ZnAl2O4:Eu novel phosphor: SEM and mechanoluminescence characterization synthesized by solution combustion technique

Eu doped ZnAl₂O₄ phosphors were synthesized by the solution combustion technique using carbohydrazide as a fuel. Mechanoluminescence (ML) was excited impulsively by dropping a piston of 0.7 kg onto the phosphors. Two distinct peaks were observed in the ML glow curve of the γ‐ray irradiated ZnAl₂O₄:Eu phosphors. Dependence of ML on various parameters as impact velocity of the piston dropped on to it, mass of the sample, gamma ray doses given to the sample and ML spectra have been studied. ML emission spectrum showed the characteristic emission of Eu³⁺ ion in this system. ML is observed to be optimum for the sample having 0.2 mol% of Eu in the ZnAl₂O₄ phosphor. XRD result confirms formation of the phosphors. SEM characterization shows its surface morphology. This novel phosphor may be a potential candidate for dosimetric use due to its linear dose response. Copyright © 2014 John Wiley & Sons, Ltd.     

Lyoluminescence,thermoluminescence and mechanoluminescence studies in γ‐ray irradiated Dy3+ activated potassium chloride phosphor for accidental radiation dosimetry

The lyoluminescence (LL), thermoluminescence (TL) and mechanoluminescence (ML) of γ‐ray‐irradiated coloured powder of KCl:Dy (0.05–0.5 mol%) phosphors are reported in this paper. To understand the mechanism of LL and ML, the LL and ML spectra are compared with TL studies. The variation of intensity of respective luminescence with different γ‐ray doses and with different concentrations of Dy³⁺ ion doped in KCl is found to be similar in nature. The intensities differ from each other, but their nature is found to be similar with γ‐ray exposures. The ML glow peak intensity is linear up to high 1 kGy exposure as compared to LL (up to 0.5 kGy) and TL (up to 0.75 kGy) techniques. Therefore, according to our results, the recommendation is that KCl:Dy (0.1 mol%) phosphor prepared by wet chemical technique is useful for high‐dose measurements using the ML technique for accidental radiation dosimetry. Copyright © 2011 John Wiley & Sons, Ltd.     

Enhancement of the luminescence properties of Sr3(PO4)2:Dy3+,Li+ white‐light‐emitting phosphors by charge compensator Li+ co‐doping

Sr₃(PO₄)₂:Dy³⁺,Li⁺ phosphors were prepared using a simple high temperature solid method for luminescence enhancement. The structures of the as‐prepared samples agreed well with the standard phase of Sr₃(PO₄)₂, even when Dy³⁺ and Li⁺ were introduced. Under ultraviolet excitation at 350 nm, the Sr₃(PO₄)₂:Dy³⁺ sample exhibited two emission peaks at 483 nm and 580 nm, which were due to the ⁴F_9/2 → ⁶H_15/2 and ⁴F_9/2 → ⁶H_13/2 transitions of Dy³⁺ ions, respectively. A white light was fabricated using these two emissions from the Sr₃(PO₄)₂:Dy³⁺ phosphors. The luminescence properties of Sr₃(PO₄)₂:Dy³⁺,Li⁺ phosphors, including emission intensity and decay time, were improved remarkably with the addition of Li⁺ as the charge compensator, which would promote their application in near‐ultraviolet excited white‐light‐emitting diodes.     

