Experimental Section

Materials

Cyclohexane (C6H12) and tetraethyl orthosilicate ((C2H5O)4Si, TEOS) were obtained from Aladdin. Cetyltrimethylammonium bromide (C19H42BrN, CTAB) was bought from Sinopharm Chemical Reagent Co., Ltd. Triethanolamine (C6H15NO3, TEA) and aniline were received from Sigma-Aldrich. Ammonium molybdate tetrahydrate ((NH4)6Mo7O24·4H2O, AMT), thiourea (CH4N2S), ammonium metatungstate ((NH4)6H2W12O10·_x_H2O), sodium hydroxide (NaOH), ammonium persulfate (APS), and commercial molybdenum disulfide (MoS2) were purchased from Shanghai Macklin Biochemical Co., Ltd. All chemical reagents were used as received without further purification. Deionized water was used throughout the experiments.

Material Preparation

Preparation of CTAB-Decorated Mesoporous Silica (mSiO2@CTAB)

The synthesis of mSiO2@CTAB was carried out in an oil–water biphasic stratification reaction system, in which TEOS was used as a silica source for self-assembly at the oil–water interface, and CTAB served as a pore-forming agent in the aqueous phase. Specifically, 6 g of CTAB and 0.75 mL of TEA solution (0.3 g mL−1) were dissolved in 60 mL of deionized water and stirred at 300 r min−1 for 30 min at 60 °C. Afterward, 16 mL of cyclohexane and 4 mL of TEOS were added to the solution and stirred for 12h. The products were collected by centrifugation and washed three times with ethanol to remove unreacted species, while preserving CTAB in the nanopores of mesoporous silica (mSiO2).

Preparation of Nitrogen-Doped Carbon Bridged MoS2 Heterostructures (MoS2–N–C)

Specifically, 0.3 g of mSiO2@CTAB and 4.1 g of AMT were dispersed in 20 mL of deionized water by ultrasonication until a uniform suspension was obtained. The mixture was then filtered under vacuum through a Büchner funnel three times. The collected product was dried overnight at 80 °C to yield mSiO2@CTAB-MoO_x_ hybrid precursor. Notably, the amount of AMT was calculated according to Eq. 1, under the assumption that the pore volume of mSiO2@CTAB was completely filled with MoO3, and an additional 50% excess was introduced to ensure sufficient loading:where \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$${V}{\mathrm{p}\mathrm{o}\mathrm{r}\mathrm{e}}$$\end{document}Vpore is the pore volume of mSiO2@CTAB, \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$${m}{{\mathrm{m}\mathrm{S}\mathrm{i}\mathrm{O}}{2}@\mathrm{C}\mathrm{T}\mathrm{A}\mathrm{B}}$$\end{document}mmSiO2@CTAB is the amount of mSiO2@CTAB, \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$${\rho}{{\mathrm{M}\mathrm{o}\mathrm{O}}{3}}$$\end{document}ρMoO3 is the density of MoO3, \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$${\mathrm{M}\mathrm{W}}{{\mathrm{M}\mathrm{o}\mathrm{O}}{3}}$$\end{document}MWMoO3 is the molecular weight of MoO3, and \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$${\mathrm{M}\mathrm{W}}{\mathrm{A}\mathrm{M}\mathrm{T}}$$\end{document}MWAMT is the molecular weight of AMT.

1\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$m_{{{\mathrm{AMT}}}} = \frac{{V_{{{\mathrm{pore}}}} \times m_{{{\mathrm{mSiO}}_{{2}} {\mathrm{@CTAB}}}} \times \rho_{{{\mathrm{MoO}}_{{3}} }} \times {\mathrm{MW}}_{{{\mathrm{AMT}}}} }}{{7 \times {\mathrm{MW}}_{{{\mathrm{MoO}}_{{3}} }} }} \times \left( {1 + 50\% } \right)$$\end{document}mAMT=Vpore×mmSiO2@CTAB×ρMoO3×MWAMT7×MWMoO3×1+50%

In the subsequent step, two separate alumina boats containing 1.2 g of thiourea and 0.6 g of mSiO2@CTAB-MoO_x_ hybrid precursor were placed at the upstream and downstream ends of a tube furnace, respectively, under an argon flow rate of 40 mL min−1. To minimize thiourea volatilization during heating, the boat containing thiourea was covered with an alumina lid. The samples were annealed at 600, 700, and 800 °C for 2h under an argon atmosphere to obtain the mSiO2@MoS2–N–C composites. After natural cooling, the mSiO2 template in the composites was removed by etching in 3 M NaOH aqueous solution. The as-synthesized materials were collected by centrifugation, thoroughly washed with deionized water, and dried overnight at 80 °C, yielding the final products denoted as MoS2–N–C600, MoS2–N–C700, and MoS2–N–C800, respectively.

