Battery cell and method for producing the same, battery device, electric device, energy storage device

Abstract

The application relates to the field of batteries, and provides a battery monomer, a preparation method of the battery monomer, a battery device, a power utilization device and an energy storage device. The battery monomer comprises a shell, an electrode core assembly and an electrolyte in the shell; the electrode core assembly is formed by stacking or winding a positive electrode sheet, a diaphragm and a negative electrode sheet; the diaphragm comprises a base body, a friction nanofiber layer, a dielectric encapsulation layer and a coupling electrode which are sequentially arranged; and the electrolyte contains nanoparticles. The application is at least beneficial to improving the performance of the battery monomer and realizing autonomous dispersion of energy supply.

Description

Technical Field

[0001] This application relates to the field of batteries, and in particular to a battery cell and its preparation method, a battery device, an electrical device, and an energy storage device. Background Technology

[0002] In advanced rechargeable batteries, adding functional nanoparticles to liquid electrolytes has become an important strategy for improving battery performance. For example, solid electrolyte nanoparticles such as LLZTO can form an ion-conducting network on the surface of silicon anodes, alleviating volume expansion; Li3N nanoparticles can improve the lithium affinity of lithium metal anodes; and in lithium-sulfur batteries, polar nano-additives can adsorb polysulfides and suppress the shuttle effect. Summary of the Invention

[0003] This application provides a battery cell and its preparation method, a battery device, an electrical device, and an energy storage device, which at least facilitate the realization of autonomous and decentralized energy supply.

[0004] This application provides a single battery cell, comprising: The housing and the cell assembly and electrolyte located within the housing; The battery cell assembly is formed by stacking or winding positive electrode plates, separators and negative electrode plates; The diaphragm comprises a substrate, a triboelectric nanofiber layer, a dielectric encapsulation layer, and a coupling electrode arranged sequentially. The electrolyte contains nanoparticles; The triboelectric nanofiber layer and the coupling electrode form a capacitive coupling structure through the dielectric encapsulation layer. Under the vibration of the battery cell, the capacitive coupling structure generates an alternating electric field that acts on the electrolyte to drive the dispersion of the nanoparticles.

[0005] Optionally, the matrix material includes at least one of polypropylene, polyethylene, polyimide, and polyetheretherketone.

[0006] Optionally, the triboelectric nanofiber layer may comprise a combination of PTFE and PVDF fibers, or a combination of FEP and PI fibers.

[0007] Optionally, the dielectric encapsulation layer may be made of Al2O3 thin film or SiN. x film.

[0008] Optionally, the coupling electrodes are in the form of interdigitated fingers, mesh, or concentric rings.

[0009] Optionally, the material of the coupling electrode may include a corrosion-resistant conductive material.

[0010] Optionally, the nanoparticles have a particle size of 30 nm to 80 nm, and their surface is modified by carboxylation or sulfonation. They exhibit a zeta potential ≤ -25 mV in the electrolyte and an electrophoretic mobility μ. e (0.5~5)×10 -8 m 2 V -1 s -1 .

[0011] Optionally, the nanoparticles include functional inorganic nanoparticles.

[0012] Optionally, the functional inorganic nanoparticles include ceramic nanoparticles.

[0013] Optionally, the ceramic nanoparticles include ceramic electrolyte nanoparticles.

[0014] Optionally, the diaphragm further includes a microgap support layer and an RC network, wherein the microgap support layer is disposed between the substrate and the triboelectric nanofiber layer, and the RC network is disposed on the coupling electrode.

[0015] Optionally, the RC network includes a current-limiting resistor and a coupling capacitor.

[0016] This application also provides a method for preparing a battery cell, comprising: Provide a battery cell assembly, the battery cell assembly being formed by stacking or winding a positive electrode sheet, a separator and a negative electrode sheet; A housing is provided to house the battery cell assembly within the housing; Provide electrolyte and inject the electrolyte into the housing; Perform the formation step; The diaphragm comprises a substrate, a triboelectric nanofiber layer, a dielectric encapsulation layer, and a coupling electrode arranged sequentially, and the electrolyte contains nanoparticles.

[0017] Optionally, the method for generating the triboelectric nanofiber layer includes electrospinning or thin film stretching; the method for generating the dielectric encapsulation layer includes plasma-enhanced atomic layer deposition.

[0018] Optionally, the diaphragm further includes a microgap support layer and an RC network, wherein the microgap support layer is disposed between the substrate and the triboelectric nanofiber layer, and the RC network is disposed on the coupling electrode. The method for generating the microgap support layer includes hot pressing or UV imprinting.

[0019] In another aspect, this application provides a battery device comprising a battery cell as described above or a battery cell prepared by the method described above, wherein the battery device comprises one or more of a battery module, a battery pack, and an energy storage battery.

[0020] In another aspect, this application provides an electrical device that includes a battery device as described above, the battery device being used to provide electrical energy.

[0021] Another aspect of this application provides an energy storage device, which includes a battery device as described above, the battery device being used to store electrical energy.

[0022] The technical solution provided in this application has at least the following advantages: Based on the concept of "vibration energy harvesting - electric field driving - particle dispersion", this application proposes a self-powered nanoparticle dispersion system integrated inside the battery. The core of this system is to construct a TENG functional layer on the separator, which converts the vibration energy generated during daily battery use into an alternating electric field, driving charged nanoparticles to move continuously in the electrolyte and achieving a long-term stable dispersion state.

[0023] The battery cells provided in this application can be widely used in energy storage fields requiring high energy density and long cycle life, including high-end electric vehicle battery systems, portable electronic devices, and large-scale energy storage power stations. These battery cells are expected to overcome existing bottlenecks, achieving comprehensive improvements in energy density, cycle life, and safety performance, enabling high-capacity battery cells suitable for long-term energy storage applications, such as energy storage systems that can operate continuously for 4 to 8 hours at rated power. This provides key technological support for the development of next-generation high-performance electrochemical energy storage systems. Attached Figure Description

[0024] One or more embodiments are illustrated by way of example with corresponding pictures in the accompanying drawings. These illustrations do not constitute a limitation on the embodiments. Unless otherwise stated, the pictures in the accompanying drawings do not constitute a limitation on scale. In order to more clearly illustrate the technical solutions in the embodiments of this application or in the conventional technology, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0025] Figure 1 The flowchart corresponds to the method for preparing a single battery cell provided in the embodiments of this application. Detailed Implementation

[0026] As the background technology indicates, nanoparticles face significant stability challenges in liquid electrolytes. Due to van der Waals forces, nanoparticles tend to aggregate into micron-sized clusters; density differences cause particle sedimentation, creating "dead zones" at the bottom of the battery; and uneven deposition at the interface leads to excessively high local current densities, accelerating battery failure. These problems become increasingly severe during long-term storage and cycling, becoming a bottleneck restricting the application of nanoparticle additives.

[0027] Traditional solutions primarily rely on chemical dispersants, such as surfactants and polymer stabilizers. However, these chemical additives increase electrolyte viscosity, reduce ionic conductivity, and may participate in side reactions. More importantly, chemical dispersion is passive and time-sensitive; once the dispersant fails, particle aggregation becomes irreversible.

[0028] Meanwhile, batteries inevitably experience vibrations during practical use, such as low-frequency vibrations of 1Hz to 50Hz generated by the movement of electric vehicles and portable devices. This vibrational energy is typically considered interference rather than a resource. If this vibrational energy could be converted into usable driving force, it would provide a continuous energy source for the dispersion of nanoparticles.

[0029] Triboelectric nanogenerators (TENGs) have made significant progress in energy harvesting in recent years, efficiently converting mechanical energy into electrical energy. Based on the principles of triboelectricity and electrostatic induction, TENGs can generate high-voltage, low-current outputs. Combining TENG technology with the management of nanoparticles within batteries holds promise for realizing a novel active dispersion strategy.

[0030] To address the dispersion problem of nanoparticles in electrolytes, existing technologies mainly fall into the following categories. Chemical dispersion methods prevent aggregation by grafting polymer chains or small molecule ligands onto the surface of nanoparticles, utilizing steric hindrance or electrostatic repulsion. Typical surface modifications include PEGylation, carboxylation, and quaternization. This method shows significant initial effectiveness, but the modified layer may degrade in the electrochemical environment, leading to a gradual loss of dispersibility.

[0031] Mechanical dispersion methods use high-speed shearing, ball milling, or ultrasonic treatment to break up existing agglomerates. However, these methods are typically implemented during the battery fabrication stage and cannot address the problem of re-agglomeration during use. Some studies have attempted to apply ultrasound or vibration to the outside of the battery, but this results in low energy transfer efficiency and may damage the battery structure.

[0032] Thickener strategies increase electrolyte viscosity by adding polymers such as PVDF and CMC, thus slowing down particle sedimentation. However, high viscosity severely affects ion transport, leading to a decrease in rate performance. Moreover, thickening only delays, rather than prevents, sedimentation.

[0033] Magnetic-assisted dispersion involves incorporating magnetic components into particles, which are then moved by an external magnetic field. However, this requires an additional magnetic field device, increasing system complexity, and the magnetic materials may affect battery performance.