Luminescence in Li3Al2(PO4)3:Eu2+

A series of efficient Li₃Al₂(PO₄)₃:Eu²⁺ novel phosphors were synthesized by the facile combustion method. The effects of dopant on the luminescence behavior of Li₃Al₂(PO₄)₃ phosphor were also investigated. The phosphors were characterized by X‐ray diffraction, field emission scanning electron microscope and photoluminescence techniques. The result shows that all samples can be excited efficiently by near‐ultraviolet excitation under 310 nm. The emission was observed for Li₃Al₂(PO₄)₃:Eu²⁺ phosphor at 425 nm, which corresponded to the d → f transition. The concentration quenching of Eu²⁺ was observed in Li₃Al₂(PO₄)₃:Eu²⁺ when the Eu concentration was at 0.5 mol%. The prepared powders exhibited intense blue emission at the 425 nm owing to the Eu²⁺ ion by Hg‐free excitation at 310 nm (i.e., solid‐state lighting excitation). Consequently, the availability of such a phosphor will significantly help in the development of blue‐emitting solid‐state lighting applications. Copyright © 2012 John Wiley & Sons, Ltd.     

Luminescence characterization of KBaPO4:RE (RE = Sm3+,Eu3+,Dy3+) phosphors

KBaPO₄ luminescent powdered phosphors doped with rare earth elements (RE = Sm³⁺,Eu³⁺,Dy³⁺) were successfully synthesized using a wet chemical method to identify the most suitable phosphor for solid‐state lighting based on the measurement of their emission spectra at excitation wavelengths. The X‐ray diffraction pattern of the as‐prepared KBaPO₄ was well matched with its standard JCPDS file no. 330996, indicating the formation of the desired compound. Scanning electron microscopy images revealed irregular morphology, the material crystallized particles aggregated and were non‐uniform with particle sizes ranging from 1 to 100 μm. Photoluminescence excitation and emission spectra clearly indicated that the phosphor containing the Sm³⁺‐activated KBaPO₄ phosphors could be efficiently excited at 403 nm and exhibited an emission mainly including two wavelength peaks at 559 nm and 597 nm. The phosphor containing the Eu³⁺‐activated KBaPO₄ phosphors could be efficiently excited at 396 nm and exhibited a bright red emission mainly including two wavelength peaks at 594 nm and 617 nm. The phosphor containing the Dy³⁺‐activated KBaPO₄ phosphors could be efficiently excited at 349 nm and exhibited wavelength peaks at 474 nm and 570 nm.     

Systematic study of photoluminescence,lyoluminescence and mechanoluminescence in Ce3+‐ and Eu3+‐activated Li3PO4 phosphors

Li₃PO₄ phosphor was prepared using a modified solid‐state diffusion technique. In this work, photoluminescence, lyoluminescence and mechanoluminescence studies were carried out in a Li₃PO₄ microcrystalline powder doped with different rare earths. In photoluminescence studies, characteristic emission of Ce and Eu was observed. The lyoluminescence glow curves of Li₃PO₄ microcrystals show that lyoluminescence intensity initially increases with time and then decreases exponentially. The decay time consists of two components for all masses. The dependence of decay time, especially the longer component, on mass has been investigated. Experiments on γ‐irradiated crystals have proved that the light emission originates from the recombination of released F‐centres with trapped holes (V₂‐centres) at the sulfuric acid–solid interface. Incorporation of bivalent alkali in solid lithium phosphate leads to an enhancement of lyoluminescence. A possible explanation for the experimental results has been attempted. The phosphor has a mechanoluminescence single glow peak. Mechanoluminescence intensity under various loading conditions was investigated. It is observed that mechanoluminescence intensity increases with increasing impurity concentration and increasing piston impact velocity. The results may be considered as only being of academic interest in solid‐state materials. Copyright © 2013 John Wiley & Sons, Ltd.     

Effect of UV irradiation on different types of luminescence of SrAl2O4:Eu,Dy phosphors

This paper reports the luminescence behavior of Sr_0.097Al₂O₄:Eu_0.01,Dy_0.02 phosphors under UV‐irradiation. The effect of UV‐irradiation on afterglow (AG), thermoluminescence (TL) and mechanoluminescence (ML) of Sr_0.097Al₂O₄:Eu_0.01,Dy_0.02 phosphors is investigated. The space group of Sr_0.097Al₂O₄:Eu_0.01,Dy_0.02 phosphors is monoclinic P2₁. The prepared phosphors exhibit a long AG, intense TL and ML. It is found that the AG, ML intensity and TL increase with increasing duration of irradiation time. The ML intensity decreases with successive impact of the load onto the phosphors, whereby the diminished ML intensity can be recovered by UV‐irradiation. Copyright © 2016 John Wiley & Sons, Ltd.     