Furthermore, nitrogen-doped carbon bridged WS2 heterostructures (WS2–N–C700) were obtained under identical conditions to MoS2–N–C700 by replacing 4.1 g of AMT with 3.5 g of ammonium metatungstate.

Preparation of Physical Hybrid of Nitrogen-Doped Carbon and MoS2 (MoS2/NC)

Nitrogen-doped carbon was derived from polyaniline. In detail, 1.6 mL of aniline was dispersed in 40 mL of ethanol and 10 mL of water, while 4.0 g of APS was dissolved in 10 mL of water. The APS solution was then added to the aniline solution. The mixture was kept stirring for 6h to finish the polymerization process. After centrifugation with water and ethanol alternatively, polyaniline was obtained and dried overnight at 80 °C for use. The product was pyrolyzed at 700 °C for 2h under Ar to yield nitrogen-doped carbon (NC). The ramping rate was 10 °C min−1. Finally, MoS2/NC was prepared by uniformly mixing commercial MoS2 with nitrogen-doped carbon at a weight ratio of 3:1 according to the TG analysis of MoS2–N–C700.

Characterization

The morphology and microstructure were recorded through field emission scanning electron microscope (FESEM, Hitachi SU8220) and transmission electron microscope (TEM, FEI, Thermo Talos F200S). The crystal structures were analyzed by X-ray diffraction (XRD, Rigaku Ultima IV) equipped with Cu _K_α radiation (λ = 1.5418 Å). Raman spectra were collected on a HORIBA Jobin Yvon LabRAM HR Evolution spectrometer with a laser wavelength of 532 nm. Electron paramagnetic resonance (EPR) spectra were examined using Bruker EMXplus-10/12. Thermogravimetric (TG) analysis was conducted on a NETZSCH/STA449F5 instrument under an air atmosphere from 30 to 700 °C at a heating rate of 10 °C min−1. During TG measurements, the carbon component was completely oxidized into CO2, while MoS2 was converted into MoO3. Therefore, the final residual mass corresponds to MoO3. Based on the stoichiometric relationship between MoS2 and MoO3, the MoS2 content in the composite was calculated from the residual mass according to their molecular weights, and the carbon content was subsequently determined from the overall mass loss. The Brunauer–Emmett–Teller (BET) surface area was analyzed by nitrogen adsorption/desorption in an advanced specific surface area and micropore analyzer (BSD-660 M, Beishide Instrument). The pore size distribution plots were recorded from the adsorption branch of the isotherms based on the Barrett–Joyner–Halenda (BJH) model. X-ray photoelectron spectroscopy (XPS) measurement was performed on an ESCALAB 250 X-ray photoelectron spectrometer with an Al K_α radiation source, with all binding energies referenced to the C 1_s peak at 284.8 eV. X-ray absorption near-edge structure (XANES) spectra were collected using a laboratory-based XAFS instrument (easyXAFS300+ , easyXAFS LLC) equipped with a Rowland-circle geometry. An Ag-anode X-ray tube operated at 40 kV and 25 mA was employed as the excitation source, together with a Si (12 12 0) spherically bent crystal analyzer and a silicon drift detector (KETEK). The extended X-ray absorption fine structure (EXAFS) spectrum was extracted from the XANES data using Athena software.

Electrochemical Measurements

The as-prepared electrode materials were mixed with Super P carbon as a conductive agent and polyvinylidene fluoride (PVDF) as a binder in N-methyl-2-pyrrolidone (NMP) at a mass ratio of 7:2:1 to form a uniform slurry. The slurry was coated onto copper foil substrates and dried under vacuum at 80 °C for 12 h. Circular disks with a diameter of 10 mm were then punched out as working electrodes. CR2032-type coin cells were assembled in an argon-filled glove box (oxygen and water are less than 0.01 ppm), employing Celgard 2500 polypropylene film (obtained from Canrd Technology Co., Ltd.) as the separator and 1 M LiPF6 dissolved in a mixed solvent of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC) (1:1:1 by volume) as the electrolyte. The mass loading of anode materials was 1.1–1.3 mg cm−2 unless otherwise stated.

To investigate the electrochemical properties of the electrode materials, galvanostatic charge/discharge (GCD) tests were performed at room temperature using a Neware battery testing system (MIHW-200-160CH-B) in the voltage window of 0.01–3.0 V (vs. Li/Li+). Cyclic voltammetry (CV) tests were carried out on a Princeton VersaSTAT 3F electrochemical workstation, employing scan rates from 0.1 to 1.0 mV s−1 to evaluate redox characteristics and reaction kinetics. Additionally, electrochemical impedance spectroscopy (EIS) measurements were conducted using a DH7000D electrochemical workstation (Donghua Analytical Instruments Co., Ltd.) with an amplified voltage of 5 mV, over a frequency range from 0.01 Hz to 100 kHz.

