Regeneration of spent lithium manganate into cation‐doped and oxygen‐deficient MnO2 cathodes toward ultralong lifespan and wide‐temperature‐tolerant aqueous Zn‐ion batteries

Manganese‐based compounds have been regarded as the most promising cathode materials for rechargeable aqueous zinc‐ion batteries (AZIBs) due to their high theoretical capacity. Unfortunately, aqueous Zn–manganese dioxide (MnO2) batteries have poor cycling stability and are unstable across a wide temperature range, severely limiting their commercial application. Cationic preinsertion and defect engineering might increase active sites and electron delocalization, which render the high mobility of the MnO2 cathode when operated across a wide temperature range. In the present work, for the first time, we successfully introduced lithium ions and ammonium ions into manganese dioxide (LNMOd@CC) by an electrodeposition combined with low‐temperature calcination route using spent lithium manganate as a raw material. The obtained LNMOd@CC exhibits a high reversible capacity (300 mAh g−1 at 1 A g−1) and an outstanding long lifespan of over 9000 cycles at 5.0 A g−1 with a capacity of 152 mAh g−1, which is significant for both the high‐value recycling of spent lithium manganate batteries and high‐performance modification for MnO2 cathodes. Besides, the LNMOd@CC demonstrates excellent electrochemical performance across wide temperature ranges (0–50°C). This strategy simultaneously alleviates the shortage of raw materials and fabricates electrodes for new battery systems. This work provides a new strategy for recovering cathode materials of spent lithium‐ion batteries and designing aqueous multivalent ion batteries.

2022G02022; Natural Science Foundation of Distinguished Young Scholars for Fujian Province, Grant/Award Number: 2019J06015 ranges (0-50°C). This strategy simultaneously alleviates the shortage of raw materials and fabricates electrodes for new battery systems. This work provides a new strategy for recovering cathode materials of spent lithiumion batteries and designing aqueous multivalent ion batteries.

K E Y W O R D S
aqueous zinc-ion batteries, electrodeposition, MnO 2 , oxygen defects, spent lithium manganate

| INTRODUCTION
Currently, the electrification of power has changed the global landscape of fossil fuel-dominated energy sources, chief among them is the boom in electric vehicles. 1,2 The strong momentum in the power market has also stimulated a significant increase in the consumption of lithium-ion batteries (LIBs) and upstream raw materials. However, a large number of LIBs have entered the endof-life period and are about to be retired due to the limitation of the service life of LIBs. [3][4][5][6][7][8] Among the various types of LIBs, lithium manganate (LiMn 2 O 4 )based batteries are widely used because of their low cost, low toxicity, and high energy density. However, along with long-term consumption, large amounts of waste LiMn 2 O 4 batteries have been generated, which will cause great harm to the environment and human beings without proper treatment and if directly discharged into the natural environment. 9,10 Rechargeable aqueous zinc ion batteries (AZIBs) as promising alternatives to LIBs have been intensively explored due to their great safety, low cost, and environmental friendliness. [11][12][13] Therefore, the recycling of used lithium manganate materials and their application to AZIBs will become a hot spot in the field of battery research.
The positive electrode materials for AZIBs can be broadly classified into: manganese-based oxides, vanadium-based oxides, organic compounds, polyanionic materials, Prussian blue analogs, and so forth. Among them, MnO 2 stands out for being a nontoxic, cheap, and abundant substance on earth. [14][15][16][17][18][19][20] Especially, the ideal theoretical discharge capacity of about 308 mAh g −1 makes it a candidate cathode for AZIBs. 21,22 Nevertheless, low intrinsic conductivity, sluggish Zn 2+ diffusion kinetics, and crystal structure collapse after Zn 2+ insertion of manganese-based oxides have seriously affected their electrochemical performance. Recently, much effort has been given to improving the stability of materials across a wide temperature range during charging and discharging. 23,24 To mitigate the above disadvantages, the commonly used strategic approach includes a combination of physical coating and preintercalation, rational structure engineering, and doping strategies. 25 For instance, the electrical conductivity of MnO 2 materials can be increased by hybridizing with carbon and other highly conductive elements. In addition, the defect engineering techniques (e.g., cation doping and oxygen defects) not only help increase the conductivity by reducing the electrostatic attraction between the host lattice and the injected Zn 2+ but also serve as one of the effective strategies to enhance ionic bonding, thus optimizing the structural stability of the material to ensure fast and stable diffusion kinetics of Zn 2+ across a wide temperature range. In general, manganese dioxide cathode materials can be obtained by sol-gel derivatization, hydrothermal techniques, and chemical and co-precipitation methods. 26,27 However, the majority of the aforementioned tactics rely on nonscalable material synthesis processes (e.g., hydrothermal techniques). Applying it to the mass manufacture of high-performance MnO 2 cathode materials is still challenging, thus limiting the application of AZIBs in large-scale energy storage systems. 28,29 In addition, the traditional synthesis process route for cathode electrodes is extremely complex, including material combination, coating, and sheet cutting. Especially, the presence of polymer binders limits the proper use of active material surfaces. 30 Therefore, it is essential to obtain a green approach, and improving the flexible preparation of cathode electrodes is still a huge challenge.