Energy transfer in M5(PO4)3 F:Eu2+,Ce3+ (M = Ca and Ba) phosphors

M₅(PO₄)₃ F:Eu²⁺ (M = Ca and Ba) co‐doped with Ce³⁺ phosphors were successfully prepared by the combustion synthesis method. The introduction of co‐dopant (Ce³⁺) into the host enhanced the luminescent intensity of the M₅(PO₄)₃ F:Eu²⁺ (M = Ca and Ba) efficiently. Previously, we have reported the synthesis and photoluminescence properties of same phosphors. The aim of this article is to report energy transfer mechanism between Ce³⁺?Eu²⁺ ions in M₅(PO₄)₃ F:Eu²⁺ (M = Ca and Ba) phosphors, where Ce³⁺ ions act as sensitizers and Eu²⁺ ions act as activators. The M₅(PO₄)₃ F:Eu²⁺ (M = Ca and Ba) co‐doped with Ce³⁺ phosphor exhibits great potential for use in white ultraviolet (UV) light‐emitting diode applications to serve as a single‐phased phosphor that can be pumped with near‐UV or UV light‐emitting diodes. Copyright © 2013 John Wiley & Sons, Ltd.     

Electrochemical and Structural Investigation of Calcium Substituted Monoclinic Li3V2(PO4)3 Anode Materials for Li‐Ion Batteries

In this work, the effect of Li⁺ substitution in Li₃V₂(PO₄)₃ with a large divalent ion (Ca²⁺) toward lithium insertion is studied. A series of materials, with formula Li_3?2xCa_xV₂(PO₄)₃/C (x = 0, 0.5, 1, and 1.5) is synthesized and studied in the potential region 3–0.01 V versus Li⁺/Li. Synchrotron diffraction demonstrates that Li₃V₂(PO₄)₃/C has a monoclinic structure (space group P2₁/n), while Ca_1.5V₂(PO₄)₃/C possesses a rhombohedral structure (space group R‐3c). The intermediate compounds, Li₂Ca_0.5V₂(PO₄)₃/C and LiCaV₂(PO₄)₃/C, are composed of two main phases, including monoclinic Li₃V₂(PO₄)₃/C and rhombohedral Ca_1.5V₂(PO₄)₃/C. Cyclic voltammetry reveals five reduction and oxidation peaks on Li₃V₂(PO₄)₃/C and Li₂Ca_0.5V₂(PO₄)₃/C electrodes. In contrast, LiCaV₂(PO₄)₃/C and Ca_1.5V₂(PO₄)₃/C have no obvious oxidation and reduction peaks but a box‐type voltammogram. This feature is the signature for capacitive‐like mechanism, which involves fast electron transfer on the surface of the electrode. Li₃V₂(PO₄)₃/C undergoes two solid‐solution and a short two‐phase reaction during lithiation and delithiation processes, whereas Ca_1.5V₂(PO₄)₃/C only goes through capacitive‐like mechanism. In operando X‐ray absorption spectroscopy confirms that, in both Li₃V₂(PO₄)₃/C and Ca_1.5V₂(PO₄)₃/C, V ions are reduced during the insertion of the first three Li ions. This study demonstrates that the electrochemical characteristic of polyanionic phosphates can be easily tuned by replacing Li⁺ with larger divalent cations.     