[0034] The electric field-driven method utilizes the electrophoretic motion of charged particles in an electric field to achieve dispersion. However, applying an external electric field inside the battery can interfere with normal electrochemical processes; therefore, this method is mainly used for pretreatment outside the battery.

[0035] Existing TENG technology is mainly used for external energy harvesting, such as powering wearable devices and environmental monitoring. A typical TENG structure includes two materials with different electronegativity as a triboelectric layer, which generates charge transfer through contact-separation. Although TENG can generate high voltage output, its direct application inside batteries faces many challenges, including material compatibility, electrochemical stability, and electrical isolation from the main circuit.

[0036] Existing technologies have fundamental shortcomings in solving the problem of nanoparticle dispersion, mainly in the following aspects: First, there is a lack of a continuous driving mechanism. Chemical dispersants are added once and degrade over time; mechanical treatment is intermittent and cannot be sustained; external sources require additional energy input and are unsustainable. No method can provide a continuous and stable dispersive driving force throughout the entire battery lifespan.

[0037] Secondly, it relies on passive defense rather than active control. Existing methods primarily delay aggregation and sedimentation, rather than actively breaking down existing aggregations or reversing sedimentation. Once particles aggregate or settle, it is difficult to restore them to a dispersed state. This passivity leads to a one-way decline in performance.

[0038] Third, it has poor compatibility with battery systems. Chemical additives may participate in side reactions; external physical fields may interfere with electrochemical processes; mechanical stirring may damage the electrode structure. Existing methods often improve dispersibility at the expense of certain performance characteristics.

[0039] Fourth, the uncontrollability of interfacial deposition. Even if the particles are well dispersed in the bulk phase, the deposition at the electrode interface is still random and non-uniform. Especially in high current density regions, particles tend to accumulate rapidly, forming "hot spots" and accelerating local failure.

[0040] Fifth, the issue of energy source. Active distributed energy requires energy input, but drawing power from the battery itself reduces energy efficiency; external power increases system complexity. There is a lack of an energy solution that neither consumes battery energy nor requires external power.

[0041] Finally, there are challenges related to batch consistency and scalability. The effectiveness of chemical modifications depends on precise synthesis conditions; the uniformity of mechanical processing is difficult to guarantee; and the application of external fields requires complex equipment. These factors lead to large batch-to-batch variations, making large-scale production difficult.

[0042] In the description of the embodiments of this application, the technical terms "first", "second", etc. are used only to distinguish different objects and should not be construed as indicating or implying relative importance or implicitly indicating the number, specific order or primary and secondary relationship of the indicated technical features.

[0043] In the description of the embodiments of this application, "multiple" means two or more, unless otherwise explicitly specified.

[0044] In this document, the term "embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of this application. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment mutually exclusive with other embodiments. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described herein can be combined with other embodiments.

[0045] The embodiments of this application will now be described in detail with reference to the accompanying drawings. However, those skilled in the art will understand that many technical details have been provided in the embodiments of this application to facilitate a better understanding of the application. However, the technical solutions claimed in this application can be implemented even without these technical details and various variations and modifications based on the following embodiments.

[0046] This application provides a single battery cell, comprising: The housing and the cell assembly and electrolyte located within the housing; The battery cell assembly is formed by stacking or winding positive electrode plates, separators and negative electrode plates; The diaphragm comprises a substrate, a triboelectric nanofiber layer, a dielectric encapsulation layer, and a coupling electrode arranged sequentially. The electrolyte contains nanoparticles; The triboelectric nanofiber layer and the coupling electrode form a capacitive coupling structure through the dielectric encapsulation layer. Under the vibration of the battery cell, the capacitive coupling structure generates an alternating electric field that acts on the electrolyte to drive the dispersion of the nanoparticles.

[0047] Based on the concept of "vibration energy harvesting - electric field driving - particle dispersion", this application proposes a self-powered nanoparticle dispersion system integrated inside the battery. The core of this system is to construct a TENG functional layer on the separator, which converts the vibration energy generated during daily battery use into an alternating electric field, driving charged nanoparticles to move continuously in the electrolyte and achieving a long-term stable dispersion state.

[0048] Compared to existing passive dispersion strategies, this application achieves a paradigm shift from passive to active, from one-off to continuous, and from externally powered to self-powered. The TENG unit exhibits excellent chemical stability and triboelectric properties. A suitable gap is maintained through a micropillar support structure, ensuring effective charge separation even under minute vibrations.

[0049] The key innovation of this application lies in its capacitive coupling architecture. The charge generated by the TENG is not directly injected into the electrolyte, but rather capacitively coupled through a dielectric encapsulation layer. This design ensures complete electrical isolation: the triboelectric layer has no direct contact with the electrolyte, avoiding chemical reactions; there is no direct current injection, so it does not interfere with the main electrochemical process; it only transmits an alternating electric field, achieving pure field-effect drive. This system does not change the nominal voltage and polarity of the battery, and does not provide energy output, only field-effect assistance.

[0050] Optionally, the matrix material includes at least one of polypropylene, polyethylene, polyimide, and polyetheretherketone.

[0051] Optionally, the matrix is ​​a commercially available polypropylene or polypropylene / polyethylene / polypropylene (PP / PE / PP) three-layer composite membrane with a thickness of 12μm~20μm, optionally 15μm~18μm, a porosity of 35%~45%, and a pore size of 80nm~150nm. When the ALD process temperature is >130℃, the membrane is replaced with a polyimide (PI) or polyetheretherketone (PEEK) matrix. The membrane provides basic ion transport channels and mechanical support.

[0052] Optionally, the triboelectric nanofiber layer may comprise a combination of PTFE and PVDF fibers, or a combination of FEP and PI fibers.

[0053] The friction nanofibers are primarily selected using a PTFE / PVDF combination, with FEP / PI as an alternative. For the PTFE layer, two process routes can be chosen: (1) electrospinning a mixture of PTFE dispersion and PVA, followed by short-term sintering at 300℃~360℃ in an inert atmosphere to remove the sacrificial binder (residual carbon <0.5wt%); (2) using expanded polytetrafluoroethylene (ePTFE) film micro-stretching or FEP film as equivalent replacements. The PVDF nanofibers have a diameter of 100nm~300nm and an areal density of 0.1mg / cm³. 2 ~0.4mg / cm 2 .

[0054] Optionally, the dielectric encapsulation layer may be made of Al2O3 thin film or SiN. x film.

[0055] The dielectric encapsulation layer is crucial for achieving capacitive coupling. Al₂O₃ or SiN can be prepared using plasma-enhanced atomic layer deposition (PEALD) at temperatures ranging from 80°C to 120°C. x Thin film, thickness 3nm~8nm, optional 5nm~6nm. The encapsulation layer completely covers the tribofiber layer, with a pinhole rate <1% and a dielectric strength ≥3MV / cm. Al₂O₃ / AlF₃ / SiN are available as options. x Composite bilayer (3nm+3nm) is used as an anti-pinhole enhancement scheme.

[0056] Optionally, the coupling electrodes are in the form of interdigitated fingers, mesh, or concentric rings.

[0057] Another important function of TENG in this application is interface enhancement. This is because the electric field not only acts on the bulk phase but also influences the migration and deposition process of particles towards the electrode. By optimizing the electrode pattern (interdigitated or mesh structure), the electric field distribution can be controlled, guiding particles to spread uniformly on the electrode surface, avoiding localized accumulation, forming a continuous ion-conducting network, and controlling the pore blockage area to below 5%. The coupling electrodes are designed with interdigitated, mesh, or concentric ring patterns to optimize the electric field distribution. Edge setbacks are ≥500μm, and annular insulating barriers are provided to avoid edge effects. The total patterned coverage area of ​​the dielectric encapsulation layer and coupling electrodes is ≤15% of the diaphragm projected area.

[0058] Optionally, the material of the coupling electrode may include a corrosion-resistant conductive material.

[0059] Optionally, the corrosion-resistant conductive material includes ITO, TiN or graphene, and metal electrodes (such as Al) may also be considered.

[0060] Optionally, the thickness of the coupling electrode is 5nm~15nm, and optionally 8nm~10nm.

[0061] Optionally, the nanoparticles have a particle size of 30 nm to 80 nm, and their surface is modified by carboxylation or sulfonation. They exhibit a zeta potential ≤ -25 mV in the electrolyte and an electrophoretic mobility μ. e (0.5~5)×10 -8 m 2 V -1 s -1 .

[0062] Surface functionalization of nanoparticles is a prerequisite for the effective operation of the system. By modifying LLZTO particles with carboxyl or sulfonic acid groups, a negative charge can be achieved, with the zeta potential controlled below -25 mV, corresponding to an electrophoretic mobility μ. e (0.5~5)×10 -8 m²V -1 s -1 Under an alternating electric field ranging from 0.5 V / cm to 3 V / cm, the particles achieve migration velocities of v = 0.25 μm / s to 1.5 μm / s. At low frequencies, electrophoresis dominates, driving the directional migration of particles; at high frequencies, dielectrophoresis dominates, generating local perturbations.

