Ti4+ with empty 3d orbitals effectively solves the problems of insufficient lithium supply and slow electron transfer in LFP systems. Ti 2-LNO not only compensates for irreversible lithium loss of LFP but also optimizes ion/electron transport by tuning orbital coupling, reduces polarization, and suppresses side reactions by forming stable CEI films. The LFP with 10 wt% Ti 2-LNO system exhibits excellent rate performance (with a discharge capacity of 87.2 mA h g−1 after 1000 cycles at 5C) and cycle stability (with 94.8% capacity retention after 500 cycles at 1C), sustaining 98.6% capacity retention after 200 cycles at 0.5C in LFP‖graphite. This work provides a practical design strategy for high-performance pre-lithiation additives and offers reliable technical support for high-efficiency, long-life lithium-ion battery systems.

Author contributions

Na Tian: writing – review & editing, writing – original draft, visualization, and methodology. Xing Liu: software, investigation, and formal analysis. Kangyu Zhou: software, investigation, and formal analysis. Xiaolin Deng: methodology and investigation. Shuting Kong: formal analysis, investigation. Xiuli Jia: supervision and methodology. Peixin Zhang: writing – review & editing and supervision. Lipeng Zhang: writing – review & editing and supervision. Yanyi Wang: writing – review & editing, supervision, resources, and conceptualization. Dingtao Ma: writing – review & editing, supervision, resources, and project administration.

Conflicts of interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Supplementary Material

SC-OLF-D6SC06091A-s001

Acknowledgments

This research was supported by the Scientific Foundation for Youth Scholars of Shenzhen University (806-000034080180 and 827-0001004), the National Natural Science Foundation of China (No. 22178221 and 22208221), the Shenzhen Science and Technology Program (No. JCYJ20220818095805012 and JCYJ20230808105109019), the Natural Science Foundation of Guangdong Province (No. 2024A1515011078 and 2024A1515011507), and the Guangdong Basic and Applied Basic Research Foundation (2026A1515010368 and 2023A1515011122). Besides, the authors thank the Instrumental Analysis Center of Shenzhen University for the assistance with the Electron Microscope technical support.

Data availability

The data supporting this article have been included as part of the supplementary information (SI). Supplementary information is available. See DOI: https://doi.org/10.1039/d6sc06091a.

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Associated Data

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Supplementary Materials

SC-OLF-D6SC06091A-s001
SC-OLF-D6SC06091A-s001.pdf (2.1MB, pdf)

Data Availability Statement

The data supporting this article have been included as part of the supplementary information (SI). Supplementary information is available. See DOI: https://doi.org/10.1039/d6sc06091a.

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