Nd3+‐Yb3+/Nd3+‐Yb3+‐Li+ co‐doped Gd2O3 phosphors for up and down conversion luminescence

Frequency up‐conversion (UC) emission from the Nd³⁺‐Yb³⁺/Nd³⁺‐Yb³⁺‐Li⁺ co‐doped gadolinium oxide (Gd₂O₃) phosphors prepared by the solution combustion technique in the visible range have been studied by using 980 nm near infrared (NIR) laser diode excitation. The crystalline structure and formation of the cubic phase has been confirmed with the help of X‐ray diffraction (XRD) studies. XRD peak shifts have been found towards the lower diffraction angle side in the case of the Nd³⁺‐Yb³⁺‐Li⁺ co‐doped phosphors. Surface morphology and particle size information have been observed by using field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) analysis. Down‐conversion emission study under 351 nm excitation in the visible region for the Nd³⁺‐Yb³⁺/Nd³⁺‐Yb³⁺‐Li⁺ co‐doped phosphors has been performed. The UC emission bands lying in the green and red region arising from the Nd³⁺ ions have been enhanced by ~260 times, ~113 times due to incorporation of Li⁺ ions in the Nd³⁺‐Yb³⁺ co‐doped phosphors. Photometric characterization has been done for the Nd³⁺‐Yb³⁺/Nd³⁺‐Yb³⁺‐Li⁺ co‐doped phosphors. The present study suggests the capability of the synthesized phosphors in near‐infrared (NIR) to visible upconverter and luminescent device applications.     

Mechanoluminescence of SrAl2O4:Eu,Dy nanophosphors induced by low impact velocity

The present paper reports the impulsive excitation of mechanoluminescence (ML) in Sr_0.97Al₂O₄:Eu_0.01,Dy_0.02 nanophosphors prepared using a combustion technique. The phosphors are characterized using X‐ray powder diffraction (XRD), high‐resolution transmission electron microscopy (HRTEM) and photoluminescence (PL). The XRD results show that the samples exhibit a monoclinic α‐phase in the crystal structure. The space group of SrAl₂O₄:Eu,Dy nanophosphors is monoclinic P2₁. The PL and ML spectra of SrAl₂O₄:Eu,Dy nanophosphors are excited using light with a wavelength of 365 nm and emission is found at 516 nm. The prepared nanophosphors exhibits an intense ML that can be seen in daylight with the naked eye. When a sample powder is deformed impulsively by the impact of a moving piston, the ML intensity initially increases linearly with time, attains a peak value, I_m, at time t_m, and then decreases with time. The peak ML intensity, I_m, and total ML intensity, I_T, increase linearly with applied pressure and impact velocity. The ML intensity decreases with successive impacts of load onto the phosphors, and the diminished ML intensity can be approximately recovered by UV irradiation. The activation energy using thermoluminescence is found to be 0.57 eV for SrAl₂O₄:Eu,Dy nanophosphors. Copyright © 2016 John Wiley & Sons, Ltd.     

Optical properties and energy transfer of Eu2+/Ce3+ co‐activated Na3Ca6(PO4)5 phosphor

Ce³⁺/Eu²⁺ co‐doped Na₃Ca₆(PO₄)₅ phosphors were prepared using a combustion‐assisted synthesis method. X‐Ray powder diffraction (XRD) analysis confirmed the formation of a Na₃Ca₆(PO₄)₅ crystal phase. Na₃Ca₆(PO₄)₅:Eu²⁺ phosphors have an efficient bluish‐green emission band that peaks at 489 nm, whereas Ce³⁺‐doped Na₃Ca₆(PO₄)₅ showed a bright emission band at 391 nm. Analysis of the experimental results suggests that enhancement of the Eu²⁺ emission intensity in co‐doped Na₃Ca₆(PO₄)₅:Eu²⁺,Ce³⁺ phosphors is due to a resonance‐type energy transfer from Ce³⁺ to Eu²⁺ ions, which is predominantly governed by an exchange interaction mechanism. These results indicate that Ce³⁺/Eu²⁺ co‐doped Na₃Ca₆(PO₄)₅ is potentially useful as a highly efficient, bluish‐green emitting, UV‐convertible phosphor for white‐light‐emitting diodes. Copyright © 2014 John Wiley & Sons, Ltd.     