Electrodeposition is an inexpensive, simple, and binder-free method for the preparation of manganesebased materials. Owing to its high selectivity, high efficiency, low byproducts, and easily adjustable current and voltage for the synthesis process, it has been receiving more and more attention in recent years. [31][32][33] Moreover, because the material synthesized by this method has good adhesion to the collector fluid, there is no need to add adhesives and conductive agents to the collector fluid. 34 The cations in solution during electrodeposition are able to be pre-embedded in the original MnO 2 lattice, which contributes to accelerate the ion/ electron dynamics, allowing to provide a stable material structure effectively. 20 Figure 1 schematically demonstrates the simple synthetic procedure of the fabricated LNMO d @CC composite. In brief, the thin films of manganese oxide were synthesized in a three-electrode cell with a carbon cloth substrate by electrodeposition. Before the deposition, hydrophilization of carbon cloth was carried out by a cyclic voltammetry (CV) method in 2 M H 2 SO 4 between −0.9 and 2.5 V cycled for three cycles, washed with deionized water, and used as the anode electrode for the working electrode. As shown in Supporting Information: Figure S1, the contact angle of water drops on the carbon cloth is measured after electrochemical treatment. The treated carbon cloth becomes hydrophilic (soaked water droplets

| Electrochemical measurements
The electrochemical properties of the LNMO d @CC composite were measured using CR2025-type coin cells with a Zn foil metal sheet as the counter/reference electrodes. The mass loading of the active materials was approximately 1-1.5 mg cm −2 . In the zinc-ion batteries, the electrolyte has employed the solution of 2 M ZnSO 4 with 0.2 M MnSO 4 . A Neware battery test (CT-4008T-5V50mA-164) system was employed to test the Zn storage performances with a voltage range of 0.8-1.8 V. CV was performed with an Ivium-n-Stat electrochemical workstation at various scan rates (vs. Zn/Zn 2+ ).

| RESULTS AND DISCUSSION
The synthesis schematic in Figure 1 demonstrates the simple electrochemical deposition and synthesis strategy of LNMO d @CC. In brief, the Li + /NH 4 + preintercalated α-MnO 2 cathode with oxygen defects is synthesized through the spent lithium manganese acid battery leaching solution. Among them, the Li + comes from the original solution, and the ammonium ion is from the NH 3 ·H 2 O that regulates the pH of the solution. Figure 2 shows typical pictures from scanning electron microscopy (SEM) and transmission electron microscopy (TEM) of the LNMO d @CC material. As shown in Figure 2A,B and Supporting Information: Figure S1, the α-MnO 2 film is successfully coated and consists of many ultrathin fibers on carbon cloth (CC). The detailed structure of LNMO d @CC is monitored by SEM in Figure 2B, which shows that nanoflower-like morphology offers a large surface area and channels for electrolyte immersion and ion transport. MnO 2 in MO@CC has a nanorod morphology (Supporting Information: Figure S2). As shown in Figure 2C, highresolution transmission electron microscopy (HRTEM) images further indicate that the LNMO d @CC nanosheet material exhibits a polycrystalline structure with a lattice spacing of ≈0.490 nm, corresponding to the (200) plane of MnO 2 . The HRTEM image of Figure 2D and its enlargement further reveal the crystal structure (dark F I G U R E 2 Scanning electron microscopy images of (A, B) LNMO d @CC; transmission electron microscopy images of (C-E) of LNMO d @CC; (F) representative atomic model of LNMO d ; and (G) elemental mapping results of the LNMO d @CC composite for C (green), Mn (blue), O (pink), and N (red). streaks) of MnO 2 , whereas a slight deformation of the Mn atomic column in Figure 2E can be observed, which may be related to oxygen defects. The preintercalated Li + / NH 4 + can reside in the manganese dioxide tunnels, as illustrated in the atomic model ( Figure 2F). Additionally, the elemental mapping images ( Figure 2G) reveal the uniform distribution of C, N, O, and Mn elements on the carbon cloth in the LNMO d @CC composite, indicating the presence of doped nitrogen elements in these nanosheets. 