[0063] Optionally, the nanoparticles include functional inorganic nanoparticles.

[0064] Optionally, the functional inorganic nanoparticles include ceramic nanoparticles.

[0065] Optionally, the ceramic nanoparticles include ceramic electrolyte nanoparticles.

[0066] Optionally, the ceramic nanoparticles are represented by LLZTO, with a particle size of 30nm~80nm, optionally 40nm~60nm.

[0067] Optionally, the concentration of the ceramic nanoparticles in the electrolyte is 0.3wt%~0.8wt%, such as 0.5wt%. For the LiPF6 / EC system, LLZTO can also serve as an acid-trapping site for HF.

[0068] Optionally, the diaphragm further includes a microgap support layer and an RC network, wherein the microgap support layer is disposed between the substrate and the triboelectric nanofiber layer, and the RC network is disposed on the coupling electrode.

[0069] Optionally, the microgap support layer is formed on the diaphragm surface by hot pressing or UV imprinting, comprising a regularly arranged array of micropillars or dispersed polymer microspheres. The micropillars have a diameter of 5 μm to 20 μm, optionally 8 μm to 12 μm; a height of 3 μm to 15 μm, optionally 5 μm to 10 μm; and a spacing of 50 μm to 150 μm, optionally 80 μm to 100 μm. The microgap support layer ensures that an appropriate gap is maintained between the friction pairs, allowing for periodic contact-separation under vibration.

[0070] Optionally, the RC network includes a current-limiting resistor and a coupling capacitor.

[0071] Optionally, the current-limiting resistor R ≥ 10MΩ~100MΩ, implemented using a thin-film resistor or printed resistor. The coupling capacitor C ≤ 1nF~10nF is used for filtering and blocking DC. The RC network ensures that the TENG output is coupled to the electrolyte only in the form of an alternating electric field. System verification standard: After electrolyte wetting, the insulation resistance between the coupling electrode and the tab under 0~5V DC bias is ≥ 10. 8 Ω·cm 2 DC component leakage ≤10 Hz in the 10Hz~100Hz range -8 A / cm 2 (Lock-in amplifier + DC blocking capacitor test).

[0072] Safety is a core consideration in this design. DC leakage is controlled to within 10 nF using a high-resistance current-limiting network (R≥10MΩ) and coupling capacitors (C≤10nF). -8 A / cm 2 The following applies: TENG coupling can be shut off during formation and charge / discharge cycles of ≥1C to avoid polarization superposition; at other times, it operates adaptively from 1Hz to 50Hz. All materials have undergone rigorous screening to ensure long-term stability in the electrolyte.

[0073] The operating parameters of the battery cell in this application are designed to generate a localized alternating electric field of 0.1V / cm to 5V / cm at a vibration frequency of 1Hz to 50Hz (selectably 10Hz to 80Hz), with a selectable value of 0.5V / cm to 3V / cm. Under these conditions, a particle migration velocity of v = 0.25μm / s to 1.5μm / s is achieved. In some embodiments, the coupling branch can be switched on and off via an external control circuit.

[0074] Membrane performance is guaranteed: porosity decreases by <5% after film formation, Gurley value increases by <15%, and internal ionic conductivity decreases by <10% after wetting. The system includes a one-time melt-off point or laser-cut break point as a failure bypass protection.

[0075] The system is applicable to various battery systems. In silicon anode lithium-ion batteries, it promotes the uniform distribution of LLZTO particles in the SEI; in lithium-sulfur batteries, it guides polar particles to adsorb polysulfides; and in high-nickel cathode systems, it forms a protective interface layer. The system can also employ piezoelectric nanogenerators (PENGs) or electromechanical rectifiers as equivalent energy harvesting units.

[0076] This application also provides a method for preparing a battery cell, such as... Figure 1 As shown, it includes: S1. Provide a battery cell assembly, wherein the battery cell assembly is formed by stacking or winding a positive electrode sheet, a separator and a negative electrode sheet; S2. Provide a housing and place the battery cell assembly inside the housing; S3. Provide electrolyte and inject the electrolyte into the casing; S4. Perform the formation step; The diaphragm comprises a substrate, a triboelectric nanofiber layer, a dielectric encapsulation layer, and a coupling electrode arranged sequentially, and the electrolyte contains nanoparticles.

[0077] Optionally, the method for generating the triboelectric nanofiber layer includes lamination, specifically: laminating the prepared nanofibers on the substrate surface at 80℃~100℃ and 0.5MPa~1MPa for 30s~60s to ensure a strong bond.

[0078] For the PTFE / FEP combination, FEP nanofibers are bonded to the membrane substrate, and PTFE nanofibers are the outer free layer; for the PVDF / PI combination, PI nanofibers are bonded to the membrane substrate, and PVDF nanofibers are the outer free layer.

[0079] Optionally, a triboelectric nanofiber layer is provided on both sides of the substrate. For example, a PTFE / FEP layer (with a higher potential) is provided on the side facing the positive electrode. After gaining electrons, it becomes negatively charged, which is beneficial for driving negatively charged functional nanoparticles (such as LLZTO with ζ≤-25mV) to migrate to the positive electrode interface; a PVDF / PI layer is provided on the side facing the negative electrode.

[0080] Optionally, the method for generating the nanofibers includes electrospinning or thin film stretching; the method for generating the dielectric encapsulation layer includes plasma-enhanced atomic layer deposition.

[0081] Optionally, the steps of the electrospinning method include (taking PTFE and PVDF as examples): In the preparation of PTFE fibers, a PTFE dispersion (60 wt%) and PVA (5 wt%) were mixed as the spinning solution, with a viscosity of 800 cP~1200 cP. Spinning parameters were: voltage 15 kV~20 kV, flow rate 0.5 mL / h~1.0 mL / h, and receiving distance 15 cm~20 cm. After spinning and film formation, the fibers were sintered at 300℃~360℃ for 10 min~20 min under nitrogen protection to achieve PTFE microfiber fusion and PVA removal (residual carbon <0.5 wt%, verified by TGA).

[0082] When preparing PVDF fibers, PVDF is dissolved in a DMF / acetone (volume ratio 7:3) mixed solvent at a concentration of 15wt%~20wt%. Spinning parameters: voltage 12kV~18kV, flow rate 0.8mL / h~1.2mL / h. Ambient humidity control <40%.

[0083] Optionally, the steps of the thin film stretching method include (taking ePTFE and FEP as examples): Commercial ePTFE films (thickness 5μm~20μm) are micro-stretched, or FEP films are plasma-treated to enhance their triboelectric properties, and then thermally bonded to the substrate.

[0084] Optionally, the steps of the plasma-enhanced atomic layer deposition method include: Low-temperature Al2O3 was prepared using the PEALD process. Trimethylaluminum (TMA) and H2O plasma were used as precursors, and the deposition temperature was 80℃~120℃. Each cycle consisted of a 0.1s TMA pulse, a 5s N2 purge, a 2s H2O plasma purge, and a 5s N2 purge. 30~80 cycles were performed to obtain Al2O3 layers with a thickness of 3nm~8nm.

[0085] For anti-pinhole enhancement, an Al2O3 / AlF3 composite bilayer is used: first deposit 3nm Al2O3, then deposit 3nm AlF3.

[0086] Encapsulation layer quality control: Pinhole detection is performed using an electrochemical method (leakage current <10nA / cm). 2 The test uses both dye penetration method and dielectric withstand voltage test to confirm ≥3MV / cm.

[0087] Optionally, the method for fabricating the coupling electrode includes (taking ITO electrode and TiN electrode as examples): ITO electrodes were deposited by magnetron sputtering. The target material was In2O3:SnO2 (90:10), the sputtering power was 50W~100W, and the substrate temperature was <100℃. The deposition rate was 0.5nm / min~1.0nm / min, resulting in ITO layers with a thickness of 8nm~12nm.

[0088] The TiN electrode is produced by reactive sputtering: Ti is used as the target, Ar / N2 is used as the mixed atmosphere, and the volume ratio of N2 is controlled to be 10%~20%.

[0089] The graphene electrode is produced by CVD graphene transfer or reduced graphene oxide spraying.

[0090] Electrode patterning employs a mask method. Interdigitated structures: finger width 30μm~50μm, spacing 40μm~60μm; grid structures: grid size 100μm~200μm, linewidth 20μm~30μm; concentric ring structures: ring width 50μm~100μm, spacing 100μm~200μm. All pattern edges are recessed by ≥500μm, and a 100μm wide annular insulating barrier is provided.

[0091] Optionally, the diaphragm further includes a microgap support layer and an RC network, wherein the microgap support layer is disposed between the substrate and the triboelectric nanofiber layer, and the RC network is disposed on the coupling electrode. The method for generating the microgap support layer includes hot pressing or UV imprinting.

[0092] Optionally, the preparation method of the micro-gap support layer includes: firstly, the substrate undergoes plasma surface activation at a power of 30W~50W for a processing time of 30s~60s to increase the surface energy. For processes with high temperature resistance requirements, a PI or PEEK substrate is used. A micropillar array is formed using hot stamping technology: the substrate is placed on a pre-made silicon mold, and the PP film is held at 120℃~140℃, and the PI / PEEK film at 180℃~220℃, under a pressure of 5MPa~10MPa for 1min~3min. After cooling, the mold is removed to obtain a membrane substrate with a regular micropillar array.