Luminescent properties of novel red‐emitting M7Sn(PO4)6:Eu3+ (M = Sr,Ba) for light‐emitting diodes

Novel red‐emitting phosphors, Eu³⁺‐activated M₇Sn(PO₄)₆ (M = Sr, Ba), were synthesized at 1200°C by conventional solid‐state reaction method. The luminescent properties of M₇Sn(PO₄)₆:Eu³⁺ (M = Sr, Ba) phosphors were investigated, and the critical concentration of the activator (Eu³⁺) concentration were found to be 0.175 mol and 0.21 mol per formula unit for Sr_7‐xSn(PO₄)₆:xEu³⁺ and Ba_7‐xSn(PO₄)₆:xEu³⁺, respectively. These phosphors presented red luminescence under the excitation of 395 or 465 nm, perfectly matching with the emissions wavelength of near‐ultraviolet (UV) light‐emitting diodes (LEDs) and InGaN blue LED.     

Mechanoluminescence,thermoluminescence, photoluminescence studies on Ca3Y2Si3O12:RE3+ (RE3+ = Dy3+and Eu3+) phosphors

Dy³⁺ and Eu³⁺ activated Ca₃Y₂Si₃O₁₂ phosphors were synthesized by the solid‐state synthesis method. The phosphors were characterized by X‐ray diffraction (XRD), mechanoluminescence (ML), thermoluminescence (TL) and photoluminescence (PL) to determine structure and luminescence. For ML glow curves, only one peak was observed, as only one type of luminescence centre was formed during irradiation. The Ca₃Y₂Si₃O₁₂:Dy³⁺ TL glow curve showed a single peak at 151.55°C and the Ca₃Y₂Si₃O₁₂:Eu³⁺ TL glow curve peaked at 323°C with a small peak at 192°C, indicating that two types of traps were activated. The trapping parameters for both the samples were calculated using Chen's peak shape method. Dy³⁺‐activated Ca₃Y₂Si₃O₁₂ showed emission at 482 and 574 nm when excited by a 351 nm excitation wavelength, whereas the Eu³⁺‐activated Ca₃Y₂Si₃O₁₂ phosphor PL emission spectra showed emission peaks at 613 nm, 591 nm, 580 nm when excited at 395 nm wavelength. When excited at 466 nm, prominent emission peaks were observed at their respective positions with very slight shifts. Copyright © 2015 John Wiley & Sons, Ltd.     

Orange light‐emitting Ca3Mg3(PO4)4:Sm3+ phosphors

This work reports the photoluminescence properties of Ca₃Mg₃(PO₄)₄:Sm³⁺ phosphors that were synthesized by the combustion method. The phase formation and morphology of the prepared phosphors were analysed by X‐ray diffraction studies and scanning electron microscopy. Ca₃Mg₃(PO₄)₄:Sm³⁺ phosphors give orange light emission when excited by near‐ultraviolet (NUV) and blue light. The photoluminescence characteristics of the as‐prepared phosphors were investigated and their emission spectra showed three peaks due to ⁴G_5/2 → ⁶H_5/2, ⁴G_5/2 → ⁶H_7/2 and ⁴G_5/2 → ⁶H_9/2 transitions. The mechanism responsible for the concentration quenching of luminescence was found to be an electric dipole–dipole interaction. The CIE chromaticity coordinates suggested that the prepared phosphors are potential candidates for orange light‐emitting diodes (LEDs).     