37,38 The Li + /NH 4 + preintercalated manganese dioxide can not only expand the lattice spacing by the cation pre-embedding strategy, thus providing enough defects and active sites for zinc ion storage, but also favor the electron density distribution. 39 The X-ray diffraction (XRD) patterns of LNMO d @CC and MO@CC are depicted in Figure 3A, where the peaks located at about 18.1°, 25.7°, and 36.7°are related to the (200), (220), and (400) crystal planes of α-MnO 2 (JCPDS card No. 44-0141), respectively. 30,40 Additionally, no impurity peaks are observed in XRD patterns. It is interesting to observe that the degree delivered by the usual peak of the (200) plane of LNMO d @CC is lower than that of MO@CC, as seen in the reflection in the zoomed view. This implies that the Li + /NH 4 + preembedding in the lattice is consistent with the HRTEM results. In addition, the XRD pattern of pure carbon cloth is shown in Supporting Information: Figure S3. The Raman spectra are presented in Figure 3B. The main  [42][43][44] Electron paramagnetic resonance (EPR) spectra ( Figure 3C) indicate the existence of abundant oxygen defects in LNMO d @CC, with the g values of the LNMO d @CC signal at 2.002, which is closely related to the electrons trapped in the defective sites. [45][46][47] It is further illustrated that the successful doping of Li + /NH 4 + in the manganese dioxide material loaded on the carbon cloth results in the formation of oxygen defects. The Fourier transform infrared (FTIR) spectrum interpretation in Figure 3D was used to characterize the chemical bond (functional group) information in the LNMO d @CC composite. Between 400 and 700 cm −1 , Mn-O lattice vibrations can be observed. The characteristic peaks at 1656 and 3460 cm −1 , in particular, exhibit distinct bending and stretching vibrational modes that correspond to the constitutive water. 48 And the hydrogen bonding tends to affect LNMO d @CC as well, promoting the easy migration of zinc ions. 49 The additional peak located at 1456 cm −1 in LNMO d @CC is attributed to the bending pattern of N-H, which further confirms the preinsertion of NH 4 + . 28 The peak at about 3250 cm −1 in LNMO d @CC is corresponding to the H-bonding of N-H, and this can be recognized as the N-H…O stretching vibration. It demonstrates the presence of hydrogen bonds between NH 4 + and MnO 2 . 50 The Li + /NH 4 + are inserted into the MnO 2 , which can significantly accelerate the ionic/electronic dynamics as well as improve the structural stability. 51 In addition, nitrogen adsorption-desorption isotherms were collected for LNMO d @CC and MO@CC to study the specific surface area. As shown in Figure 3E, the specific surface area of the Brunauer-Emmett-Teller (BET) model for LNMO d @CC is 210 m 2 g −1 , which is larger than that of MO@CC (170 m 2 g −1 ). It suggests that it is more conducive to the penetration of the electrolyte and possesses more electroactive storage sites for LNMO d @CC. 24,52 X-ray photoelectron spectrum (XPS) analysis was conducted to further confirm Li + /NH 4 + and oxygen deficiencies in the preintercalated material. The full spectrum information in Supporting Information: Figure S4A, which shows the peaks of C, Li, Mn, O, and N, is consistent with the mapping analysis. As shown in the high-resolution N 1s spectrum ( Figure 3F), three obvious characteristic peaks observed in the N 1 s spectrum were associated with pyridine-N (N1 at 398.8 eV), pyrrole-N (N2 at 400.3 eV), and graphite-N (N3 at 401.8 eV); the peak at 401.8 eV is attributed to N-H, implying that the pattern of N doping is the gap doping rather than substitution of O with N. The combination of the binding energy of N 1 s at 403.1 eV can be correlated with N-O, which provides sufficient evidence for the formation of interstitial N rather than substituted N bound to Mn, which is only bound to Mn. The two Mn 2p peaks ( Figure 3G) Figure 3H). The O 1s XPS spectral peaks of the sample (Supporting Information: Figure S4B) can be inverse-folded to the lattice oxygen (530.0 eV) and oxygen vacancy (532.9 eV) contributions, and the apparently stronger oxygen vacancy peak in LNMO d @CC indicates the presence of a large number of oxygen defects.