[0093] The geometric parameters of the micropillars are precisely controlled through mold design. For the polymer microsphere support scheme, monodisperse PS or PMMA microspheres (5μm~20μm) are dispersed in ethanol and sprayed onto the substrate surface, with the coverage controlled at 20%~40%.

[0094] Optionally, the method for preparing the RC network includes: Thin-film resistors are prepared by screen printing carbon paste. After printing, they are cured at 120℃~150℃ for 30 minutes. The target resistance is 10MΩ~100MΩ, which is achieved by adjusting the line length and line width.

[0095] The capacitors used are ceramic chip capacitors (1nF~10nF, voltage rating >50V) or printed capacitors.

[0096] The leads are made of gold-plated copper wire insulated with polyimide and connected with conductive adhesive. A fuse (0.1A fusing current) is provided for safety protection.

[0097] The RC network can be fabricated using any of the existing technologies.

[0098] Optionally, the surface modification method for the nanoparticles includes: LLZTO carboxylation: LLZTO was dispersed in anhydrous ethanol (10 g / L), and γ-aminopropyltriethoxysilane (APTES) (1 mmol / g LLZTO) was added. The mixture was refluxed at 80 °C for 4 h. After centrifugation and washing, a DMF solution of succinic anhydride (2 mmol / g LLZTO) was added, and the mixture was reacted at 100 °C for 2 h.

[0099] Sulfonation: LLZTO was reacted with 1,3-propanesulfonic acid lactone (2 mmol / g LLZTO) in DMF at 120 °C for 6 h.

[0100] Surface modification verification: FTIR confirmation - COOH (1720 cm⁻¹) -1 ) or -SO3H (1040cm -1 TGA determination of organic matter 2wt%~5wt%; ζ potential test ≤-25mV; electrophoretic mobility determination μ e =(0.5~5)×10 -8 m 2 V -1 s -1 .

[0101] Optionally, electrolyte preparation methods include: Electrolyte preparation was performed in a glove box (H2O < 1 ppm). Functionalized LLZTO (0.3 wt%–0.8 wt%) was added to the basic electrolyte (LiPF6 / EC-DMC or LiTFSI / DOL-DME), followed by sonication for 10 min and high-speed shearing for 5 min. The mixture was allowed to stand to confirm no significant sedimentation.

[0102] System assembly and testing of battery cells Protect the electrodes and leads during TENG diaphragm cutting. Ensure leads are properly routed through the sealing ring during assembly.

[0103] Electrical testing: Insulation resistance ≥10 8 Ω (megohmmeter); DC leakage ≤10 -8 A / cm 2 (Electrochemical workstation); Test output voltage and electric field strength under simulated vibration (10-50Hz, 0.5g acceleration).

[0104] Inject the electrolyte containing nanoparticles and let it stand for 2 hours to fully immerse the particles.

[0105] Performance verification: Gurley value of the diaphragm increased by <15%; ionic conductivity decreased by <10%; particle agglomeration size remained <150nm (DLS monitoring); interface deposition uniformity (SEM confirmed pore blockage <5%).

[0106] Quality control: residual solvents (DMF / acetone / ethanol <10ppm each, GC-MS detection); moisture <50ppm (Karl Fischer method); residual carbon <0.5wt% (elemental analysis).

[0107] In another aspect, this application provides a battery device comprising a battery cell as described above or a battery cell prepared by the method described above, wherein the battery device comprises one or more of a battery module, a battery pack, and an energy storage battery.

[0108] In another aspect, this application provides an electrical device that includes a battery device as described above, the battery device being used to provide electrical energy.

[0109] Electrical devices include, but are not limited to, mobile phones, tablets, laptops, electric toys, power tools, electric vehicles, electric cars, ships, spacecraft, etc. Among them, electric toys can include stationary or mobile electric toys, such as game consoles, electric car toys, electric ship toys, and electric airplane toys, etc. Spacecraft can include airplanes, rockets, space shuttles, and spacecraft, etc.

[0110] Another aspect of this application provides an energy storage device, which includes a battery device as described above, the battery device being used to store electrical energy.

[0111] Energy storage devices include, but are not limited to, residential energy storage cabinets, commercial energy storage cabinets, energy storage containers, energy storage racks, energy storage power stations, energy storage battery packs, or portable energy storage systems. Energy storage devices may also include energy management systems (EMS), battery management systems (BMS), and power conversion systems (PCS).

[0112] The innovation of this application also lies in: 1. Self-powered active drive vs. externally powered passive defense Traditional chemical dispersants can only passively delay aggregation, and once they fail, they cannot be reversed; adding ultrasound or magnetic fields requires additional energy and equipment. This application utilizes environmental vibration (1-50Hz) to generate an electric field through TENG, achieving self-powered active dispersion. Vibration energy is inherent energy in battery use; converting it into a useful driving force enables energy recycling, allowing continuous operation throughout the battery's entire lifespan without external power supply.

[0113] 2. Capacitive coupling for complete isolation vs. direct application of electric field Existing electric field-driven methods directly apply voltage to the electrolyte, which interferes with the electrochemical reaction and triggers side reactions. This application achieves capacitive coupling through a 3-8nm dielectric layer, completely isolating the TENG from the electrolyte, transmitting only the alternating electric field without DC injection. The verification standard is clearly defined: insulation resistance ≥ 10 Ω. 8 Ω·cm 2 DC leakage ≤10 -8 A / cm 2 The system does not change the battery voltage or polarity, does not introduce free metal exposure, and does not induce PF5 / HF amplification.

[0114] 3. Dual-function synergy vs. single-function mechanism Traditional methods either focus solely on bulk dispersion or only address interface issues. This application simultaneously achieves: dispersion of particles in the bulk phase via electrophoresis (μ... e =(0.5~5)×10 -8 m 2 V -1 s -1 The combined motion of electrophoresis and dielectric electrophoresis continuously breaks up agglomerates, maintaining a cluster size of <150nm; at the interface, the field distribution is controlled by patterned electrodes to achieve uniform spreading, with a pore blockage area of ​​<5%, thus solving the problem of epidermal deposition.

[0115] 4. Frequency Adaptive and Intelligent Control vs. Fixed Conditions Chemical dispersions operate under fixed conditions and cannot adapt to changes. This application's TENG responds to a wide frequency range of 1Hz~50Hz vibrations, automatically converting them into a corresponding electric field output. Low-frequency (<10Hz) electrophoresis dominates, while high-frequency (>50Hz) dielectric electrophoresis dominates. The system can automatically shut down during formation and ≥1C fast charging to avoid polarization superposition; a pulse mode with a duty cycle ≤30% is set to intelligently adapt to different operating conditions.

[0116] 5. Innovative Applications of Mature Materials vs. Risks of New Materials Instead of using unproven new materials, we innovatively apply mature materials: PTFE / PVDF are standard materials in the battery field; ePTFE or FEP are used as equivalent replacements; sacrificial agents such as PVA are completely removed through sintering (residual carbon <0.5wt%); PEALD low-temperature process (80℃~120℃) ensures compatibility with PP / PE separators; all materials have undergone long-term stability verification.

[0117] 6. Multiple protection and fail-safe vs. single point of failure The design incorporates multiple protection mechanisms: RC network for current limiting and DC blocking; hardware protection via fuse; dual-criteria detection for pinholes (electrochemical + dye penetration); edge clearance ≥500μm + annular insulating barrier; and guaranteed non-degradation of separator performance (porosity decrease <5%, Gurley level increase <15%, conductivity decrease <10%). Even if the TENG fails, the basic battery function remains unaffected.

[0118] 7. Platform-based scalable design vs. dedicated solutions Adaptable to multiple systems through parameter adjustment: RC parameters (R=10MΩ~100MΩ, C=1nF~10nF) are adjustable; electrode patterns (interdigitated / grid / concentric rings) are selectable; suitable for various particles such as LLZTO, Li3N, and LiF; compatible with lithium-ion, lithium-sulfur, and sodium-ion batteries; can use PENG or electromechanical rectifiers as equivalent energy sources. Coverage area ≤15% ensures no impact on basic performance.

[0119] To verify the impact of the self-dispersion and interface enhancement system of the electrolyte within the battery based on triboelectric nanogenerators proposed in this application on the dispersion stability of nanoparticles and the battery cycle performance, this application designed a series of embodiments and comparative examples, as shown in Tables 1 to 3. These examples systematically investigated the influence of key technical elements such as the integrated TENG-separator structure, dielectric encapsulation layer, RC network, nanoparticle surface functionalization, alternating electric field driving mechanism, and coupling electrodes on the system performance. The following details the material selection, TENG-separator preparation, battery assembly, and testing methods.

[0120] The materials used in the following embodiments and comparative examples are as follows.