Effect of different temperatures to remove reduction gas on the photoluminescence properties of Eu‐doped Li2(Ba1‐xSrx)SiO4 phosphors

In this study, Eu‐doped Li₂(Ba_1‐xSr_x)SiO₄ powders (x = 0, 0.2, 0.4, and 0.6) were synthesized at 850°C in a reduction atmosphere (5% H₂ + 95% N₂) for a duration of 1 h using a solid‐state reaction method. The reduction atmosphere was infused as the synthesis temperature reached 850°C, and was removed as the temperature dropped to 800–500°C. Li₂(Ba_1‐xSr_x)SiO₄ (or Li₂BaSiO₄), (Ba,Sr)₂SiO₄ (or BaSiO₄), and Li₄SiO₄ phases co‐existed in the synthesized Eu‐doped Li₂(Ba_1‐xSr_x)SiO₄ powders. A new finding was that the reduction atmosphere removing (RAR) temperature of the Li₂(Ba_1‐xSr_x)SiO₄ phosphors had a large effect on their photoluminescence excitation (PLE) and PL properties. Except for the 800°C‐RAR‐treated Li₂BaSiO₄ phosphor, PLE spectra of all other Li₂(Ba_1‐xSr_x)SiO₄ phosphors had one broad emission band with two emission peaks centred at ~242 and ~283 nm; these PL spectra had one broad emission band with one emission peak centred at 502–514 nm. We showed that the 800°C‐RAR‐treated Li₂BaSiO₄ phosphor emitted a red light and all other Li₂(Ba_1‐xSr_x)SiO₄ phosphors emitted a green light. Reasons for these results are discussed thoroughly.     

Impact of ligand environment on optical,luminescence and thermometric behavior of A3(PO4)2:Sm3+ (A = Ca,Sr) phosphors

The present study investigates the impact of the ligand environment on the luminescence and thermometric behavior of Sm³⁺ doped A₃(PO₄)₂ (A = Sr, Ca) phosphors prepared by combustion synthesis. The structural and luminescent properties of Sm³⁺ ions in the phosphate lattices were investigated using powder X-ray diffraction (PXRD) and photoluminescence (PL) techniques. PXRD results of the synthesized phosphors exhibit the expected phases that are in agreement with their respective standards. Fourier-transform infrared (FTIR) spectroscopy confirms the presence of PO₄ vibrational bands. Upon excitation with near ultraviolet light, the PL studies indicated that Sr₃(PO₄)₂:Sm³⁺ phosphors exhibit a yellow light emission, whereas Ca₃(PO₄)₂:Sm³⁺ phosphors exhibit an emission of orange light. The PL emission results are in accordance with the CIE coordinates, with the Sr₃(PO₄)₂:Sm³⁺ phosphors showing coordinates of (0.56, 0.44), and the Ca₃(PO₄)₂:Sm³⁺ phosphors displaying coordinates of (0.60, 0.40). Thermal analysis shows improved stability of Ca₃(PO₄)₂:Sm³⁺ based on lower weight reduction in thermogravimetric analysis. The effect of temperature on the luminescence properties of the phosphor has been examined upon a 405 nm excitation. By using the fluorescence intensity ratio (FIR) method, the temperature responses of the emission ratios from the Sm³⁺: the ⁴F_3/2 → ⁶H_5/2 transition to the ⁴G_5/2 → ⁶H_7/2 and ⁴F_3/2 → ⁶H_5/2 transition to the ⁴G_5/2 → ⁶H_9/2 emissions are characterized. The Ca₃(PO₄)₂:Sm³⁺ phosphors are more sensitive as compared with the Sr₃(PO₄)₂:Sm³⁺ phosphors. The earlier research findings strongly indicate that these phosphors hold great promise as ideal candidates for applications in non-invasive optical thermometry and solid-state lighting devices.     