The electrochemical performance of the cell with the LNMO d @CC cathode was tested in an aqueous electrolyte ( Figure 4A). The decreased peaks that appear in the initial cathodic scan are situated at 1.26 and 1.38 V, as can be seen in Figure 4B. This is the result of the embedding of Zn 2+ in the sample and forming Zn x MnO 2 . During the corresponding anodic sweep, a wide oxidation peak centered at 1.56 V and a shoulder peak (1.6 V) can be expected during the first anodic cycle. 53,54 Among them, the peaks at 1.26/1.56 V and 1.38/1.6 V are attributed to Zn 2+ insertion/extraction and H + insertion/extraction. 55 Two distinct cathodic peaks at 1.26 and 1.38 V and two anodic peaks at 1.56 and 1.60 V are roughly the same in the second and third CV curves after the first cycle, illustrating that LNMO d @CC possesses remarkable cycling stability and reversibility. The CV curves of pure MO and LNMO d @CC cathodes at 0.6 mV s −1 are displayed in Figure 4C. In addition, the lower overpotential gap of the LNMO d @CC cathode (0.292 vs. 0.335 V, 0.305 vs. 0.345 V) suggests its faster kinetic process. The charge/discharge capacities at the voltage plateau of LNMO d @CC are larger than those of MO@CC, suggesting the promising prospect of LNMO d @CC for application ( Figure 4D). The rate capability test that leads for the two materials mentioned above is shown in Figure 4E, which exhibits outstanding rate performances and average reversible capacities of 306, 231, 206, 197, 188, 185, and 183 mAh g −1 at 0.5, 1.0, 2.0, 3.0, 4.0, and 5.0 A g −1 , respectively. More dramatically, the LNMO d @CC cathode can be fully recovered when the current density is restored to 500 mA g −1 , showing excellent rate performance. In comparison, the rate performances of the MO@CC electrode deliver lower capacities under the same current densities. It is shown that the complexes Li + /NH 4 + co-doped manganese dioxide nanosheets can significantly improve the multiplicative performance of the material. Meanwhile, the cycle stability of LNMO d @CC and pure sample MO@CC electrodes was also examined to further support the important role of Li + /NH 4 + . As shown in Figure 4F, the LNMO d @CC electrode, in comparison, exhibits a greater discharge capacity of 300 mAh g −1 at 1 A g −1 over 1000 cycles, whereas the capacities of the MO@CC electrodes are 124 mAh g −1 after 500 cycles. Even at an ultrahigh rate of 5 A g −1 , the LNMO d @CC cathode still worked over 9000 cycles, along with a highly stable CE of close to 100%, which significantly outperforms the performance of MO@CC ( Figure 4G). The neat MO@CC exhibits a similar layered structure to LNMO d @CC, but it is not stabilized with Li + /NH 4 + . The laminar structure facilitates the diffusion and transport of Zn 2+ , thus the MO@CC electrode achieves a high initial discharge capacity of 105 mAh g −1 at 5 A g −1 , but the capacity rapidly decreases to 50 mAh g −1 after 4100 cycles. According to the above results, LNMO d @CC is mainly attributed to Li + /NH 4 + co-doped MnO 2 nanosheets, which not only greatly reduce volume variations but also improve stability throughout cell cycling, enhancing the electrochemical performance of materials. We tested the SEM images of the electrodes after 50, 100, and 1000 cycles (Supporting Information: Figure S5). It can be seen from the SEM images that there is little difference between the electrode surface structure after the long cycle and before the cycle, indicating that the electrode has good structural stability. Therefore, LNMO d @CC with Li + /NH 4 + preintercalation has an excellent rate and cycling performance, and its performance is better than the reported AZIB manganese-based cathodes ( Figure 4H and Supporting Information: Table S1). The Zn 2+ insertion kinetics of the LNMO d @CC anode is further quantitatively interpreted by the CV curves at the different scan rates of 0.2-1 mV s −1 ( Figure 5A). As the scan rate increased, the curve gradually increased, maintaining its original shape, while the redox peak was slightly shifted, indicating relatively rapid reaction kinetics. For the peak current (i), along with the scan rates v ( ), the relationship is represented by the following equation 56,57 :

F I G U R E 4 (A) Electrochemical performance of zinc-ion half-cells: (A) Schematic diagram of zinc-ion batteries (ZIBs