[0121] The membrane substrate material is a commercially available three-layer composite membrane of polypropylene / polyethylene / polypropylene, with a thickness of 16 μm, a porosity of 38%, and a pore size of approximately 100 nm. For high-temperature process compatibility verification, a polyimide membrane with a thickness of 20 μm is used. The hot-pressing mold for the micro-gap support layer is made of monocrystalline silicon, and the micropillar array pattern is pre-fabricated using photolithography.

[0122] The materials used to prepare the triboelectric nanofiber layer include a polytetrafluoroethylene dispersion (60 wt% solids), polyvinyl alcohol (number-average molecular weight approximately 80,000 g / mol) as a spinning aid, and polyvinylidene fluoride (number-average molecular weight approximately 530,000 g / mol). The electrospinning solvent is a mixture of N,N-dimethylformamide and acetone. Alternative triboelectric materials include fluorinated ethylene propylene copolymer films and polyimide nanofibers.

[0123] The dielectric encapsulation layer was prepared using plasma-enhanced atomic layer deposition (PEALD) with trimethylaluminum and water plasma as precursors at a deposition temperature of 100°C. The anti-pinhole enhancement scheme employed an alumina / aluminum fluoride composite bilayer structure, with the aluminum fluoride layer using trimethylaluminum and anhydrous hydrogen fluoride as precursors.

[0124] The coupling electrodes are deposited using an indium tin oxide target via magnetron sputtering, with the target composition being an indium oxide to tin oxide mass ratio of 90:10. Electrode patterning is achieved using a stainless steel mask to create interdigitated or mesh structures.

[0125] The RC network components include thin-film resistors (prepared by carbon paste screen printing, with adjustable resistance from 10MΩ to 100MΩ), coupling capacitors (ceramic chip capacitors, with capacitance from 1nF to 10nF and withstand voltage of 50V), and leads (gold-plated copper wires insulated with polyimide, with a diameter of 50μm).

[0126] Functional nanoparticles, primarily lithium lanthanum zirconium tantalum oxide (LLZTO), with particle sizes ranging from 40 nm to 60 nm, were purchased from commercial suppliers. Surface functionalizing agents included 3-aminopropyltriethoxysilane and succinic anhydride for carboxylation modification, and 1,3-propanesulfonic acid lactone for sulfonation modification. Alternative nanoparticles included lithium nitride and lithium fluoride, both with particle sizes ranging from 50 nm to 80 nm.

[0127] The electrolyte matrix is ​​made by dissolving 1.0 mol / L lithium hexafluorophosphate in a mixed solvent of ethylene carbonate / dimethyl carbonate (volume ratio 1:1), with a water content of less than 20 ppm.

[0128] The positive electrode uses lithium nickel cobalt manganese oxide (NCM811) as the active material, and the negative electrode uses artificial graphite or silicon-carbon composite material. The positive electrode slurry formulation, by mass ratio, is 94% NCM811 active material, 3% Super P conductive agent, and 3% PVDF binder. The negative electrode slurry formulation, by mass ratio, is 95% graphite active material, 2% Super P conductive agent, and 3% CMC / SBR composite binder.

[0129] All the chemical reagents mentioned above are analytical grade or battery-grade materials, and are commercially available. All operations involving water- and oxygen-sensitive materials were performed in an argon-atmospheric glove box, where the water and oxygen content was controlled to be below 0.1 ppm.

[0130] The membrane pretreatment and micropillar formation process is as follows: Commercial PP / PE membranes are cut to the required size and first undergo plasma surface activation treatment at 40W RF power in an argon atmosphere for 45 seconds to improve surface energy and the adhesion of subsequent coatings. Subsequently, a micro-gap support layer is formed using hot stamping technology. The activated membrane is then placed on a pre-fabricated silicon mold and held at 130℃ and 8MPa pressure for 2 minutes. After cooling to room temperature, it is demolded to obtain a membrane substrate with a regular array of micropillars. The micropillars have a diameter of 10μm, a height of 8μm, a spacing of 100μm, and are arranged in a square array.

[0131] The triboelectric nanofiber layer was prepared using electrospinning. For the polytetrafluoroethylene (PTFE) layer, a PTFE dispersion and a polyvinyl alcohol (PVA) aqueous solution were mixed at a mass ratio of 4:1 and stirred until homogeneous to form a spinning solution with a viscosity of approximately 1000 cP. Spinning parameters were set as follows: voltage 18 kV, flow rate 0.8 mL / h, receiving distance 18 cm, ambient temperature 25 °C, and relative humidity below 35%. After spinning, the film was transferred to a tube furnace and sintered at 340 °C at a rate of 5 °C / min under high-purity nitrogen protection for 15 min, achieving PTFE microfiber fusion and complete removal of the PVA sacrificial agent. For the polyvinylidene fluoride (PVDF) nanofiber layer, PTFE was dissolved in a DMF / acetone (7:3 volume ratio) mixed solvent at a concentration of 18 wt%. Spinning parameters were set as follows: voltage 15 kV, flow rate 1.0 mL / h, and receiving distance 16 cm. The prepared PTFE nanofibers had a diameter of approximately 200 nm and an areal density of 0.25 mg / cm³. 2 The friction fiber layer was transferred onto the diaphragm micropillar array via lamination at a temperature of 90°C, a pressure of 0.8 MPa, and a time of 45 s.

[0132] The dielectric encapsulation layer was deposited using plasma-enhanced atomic layer deposition (PEALD). A diaphragm with a triboelectric fiber layer was placed in the reaction chamber at a substrate temperature of 100°C. A single cycle of alumina deposition consisted of a 0.1s trimethylaluminum pulse, a 5s nitrogen purging, a 2s water plasma (200W power), and a 5s nitrogen purging. This process was repeated 50 times to obtain an alumina dielectric layer approximately 5nm thick. For pinhole resistance enhancement, 30 cycles of alumina deposition (approximately 3nm) were performed first, followed by 30 cycles of aluminum fluoride deposition (approximately 3nm). After deposition, pinhole detection was performed using both electrochemical leakage and dye penetration methods to confirm a pinhole rate of less than 1%.

[0133] The coupling electrodes were fabricated using magnetron sputtering. The dielectrically encapsulated sample was fixed using a stainless steel mask pre-patterned with interdigitated electrode patterns, each finger 40 μm wide and 50 μm apart. Sputtering parameters included an indium tin oxide target, 80 W RF power, 0.5 Pa argon gas pressure, room temperature substrate, a deposition rate of approximately 0.8 nm / min, and a deposition time of 12 min, resulting in an electrode layer approximately 10 nm thick. The electrode pattern edge setback was designed to be 500 μm, and edge protection was achieved by additionally depositing a 100 μm wide silicon dioxide annular insulating barrier. The total coverage area of ​​the dielectric and electrode patterning was controlled to be within 12% of the membrane's projected area.

[0134] The integration of the RC network is accomplished through the following steps. Thin-film resistors are prepared by screen printing carbon paste onto the inactive areas at the edge of the diaphragm. After printing, the paste is cured at 130°C for 30 minutes. The target resistance value is achieved by adjusting the line length (5mm~20mm) and line width (0.2mm~0.5mm). Coupling capacitors (ceramic chips, 5nF) are connected by soldering with conductive silver paste. Leads are made using polyimide-insulated gold-plated copper wire, and conductive adhesive is used to fix the connection points. A thin-film fusible link (fusible current 0.1A) is installed at the series connection point of the resistor and capacitor for safety protection.

[0135] The carboxylation modification process of LLZTO nanoparticles is as follows: 10 g of LLZTO nanoparticles were dispersed in 200 mL of anhydrous ethanol and ultrasonically dispersed for 30 min to form a homogeneous suspension. 1.0 mL of 3-aminopropyltriethoxysilane was added under nitrogen protection, and the mixture was stirred at 80 °C for 4 h under reflux to graft the aminosilane coupling agent onto the particle surface. After the reaction, the particles were centrifuged (8000 rpm, 10 min) and washed three times with anhydrous ethanol. The aminated particles were redispersed in 100 mL of anhydrous DMF, and 2.0 g of succinic anhydride was added. The mixture was stirred at 100 °C for 2 h to achieve the conversion of amino groups to carboxyl groups. After the reaction, the particles were centrifuged, washed, and vacuum dried at 80 °C for 12 h to obtain carboxylated LLZTO particles. Sulfonation modification was performed using a similar process, with the aminated LLZTO particles reacted with 1,3-propanesulfonic acid lactone (2 mmol / g LLZTO) in anhydrous DMF at 120 °C for 6 h.

[0136] The surface modification effect was confirmed by Fourier transform infrared spectroscopy to include the presence of carboxyl or sulfonic acid groups. Thermogravimetric analysis determined the organic modification layer content to be 2wt%–5wt%. Zeta potential testing confirmed that the modified particles had a potential of -40mV to -30mV in a simulated electrolyte system. These characterizations were used to confirm successful functionalization and are not intended as evaluation indicators of the technical effects of the embodiments.