Tunable white light emission from single‐phased Li2SrSiO4:Dy3+ phosphors by co‐doping with Eu3+

A series of single‐phase full‐color emitting Li₂Sr_1−x−ySiO₄:xDy³⁺,yEu³⁺ phosphors were synthesized by solid‐state reaction and characterized by X‐ray diffraction and photoluminescence analyses. The samples showed emission peaks at 488 nm (blue), 572 nm (yellow), 592 nm (orange) and 617 nm (red) under 393 nm excitation. The photoluminescence excitation spectra, comprising the Eu–O charge transfer band and 4f–4f transition bands of Dy³⁺ and Eu³⁺, range from 200 to 500 nm. The Commission Internationale de I'Eclairage chromaticity coordinates for Li₂Sr_0.98−xSiO₄:0.02Dy³⁺,xEu³⁺ phosphors were simulated. By manipulating Eu³⁺ and Dy³⁺ concentrations, the color points of Li₂Sr_1−x−ySiO₄:xDy³⁺,yEu³⁺ were tuned from the greenish‐white region to white light and eventually to reddish‐white region, demonstrating that a tunable white light can be obtained by Li₂Sr_1−x−ySiO₄:xDy³⁺,yEu³⁺ phosphors. Li₂Sr_0.98−xSiO₄:0.02Dy³⁺, xEu³⁺ can serve as a white‐light‐emitting phosphor for phosphor‐converted light‐emitting diode. Copyright © 2014 John Wiley & Sons, Ltd.     

Orange‐red emitting europium doped strontium ortho‐silicate phosphor prepared by a solid state reaction method

In the present article we report europium‐doped strontium ortho‐silicates, namely Sr₂SiO₄:xEu³⁺ (x = 1.0, 1.5, 2.0, 2.5 or 3.0 mol%) phosphors, prepared by solid state reaction method. The crystal structures of the sintered phosphors were consistent with orthorhombic crystallography with a Pmna space group. The chemical compositions of the sintered phosphors were confirmed by energy dispersive X‐ray spectroscopy (EDS). Thermoluminescence (TL) kinetic parameters such as activation energy, order of kinetics and frequency factors were calculated by the peak shape method. Orange‐red emission originating from the ⁵D₀–⁷F_J (J = 0, 1, 2, 3) transitions of Eu³⁺ ions could clearly be observed after samples were excited at 395 nm. The combination of these emissions constituted orange‐red light as indicated on the Commission Internationale de l'Eclairage (CIE) chromaticity diagram. Mechanoluminescence (ML) intensity of the prepared phosphor increased linearly with increasing impact velocity of the moving piston that suggests that these phosphors can also be used as sensors to detect the stress of an object. Thus, the present investigation indicates that the piezo‐electricity was responsible for producing ML in the prepared phosphor.     

Cascade‐Type Prelithiation Approach for Li‐Ion Capacitors

An industry‐relevant method for pre‐lithiation of lithium‐ion capacitors to balance the first charge irreversibility is demonstrated, which addresses the prime bottleneck for their market integration. Based on a composite positive electrode that integrates pyrene monomers and an insoluble lithiated base, Li₃PO₄, a “cascade‐type” process involving two consecutive irreversible reactions is proposed: i) oxidative electropolymerization of the pyrene moieties releases electrons and protons; ii) protons are captured by Li₃PO₄ and exchanged for a stoichiometric amount of Li⁺ into the electrolyte. (¹H, ¹⁹F, and ³¹P) NMR spectroscopy, operando X‐ray diffraction, and Raman spectroscopy support this mechanism. By decoupling the irreversible source of lithium ions from electrons, the cascade‐type pre‐lithiation allows the simultaneous enhancement of the capacity of the positive electrode, thanks to p‐doping of the resulting polymer. Remarkably, the proton scavenging properties of Li₃PO₄ also boost the polymerization process, which enables a 16% increase in capacity without detrimental effect on power properties and cyclability. Full cells integrating a cheap carbon black based negative electrode, show much‐improved capacity of 17 mAh g^‐1_electrodes (44 F g^‐1_electrodes, 3–4.4 V) and excellent stability over 2200 cycles at 1 A g^‐1. Thanks to its versatile chemistry and flexibility this approach in principle can be applied to any kind of ion‐battery.