(2) In the formula, a and b are adjustable parameters. When b approaches 1.0, it denotes a capacitive-controlled process, while a diffusion-controlled process, with b about 0.5, leads to an electrochemical reaction. 15 Furthermore, as shown in Supporting Information: Figure S6, the contribution of the capacitance (yellow area) of the LNMO d @CC sample at 0.6 mV s −1 . As seen in Figure 5B, peak 1 and peak 2 have slopes of 0.96 and 0.86, respectively, whereas peak 3 has a b-value of 0.81. It implies that the kinetics process of the Zn 2+ storage behavior of LNMO d @CC is mainly controlled by the combination of diffusion and pseudocapacitive behavior. 58 The following equation was used to calculate the capacitance contribution fractions for each scan rate [59][60][61] : where k 1 and k 2 are constants. As depicted in Figure 5C, as the scan speeds increased from 0.2 to 0.4, 0.6, 0.8, and 1 mV s −1 , it illustrates that the pseudocapacitive processes increase from 32% to 37%, 40%, 44%, and 48%, respectively. The electrochemical behavior and dynamics of the reaction process of LNMO d @CC were analyzed by the galvanostatic intermittent titration technique (GITT) and electrochemical impedance spectroscopy (EIS). Among them, the GITT curves of the LNMO d @CC and MO@CC reflecting the ion diffusion coefficient plots are shown in Figure 5D,E and Supporting Information: Figure S7, which increase with ion insertion; the value of region I (10 −7 -10 −8 cm 2 S −1 ) is much greater than that of region II (10 −9 -10 −10 cm 2 S −1 ), and the corresponding ion coefficient of the LNMO d @CC cathode is much greater than that of the MO@CC cathode. This is attributed to the preintercalated Li + /NH 4 + embedded in the LNMO d @CC, which leads to promoting the diffusion rate of ions while accelerating the electrochemical kinetic process. Considering that the size of H + is smaller than that of Zn 2+ and that two foreign ions, H + and Zn 2+ , can be inserted into the MnO 2 structure. Since the second voltage stage is mostly produced by Zn 2+ insertion, it can be concluded that the first discharge step is driven by H + insertion. This further supports the idea that a first H + dominating insertion and a second Zn 2+ insertion take place during the discharge phase. On the other hand, EIS also confirms fast charge transfer and ion diffusion. 12,62 As displayed in Figure 5F, the LNMO d @CC cathode has a larger diffusion coefficient compared to the pure MO@CC. In particular, the preintercalated Li + /NH 4 + can speed up ion diffusion.
After 1000 cycles, it is still very consistent with the above simulation results (Supporting Information: Figure S8). The charges are transferred from Li + /NH 4 + to LNMO d @CC, which would reduce the Gibbs free energy of the NH 4 + preinsertion layer in the LNMO d @CC system. 63 In addition, Li + /NH 4 + in the preintercalated layer act as the "structural pillars" and provide effective stabilization of the lamellar structure LNMO d @CC. The Li + /NH 4 + and MnO 2 could form a strong link owing to the hydrogen bond, which successfully inhibits the structural collapse during ion insertion and extraction.
To thoroughly explain the energy storage mechanism of the LNMO d @CC with Li + /NH 4 + and the hydrogen bond, ex situ XRD, SEM, and Raman measurements were carried out at the selected states during discharge/charge cycles ( Figure 6). The ectopic XRD patterns of the LNMO d @CC cathode at critical stages of the cycling process are shown in Figure 6B, and the seven voltage points of the electrodes were selected to detect the relevant structural changes. When the battery is completely discharged, a clear ZnSO 4 (OH) 6 ·4H 2 O (ZSH) (JCPDS: 44-0673) phase may be seen in the XRD pattern. 64,65 The introduction of H + into the LNMO d @CC cathode causes the electrolyte's OH − content to increase, which is what causes the creation of this new phase. The ensuing charging procedure causes the ZSH phase to progressively vanish. [66][67][68] The battery exhibits great electrochemical predictability since it goes back to the initial stage after being fully charged. Surprisingly, the consistent structural evaluation takes place in the second cycle, further supporting the notion that LNMO d @CC maintains its structural stability during ion insertion and extraction. In addition, the ex-situ SEM images of LNMO d @CC at the initial fully discharged and charged locations demonstrate the reversible formation and disappearance of zinc hydroxide hydrates ( Figure 6D-F). 69 As shown in Figure 6C, the results are further supported by the accompanying Raman spectra, where the locations of the Zn-O bond and the Mn-O junction are indicated by the gray and yellow rectangles, respectively. As the voltage changes, the Zn-O bond periodically grows and drops, whereas the Mn-O bond experiences very little change. Morphological changes were further analyzed by SEM. Among them, the initial structure of manganese dioxide loaded on a carbon cloth is shown in Figure 6D. The microflakes appear in the first fully discharged state in Figure 6E, which is a representative pattern of the ZnMn 2 O 4 phase. During the subsequent charging process, the microflake gradually disappeared and the morphology returned to the initial nanosheet structure ( Figure 6F), demonstrating that zinc ions can be well embedded and detached. 