[0137] Electrolytes containing functionalized nanoparticles were prepared in an argon-filled glove box. Using a baseline formulation as an example, 0.5 g of carboxylated LLZTO particles (corresponding to a concentration of 0.5 wt%) were added to 100 g of basic electrolyte (1.0 M LiPF6 / EC-DMC). The mixture was first ultrasonically dispersed for 10 min (100 W, 40 kHz), followed by high-speed shear dispersion for 5 min (10,000 rpm). After dispersion, the mixture was allowed to stand and observed. Once no significant sedimentation was observed, it was sealed and stored for later use.

[0138] In this application, pouch cells were used for verification testing. Except for the application expansion verification group (Example 15 uses a silicon-carbon anode system and Example 16 uses a lithium-sulfur battery system), the other examples and comparative examples all used 3Ah NCM811 / graphite pouch cells as a unified test platform and adopted a single-layer stacked structure.

[0139] For the positive electrode preparation, NCM811, Super P, and PVDF were mixed in N-methylpyrrolidone at a mass ratio of 94:3:3 to form a slurry with a solid content of 55%. The slurry was then coated onto a 15 μm thick aluminum foil current collector using a doctor blade coater, achieving a coating surface density of (20 ± 0.5) mg / cm³. 2 After vacuum drying at 120℃ for 12 hours, the material was rolled to achieve a compaction density of 3.3 g / cm³. 3 The negative electrode was prepared by mixing graphite, Super P, and CMC / SBR in deionized water at a mass ratio of 95:2:3 to form a slurry, which was then coated onto an 8 μm thick copper foil current collector. The coating surface density was (12±0.3) mg / cm². 2 After drying, it is rolled and compacted to a density of 1.5 g / cm³. 3 .

[0140] Battery assembly was carried out in a dry chamber with a dew point below -40°C. The positive electrode, TENG-separator (or a standard separator as shown in the comparative example), and negative electrode were stacked sequentially, with the coupling electrode surface of the TENG-separator facing the positive electrode side. The RC network leads were led out through pre-drilled holes in the aluminum-plastic film and sealed with hot melt adhesive. After stacking, the cells were encapsulated in an aluminum-plastic film, with a pre-drilled electrolyte filling port. The encapsulated cells were dried in an 80°C vacuum oven for 24 hours to ensure a moisture content below 50 ppm.

[0141] The electrolyte injection process involves injecting a prepared electrolyte containing nanoparticles into the battery. The injection volume is determined based on the battery's design capacity (approximately 3.5 g / Ah). After injection, the battery is left to stand under a vacuum of -85 kPa for 30 minutes to promote wetting, followed by sealing.

[0142] The formation process employs a low-current stepped charging strategy. After electrolyte injection, the battery is left to stand at a constant temperature of 45℃ for 24 hours to allow for full electrolyte wetting and to establish good interfacial contact between the TENG-separator and the electrodes. Formation is first performed by constant current charging at 0.02C to 3.0V, followed by a 10-minute rest period, then charging at 0.05C to 3.5V, followed by a 10-minute rest period, and finally charging at 0.1C to 4.3V, with the voltage maintained at a constant level until a 0.05C cutoff is achieved. After formation, the battery is discharged at 0.1C to 2.8V, and the first-cycle capacity and coulombic efficiency are recorded.

[0143] Five parallel samples were prepared for each embodiment and comparative example for testing. The data were averaged, and the typical test error was within ±5%. As shown in Table 4.

[0144] The system characteristic test includes three items. The insulation resistance test is performed using a digital megohmmeter. The test conditions are: after electrolyte immersion, a 0-5V DC bias is applied between the coupling electrode and the battery tab, and the steady-state resistance value is recorded in Ω·cm. 2 The calculation was normalized using the effective area of ​​the coupling electrode. DC leakage current testing was performed using an electrochemical workstation, measuring steady-state leakage current under a 0–5V DC bias, with units of A / cm². 2 Similarly, the effective area of ​​the coupling electrode is normalized. The TENG output voltage is tested using a vibration table and a digital oscilloscope. The vibration table is set with adjustable frequency from 10Hz to 50Hz and acceleration of 0.5g. The oscilloscope records the peak voltage of the TENG output.

[0145] The dispersion effect test included two parts. The agglomeration particle size test was conducted using a dynamic light scattering instrument. Samples were taken from the electrolyte containing nanoparticles, diluted to an appropriate concentration, and the D50 particle size value was recorded in nanometers. Each sample was measured three times, and the average value was taken. The dilution before testing was only for instrument measurement purposes and did not change the relative dispersion trend between different embodiments. The settling time test was conducted visually. The electrolyte containing nanoparticles was placed in a transparent glass bottle and allowed to stand. The time it took for obvious stratification to occur was recorded in hours.

[0146] The membrane performance test includes two parts. The Gurley value test is conducted using a permeability meter according to standard methods, measuring the time required for 100 mL of air to pass through the membrane. The rate of change of the Gurley value of the TENG-membrane relative to the original membrane is calculated. The rate of change is equal to the TENG-membrane Gurley value minus the original membrane Gurley value, divided by the original membrane Gurley value, multiplied by 100%. The ionic conductivity test uses electrochemical impedance spectroscopy (EIS). The membrane is sandwiched between two stainless steel blocking electrodes to form a symmetrical cell. After adding electrolyte for wetting, impedance testing is performed in the frequency range of 0.01 Hz to 1 MHz. The ionic conductivity σ (unit: S / cm) can be calculated using the following formula: σ = L / (R × S), where L is the membrane thickness (cm), R is the bulk resistance (Ω) obtained from the high-frequency intercept of the EIS spectrum, and S is the effective area of ​​the test electrode (cm²). 2 The retention rate of ionic conductivity η can be calculated using the following formula: η = (σ TENG / σ0)×100%, where σ TENG σ0 represents the ionic conductivity of the TENG-diaphragm, and σ0 represents the ionic conductivity of the original diaphragm.

[0147] Battery performance testing includes four components. The first-cycle coulombic efficiency is recorded during the formation process and is equal to the first discharge capacity divided by the first charge capacity multiplied by 100%. The room-temperature cycle capacity retention test is conducted at 25°C with a charge / discharge regime of 1C constant current charging to the upper limit voltage of 4.3V, constant voltage charging to the current cutoff point of 0.05C, and then 1C constant current discharging to the lower limit voltage of 2.8V. The discharge capacity is recorded at the 200th and 500th cycles, and the capacity retention rate is equal to the Nth discharge capacity divided by the first discharge capacity multiplied by 100%. The high-temperature cycle capacity retention test is conducted in a 45°C constant-temperature chamber using the same charge / discharge regime as at room temperature, and the capacity retention rate is recorded at the 200th cycle.

[0148] Based on the above experimental design, this application conducted systematic tests on all embodiments and comparative examples. The test results are analyzed and discussed below from four aspects: core innovation verification, process parameter optimization, material selection verification, and application expansion, as shown in Tables 5 and 6.

[0149] 1. Verification of the technical effectiveness of TENG active distribution mechanism By comparing the test data of the baseline Example 1 and Comparative Example 1, a significant performance improvement brought about by the triboelectric nanogenerator system can be clearly observed. In Example 1, the aggregate size D50 of the LLZTO nanoparticles was 125 nm, and the settling time exceeded 168 h, while in the conventional non-TENG structure of Comparative Example 1, the aggregate size increased sharply to 580 nm, and the settling time dropped sharply to 18 h. This difference of more than 4 times in particle size and nearly 10 times in settling time directly verifies the effectiveness of the vibration energy harvesting, electric field driving, and particle dispersion technology route of this application. From the perspective of battery performance, the huge difference in dispersion state directly translates into a significant difference in cycle stability. After 500 cycles at 25°C, the capacity retention rate of Example 1 reached 87.2%, while that of Comparative Example 1 was only 65.2%, a difference of more than 22 percentage points. In Comparative Example 1, the rapidly aggregated and settled nanoparticles could not form a uniformly distributed ion-conducting network at the electrode interface, resulting in uneven local current density and a continuous increase in interfacial impedance, ultimately accelerating capacity decay. The 45°C high-temperature cycling test further confirmed this analysis. The capacity retention rate of Example 1 after 200 cycles was 83.5%, while that of Comparative Example 1 was reduced to 58.5%. High temperature accelerated the aggregation kinetics, causing the system without an active dispersion mechanism to fail more quickly.

[0150] 2. Security Verification of Capacitively Coupled Zero-Injection Architecture The dielectric encapsulation layer is a core component for realizing the capacitively coupled zero-injection architecture, and the experimental results of Comparative Example 2 strongly demonstrate its indispensability. Although Comparative Example 2 retains the complete TENG structure, it lacks the alumina dielectric layer, and its insulation resistance is only 2.8 × 10⁻⁶. 5 Ω·cm 2 Compared to 3.5 × 10 in Example 1 8 Ω·cm 2 The DC leakage current decreased by three orders of magnitude, reaching 3.5 × 10⁻⁶. -6 A / cm 2 Compared to 6.5 × 10 in Example 1 -9 A / cm 2 This represents an increase of nearly three orders of magnitude. This drastic deterioration in electrical isolation performance leads to direct contact between the triboelectric layer and the electrolyte, triggering persistent side reactions. Macroscopically, this manifests as a decrease in the first-cycle coulombic efficiency from 88.2% in Example 1 to 79.8% in Comparative Example 2, and a decrease in capacity retention after 500 cycles from 87.2% to 71.5%. Without dielectric layer protection, the charge generated by the TENG is directly injected into the electrolyte system, not only interfering with normal electrochemical processes but also potentially inducing electrolyte decomposition and the accumulation of interfacial byproducts.