After activation at 0.1 A g−1 for 5 cycles, the galvanostatic intermittent titration technique (GITT) was employed to measure the Li+ diffusion coefficients (\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$${D}{{\mathrm{L}\mathrm{i}}^{+}}$$\end{document}DLi+). The procedure involved applying a series of pulse currents at 0.1 A g−1 for 10 min followed by relaxation intervals of 60 min. The \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$${D}{{\mathrm{L}\mathrm{i}}^{+}}$$\end{document}DLi+ was determined by Eq. 2:where τ represents the constant current pulse time, and _n_m and _V_m are the molar number and molar volume of active material, respectively. S is the contact area of the electrode–electrolyte interface. ∆E__s and ∆_E_τ represent the iR drop and the potential difference in a constant current pulse during the cycling process, respectively.

2\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$D_{{{\mathrm{Li}}^{ + } }} = \frac{4}{\pi \tau }\left( {\frac{{n_{{\mathrm{m}}} V_{{\mathrm{M}}} }}{S}} \right)^{2} \left( {\frac{{\Delta E_{s} }}{{\Delta E_{\tau } }}} \right)^{2} ;\left( {\tau \ll L^{2} /D_{{{\mathrm{Li}}^{ + } }} } \right)$$\end{document}DLi+=4πτnmVMS2ΔEsΔEτ2;τ≪L2/DLi+

The relationship between current response (i) and scan rate (v) at the redox peaks in the CV curves was determined using Eq. 3:where a and b are both constants. The value of b, which is equal to the slope of linear fit of log(v) versus log(i), indicates the type of process: A value of 0.5 suggests a diffusion-controlled (battery-like) process, whereas 1.0 indicates a pseudocapacitive (capacitor-like) behavior. The specific contributions from pseudocapacitive (k_1_v) and diffusion-controlled (_k_2_v_1/2) current responses can be quantitatively obtained by Eqs. 4 and 5:orwhere _k_1 is equal to the slope of linear fit of _v_1/2 versus i / _v_1/2.

3\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$i = av^{b}$$\end{document}i=avb

4\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$i = k_{{1}} v + k_{{2}} v^{{{1}/{2}}}$$\end{document}i=k1v+k2v1/2

5\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$i/v^{{{1}/{2}}} = k_{{1}} v^{{{1}/{2}}} + k_{{2}}$$\end{document}i/v1/2=k1v1/2+k2

Device-level lithium-ion supercapacitors (LISCs) were assembled with activated carbon (AC, KURARAY YP-80F) as the cathode and the as-prepared MoS2–N–C700 as the anode. Prior to assembly, the anode material was prelithiated at 0.1 A g−1 for 5 GCD cycles. The LISCs were assembled following the same protocol as described for LIBs. The mass loading ratio of cathode to anode materials was optimized to 3:1 according to the specific capacities of the two electrodes to achieve charge balance. Such optimization ensures efficient utilization of both electrodes while effectively suppressing lithium plating on the anode side. The operating voltage window was set to 0.5–4.0 V based on the electrochemically stable potential ranges of both electrodes determined from half-cell measurements. The upper cutoff voltage was limited to 4.0 V to avoid parasitic oxidation reactions at higher potentials, which could otherwise compromise long-term cycling stability. Meanwhile, the lower cutoff voltage of 0.5 V confines the electrochemical reaction primarily within the intercalation regime, thereby mitigating excessive conversion reactions, preserving the structural integrity of MoS2, and enhancing cycling durability.

The specific capacitance (C) of the LISCs was calculated from the GCD curves using Eq. 6:where I is the constant current applied during the charge/discharge process, Δ_t_ represents the charge/discharge time, m is the mass of the cathode material, and Δ_V_ denotes the operating voltage window of LISCs, ranging from 0.5 to 4.0 V.

6\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$C = \frac{I \cdot \Delta t}{{m \cdot \Delta V}}$$\end{document}C=I·Δtm·ΔV

The energy density (E) and power density (P) were calculated using Eqs. 7 and 8:where _Δ V_ΔV is the voltage window, and _Δ t_Δt represents the charge/discharge time.

7\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$E = \frac{1}{2}C\Delta V^{2}$$\end{document}E=12CΔV2

8\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$P = \frac{E}{\Delta t}$$\end{document}P=EΔt