68 Based on the above discussions, the charge storage mechanism can be described as follows, and the corresponding illustration is shown in Figure 6G. Cathode: Zn LNMO (nondiffusion controlled), Anode: Experimentally, the Zn//LNMO d @CC electrode shows reversible performance across a wide temperature range. 12,70-74 The electrode material not only has good electrochemical cycling performance at room temperature but also shows good electrochemical performance at different temperatures. Specifically, Figure 7A shows the storage performance of the electrode material for Zn// LNMO d @CC at a high temperature of 50°C with a current density of 0.5 A g −1 , with a cell-specific capacity of 260 mAh g −1 , and a stable cycling performance of 150 cycles. In addition, Figure 7B demonstrates the cycling performance of Zn//LNMO d @CC at a low temperature of 0°C at a current density of 0.5 A g −1 . It delivers a stable capacity of 70 mAh g −1 at a low temperature of 0°C even after 850 cycles. Furthermore, as shown in Figure 7C, the stable capacity increases from 70, 185, 215, 249, 303 to 357 mA h g −1 when operating temperatures were increased from 0°C, 10°C, 20°C, 30°C, 40°C, to 50°C. The GITT curves and Zn 2+ diffusion coefficients of the LNMO d @CC electrode were determined at temperatures of 0°C and 50°C. As can be seen from Supporting Information: Figure S9, the test temperature affects the diffusion coefficient of the electrodes. The lower the temperature, the smaller the diffusion coefficient. As the temperature gradually increases, so does the diffusion coefficient. This phenomenon can be considered as enhanced ion transport kinetics at high temperatures. 75 These results indicate that the LNMO d @CC electrode is well adapted to the temperature changes because the electrode material is significantly resistant to heat and freezing. 76 The charge and discharge curves of the F I G U R E 6 Electrochemical performance of LNMO d @CC in aqueous zinc-ion batteries: (A) GCD curves of LNMO d @CC at a current density of 0.5 A g −1 ; (B) Ex situ X-ray diffraction and (C) ex situ Raman results of the LNMO d @CC cathode during charge and discharge processes. The scanning electron microscopy images of the (D) primitive, (E) first charge to 1.8 V, and (F) second discharge to 1 V of the LNMO d @CC. (G) The schematic illustration of electrochemical reaction mechanism of LNMO d @CC.
electrode materials at different temperatures are shown in Figure 7D. Two coin-type batteries, as shown in Figure 7E, successfully light up the LED sign with a voltage of 3 V. This work shows that the combination of cation preinsertion and defect engineering is a feasible way to design wide-temperature workable cathode materials for AZIBs.

| CONCLUSION
In summary, we developed a facile and environmentally friendly method to prepare LNMO d @CC composites from spent LiMn 2 O 4 powder, a spent cathode material of lithium-ion batteries. It is promising that the Li + /NH 4 + co-doping favors the electron concentration distribution and improves the ion reaction kinetics, as has been demonstrated by the experimental results. The LNMO d @CC cathode possesses a high capacity of 300 mAh g −1 at 1 A g −1 over 1000 cycles and a great cycling stability of 152 mAh g −1 up to 9000 cycles at 5 A g −1 for AZIBs. Furthermore, the LNMO d @CC also exhibits excellent performance across wide temperature ranges (0-50°C). Particularly, the ultra-thin nanoflowerlike LNMO d @CC containing oxygen-defected nanosheets provides enough active sites for zinc storage, leading to a high specific reversible capacity. The Li + /NH 4 + in the preintercalated greatly accelerate ion diffusion and charge transfer, which collectively promote fast kinetics and excellent high-rate performance. Moreover, the ionic pre-embedding stabilizes the structure and oxygen defects for boosting the electrochemical performance of manganese oxide cathodes for AZIBs. Consequently, this work provides a reference for the development of ultra-long lifespan and wide-temperature workable AZIBs. We are convinced that this sound strategy will make manganese-based materials suitable for various rechargeable batteries and offer new prospects for their use.

SUPPORTING INFORMATION
Additional supporting information can be found online in the Supporting Information section at the end of this article.