[0151] The RC network, as an auxiliary component of the capacitive coupling architecture, demonstrates its beneficial contribution to system safety in Comparative Example 3. Comparative Example 3 retains the dielectric layer but lacks the RC network; the insulation resistance remains at 4.2 × 10⁻⁶.8 Ω·cm 2 The current is within acceptable limits, but the DC leakage current has increased to 4.5 × 10⁻⁶. -7 A / cm 2 This represents an increase of approximately two orders of magnitude compared to Example 1. Although this level of leakage has not led to catastrophic consequences, it still has a measurable impact on battery performance, with a 500-cycle capacity retention of 84.5%, a decrease of 2.7 percentage points compared to Example 1. This result demonstrates that the RC network further suppresses DC component leakage through the dual effects of high-resistance current limiting and capacitive DC blocking, providing additional safety margins. The relatively mild performance degradation in Comparative Example 3 confirms the technical positioning of the RC network as an optional but beneficial feature.

[0152] 3. Verification of the necessity of surface functionalization of nanoparticles Surface functionalization is a prerequisite for achieving efficient electric field-driven dispersion, and the experimental data of Comparative Example 4 clearly reveals the necessity of this technical feature. Comparative Example 4 uses unmodified LLZTO particles, whose absolute zeta potential is only 10 mV, much smaller than the 35 mV (absolute zeta potential) of the carboxylated particles in Example 1. This indicates weak surface negative charge and poor stability. The lower surface charge density directly leads to a decrease in electrophoretic mobility, and the response speed of the particles is significantly slower under the same electric field strength. Macroscopically, this manifests as the aggregated particle size D50 of Comparative Example 4 reaching 385 nm, more than three times that of Example 1, and a settling time of only 58 h, less than one-third of that of Example 1. From the perspective of dispersion mechanism, electrophoretic mobility is proportional to zeta potential. The decrease in the absolute zeta potential from 35 mV to 10 mV means a reduction of approximately 70% in the electrophoretic driving force. This significant weakening of the driving force makes it difficult for nanoparticles to overcome the aggregation tendency caused by van der Waals forces. Battery performance data are highly correlated with dispersion state. The capacity retention rate of Comparative Example 4 after 500 cycles was 73.2%, which is 14 percentage points lower than that of Example 1, fully demonstrating that surface functionalization is a necessary condition for achieving the technical effects of this application.

[0153] 4. Verification of the superiority of alternating electric fields over constant electric fields Comparative Example 5 used an external DC power supply to generate a constant electric field instead of the alternating electric field output of the TENG. Its experimental results revealed the unique advantages of alternating electric fields in nanoparticle dispersion applications. The aggregated particle size D50 of Comparative Example 5 was 325 nm, and the settling time was 52 h. While better than Comparative Example 1 (without any electric field), it was significantly worse than Example 1 using an alternating electric field. The capacity retention rate after 500 cycles was only 69.5%, which was poor among all samples with electric field-driven capabilities. The essential difference between alternating and constant electric fields lies in the different particle motion modes. Under a constant electric field, charged particles continuously migrate along a fixed direction, easily accumulating near the electrode to form a high-concentration region, which may exacerbate local aggregation and uneven interfacial deposition. In contrast, alternating electric fields drive particles to perform periodic reciprocating motion, achieving directional transport in the low-frequency range dominated by electrophoresis and generating local perturbations in the high-frequency range dominated by dielectrophoresis. The two mechanisms work synergistically to continuously break up aggregates and maintain uniform bulk dispersion. This application utilizes TENG to directly convert environmental vibrations into alternating current output, which naturally meets the requirements of this dispersion mechanism.

[0154] 5. Verification of the necessity of coupling electrodes for electric field conduction Comparative Example 7 retains the complete TENG structure and dielectric encapsulation but lacks the coupling electrode, used to verify the irreplaceable role of the coupling electrode in electric field conduction. Experimental results show that the aggregated particle size D50 of Comparative Example 7 is as high as 520 nm, and the settling time is only 22 h. These indicators are very close to those of Comparative Example 1 (580 nm, 18 h) without any TENG structure. The capacity retention rate after 500 cycles is 67.8%, also close to 65.2% of Comparative Example 1. This quasi-failure performance clearly proves that without the field distribution design of the coupling electrode, the electric field generated by the TENG cannot be effectively conducted into the electrolyte system, and the entire dispersion mechanism is ineffective. From the perspective of electric field distribution, the interdigitated or grid pattern design of the coupling electrode establishes a clear field gradient distribution in the electrolyte, providing a clear driving force for the migration of charged particles. Without the coupling electrode, the charge distribution on the surface of the dielectric layer cannot form an effective field penetration in the electrolyte, and the electric field is confined to an extremely thin surface area, unable to act on the nanoparticles in the bulk phase. The similarity between Comparative Example 7 and Comparative Example 1 serves as a counter-evidence of the technical necessity of the complete electric field conduction link of TENG, dielectric layer, coupling electrode, and electrolyte in this application.

[0155] 6. The beneficial effect of the micro-gap support layer on system stability Comparative Example 6, lacking the micro-gap support layer, was used to verify the impact of this component on the TENG output stability. The TENG output voltage of Comparative Example 6 was only 1.8V and exhibited significant fluctuations, a decrease of approximately 44% compared to the stable 3.2V output of Example 1. This unstable electric field output led to fluctuations in the dispersion effect, with an agglomeration particle size D50 of 158nm and a settling time of 138h, both inferior to Example 1 but superior to the comparative examples lacking other key components. The 500-cycle capacity retention rate was 84.2%, a decrease of 3 percentage points compared to Example 1. The micro-gap support layer ensures stable periodic contact-separation motion under minor vibrations by maintaining an appropriate gap between the friction pairs, which is the physical basis for stable TENG output. Without the micro-gap support layer, the friction pairs may experience continuous contact or complete separation, leading to random fluctuations in charge separation efficiency. The performance degradation of Comparative Example 6 was relatively mild, similar to Comparative Example 3, confirming the beneficial but not essential technical positioning of the micro-gap support layer. However, from the perspective of product consistency and long-term reliability, the introduction of the micro-gap support layer significantly improves the engineering stability of the system.

[0156] 7. The Influence of Process Parameters on System Performance Experiments optimizing the dielectric layer thickness revealed its bidirectional impact on system performance. Example 2 uses a 3nm dielectric layer to represent the lower limit of thickness, with an insulation resistance of 1.2 × 10⁻⁶. 8 Ω·cm 2 It just satisfies the condition of being greater than or equal to 10. 8 Ω·cm 2 The system standard is met, but the safety margin is relatively small, the agglomerate particle size is 145nm, and the retention rate after 500 cycles is 84.5%, which is slightly lower than that of Example 1. Example 3 uses an 8nm dielectric layer to represent the upper limit of thickness, and the insulation resistance is increased to 4.8×10. 8 Ω·cm 2 While safety is further enhanced, the TENG output voltage drops to 2.5V, indicating that the thicker dielectric layer weakens the electric field coupling efficiency. The Gurley value change rate rises to 12.5%, approaching the upper limit of 15%, suggesting that the thicker dielectric layer hinders ion transport to some extent. In summary, a dielectric layer thickness of 5nm~6nm achieves a good balance between electrical isolation reliability and electric field coupling efficiency.

[0157] Parameter optimization experiments on nanoparticle concentration showed that the system could work effectively within the range of 0.3wt% to 0.8wt%, but an optimal range existed. Example 4 used a low concentration of 0.3wt%, with an aggregate particle size of 135nm and a retention rate of 86.0% after 500 cycles, indicating good dispersion, but the interfacial enhancement effect was slightly weakened due to the limited number of particles. Example 5 used a high concentration of 0.8wt%, increasing the aggregate particle size to 168nm and the settling time to over 138 hours, indicating that the high concentration increased interparticle interactions, placing higher demands on the dispersion system; the retention rate after 500 cycles was 83.8%, slightly lower than in Example 1. The medium concentration range of 0.5wt% to 0.6wt% achieved a good balance between dispersion difficulty and interfacial enhancement effect.

[0158] Experiments optimizing the electric field strength parameters confirmed the positive regulatory effect of the electric field on the dispersion effect. Example 6 used a weak electric field of 0.5 V / cm, resulting in slow particle migration, an aggregated particle size of 142 nm, and a retention rate of 85.2% after 500 cycles, which was acceptable but not optimal. Example 7 used a strong electric field of 3.0 V / cm, reducing the aggregated particle size to 118 nm and increasing the retention rate after 500 cycles to 86.5%, indicating that strengthening the electric field can further improve the dispersion effect. However, excessively strong electric fields may increase energy consumption and potential electrochemical interference risks; a moderate electric field strength of 1.0 V / cm to 1.5 V / cm balances dispersion effect and system safety.

[0159] The vibration frequency parameter optimization experiment verified the differences in dispersion mechanisms at different frequencies. Example 8 used a 5Hz low-frequency vibration, where the electrophoretic effect was dominant, and the particles exhibited strong directional migration characteristics, with an aggregated particle size of 138nm and a retention rate of 85.5% after 500 cycles. Example 9 used a 50Hz high-frequency vibration, which enhanced the dielectrophoretic effect and made local perturbations more obvious, with an aggregated particle size of 132nm and a retention rate of 85.8% after 500 cycles. The system can work effectively at both frequencies, confirming the good adaptability of this application to a wide frequency band of 1Hz~50Hz vibration, which is highly consistent with the vibration spectrum of the actual battery usage environment.

[0160] 8. Multi-parameter collaborative optimization Example 10 achieved the best overall performance among all samples by comprehensively optimizing the dielectric layer thickness (6nm), particle concentration (0.6wt%), electric field strength (1.5V / cm), vibration frequency (20Hz), and RC network parameters (R=30MΩ, C=8nF). The aggregate particle size D50 was only 108nm, the lowest among all examples, a further reduction of 14% compared to Example 1. The settling time exceeded 192h, more than 14% longer than Example 1. The capacity retention rate after 500 cycles reached 88.5%, an improvement of 1.3 percentage points compared to Example 1. The capacity retention rate of 85.0% after 200 cycles at 45℃ was also at the optimal level. The excellent performance of Example 10 demonstrates that there is room for synergistic optimization among the various technical parameters of this application. By jointly adjusting multiple parameters based on single-factor optimization, the system potential can be further explored, providing a clear optimization direction for formulation design in industrial applications.

[0161] 9. Verification of the universality of the material system Experimental results from the material selection verification group demonstrated the good compatibility of the proposed technology platform with different material systems. Example 11 used an FEP / PI friction pair instead of PTFE / PVDF. The TENG output voltage of 2.8V was slightly lower than the 3.2V of Example 1, but the agglomerate particle size of 138nm and the 84.8% retention rate after 500 cycles remained at a good level, proving that the alternative friction material combination can meet the system's functional requirements. Example 12 used an alumina / aluminum fluoride composite double-layer dielectric encapsulation, increasing the insulation resistance to 5.2 × 10⁻⁶. 8 Ω·cm 2 DC leakage was reduced to 3.5 × 10⁻⁶. -9 A / cm 2 Compared to Example 1, the safety indicators are further improved, with a 500-cycle retention rate of 86.8%, verifying the effectiveness of the anti-pinhole reinforcement scheme. Example 13 uses lithium nitride nanoparticles instead of LLZTO. After sulfonation modification, the zeta potential reaches -30mV, the aggregate particle size reaches 142nm, and the 500-cycle retention rate is 85.2%, proving the versatility of the technical solution of this application for different types of functional nanoparticles. Example 14 uses a polyimide membrane instead of a PP / PE membrane, which is compatible with higher temperature atomic layer deposition processes. Simultaneously, the Gurley value change rate is only 7.5%, which is better than the PP / PE matrix, and the 500-cycle retention rate is 86.2%, providing a material selection basis for high-temperature process routes.

[0162] 10. Application System Expansion and Verification The experimental results from the application expansion verification group demonstrate the application potential of this application in different battery systems. Example 15, using a complete TENG-separator system in a silicon-carbon anode / NCM811 system, showed a capacity retention of 84.8% after 500 cycles, indicating that the ionic conductive network formed by LLZTO particles on the silicon anode surface helps alleviate interface problems caused by volume expansion. Example 16, using polar nano-additives to adsorb polysulfides in a lithium-sulfur battery system, showed a capacity retention of 82.0% after 500 cycles, verifying the application value of this application in suppressing the shuttle effect. Example 17, conducting a 1000-cycle ultra-long cycle test, showed that the capacity retention at 500 cycles was consistent with the aforementioned short-term test results, indicating that the TENG system maintains stable distributed driving capability during long-term operation, without showing signs of performance degradation or structural failure, proving the feasibility of the self-powered continuous driving technology concept throughout the battery's entire life cycle.

[0163] Based on all test data, the battery electrolyte self-dispersion and interface enhancement system based on triboelectric nanogenerators presented in this application exhibits significant technical effects. Comparative experiments clearly demonstrate the necessity and contribution of each technological innovation. The TENG active dispersion mechanism, dielectric encapsulation layer, surface functionalization, alternating electric field, and coupling electrode form a complete technical loop, jointly supporting the technical effect chain of self-powering, electric field-driven, continuous dispersion, and interface enhancement.

[0164] Table 1

[0165] Table 2

[0166] Table 3

[0167] Table 4

[0168] Table 5

[0169] Table 6

[0170] The following are specific embodiments illustrating this application. The embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments used, unless otherwise specified, are all conventional products that can be obtained commercially.

[0171] Those skilled in the art will understand that the above embodiments are specific examples of implementing this application, and in practical applications, various changes in form and detail can be made without departing from the spirit and scope of this application. Any person skilled in the art can make various alterations and modifications without departing from the spirit and scope of this application; therefore, the scope of protection of this application should be determined by the scope defined in the claims.

Claims

1. A battery cell, characterized by, include: The housing and the cell assembly and electrolyte located within the housing; The battery cell assembly is formed by stacking or winding positive electrode plates, separators and negative electrode plates; The diaphragm comprises a substrate, a triboelectric nanofiber layer, a dielectric encapsulation layer, and a coupling electrode arranged sequentially. The electrolyte contains nanoparticles; The dielectric encapsulation layer completely covers the triboelectric nanofiber layer, so that the triboelectric nanofiber layer has no direct contact with the electrolyte; The surface of the nanoparticles is modified by carboxylation or sulfonic acidation, and the zeta potential in the electrolyte is ≤-25mV, with an electrophoretic mobility μ. e (0.5~5)×10 -8 m 2 V -1 s -1 .

2. The battery cell of claim 1, wherein, The matrix material includes at least one of polypropylene, polyethylene, polyimide, and polyetheretherketone.

3. The battery cell of claim 1, wherein, The triboelectric nanofiber layer comprises a combination of PTFE and PVDF fibers, or a combination of FEP and PI fibers.

4. The battery cell of claim 1, wherein, The material of the dielectric encapsulation layer comprises an Al2O3 thin film or SiN x thin film.

5. The battery cell of claim 1, wherein, The coupling electrodes are in the form of interdigitated fingers, mesh, or concentric rings.

6. The battery cell of claim 5, wherein, The material of the coupling electrode includes a corrosion-resistant conductive material.

7. The battery cell of claim 1, wherein, The nanoparticles have a particle size of 30nm to 80nm.

8. The battery cell of claim 7, wherein, The nanoparticles include functional inorganic nanoparticles.

9. The battery cell of any one of claims 1-8, wherein, The diaphragm further includes a microgap support layer and an RC network. The microgap support layer is disposed between the substrate and the triboelectric nanofiber layer, and the RC network is disposed on the coupling electrode.

10. The battery cell of claim 9, wherein, The RC network includes a current-limiting resistor and a coupling capacitor.

11. A method of producing a battery cell, characterized by, include: Provide a battery cell assembly, the battery cell assembly being formed by stacking or winding a positive electrode sheet, a separator and a negative electrode sheet; A housing is provided to house the battery cell assembly within the housing; Provide electrolyte and inject the electrolyte into the housing; Perform the formation step; The diaphragm comprises a substrate, a triboelectric nanofiber layer, a dielectric encapsulation layer, and a coupling electrode arranged sequentially, and the electrolyte contains nanoparticles; The dielectric encapsulation layer completely covers the triboelectric nanofiber layer, so that the triboelectric nanofiber layer has no direct contact with the electrolyte; The surface of the nanoparticles is modified by carboxylation or sulfonic acidation, and the zeta potential in the electrolyte is ≤-25mV, with an electrophoretic mobility μ. e (0.5~5)×10 -8 m 2 V -1 s -1 .

12. The method of claim 11, wherein the method further comprises: The method for generating the triboelectric nanofiber layer includes electrospinning or thin film stretching; the method for generating the dielectric encapsulation layer includes plasma-enhanced atomic layer deposition.

13. The method for preparing a battery cell according to claim 11, characterized in that, The diaphragm further includes a microgap support layer and an RC network. The microgap support layer is disposed between the substrate and the triboelectric nanofiber layer, and the RC network is disposed on the coupling electrode. The microgap support layer is generated by hot pressing or UV imprinting.

14. A battery device characterized by comprising: The battery device includes a battery cell prepared by the method of preparing a battery cell as described in any one of claims 1 to 10 or as described in any one of claims 11 to 13, and the battery device includes one or more of a battery module, a battery pack, and an energy storage battery.

15. An electrical device, comprising: The electrical device includes the battery device as described in claim 14, the battery device being used to provide electrical energy.

16. An energy storage device, characterized by The energy storage device includes the battery device as described in claim 14, the battery device being used to store electrical energy.

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