A hybrid conductor with continuous ion and electron transport channels, its preparation method and applications

Abstract

This invention discloses a hybrid conductor with continuous ion and electron transport channels, its preparation method, and its applications, belonging to the field of solid-state lithium metal battery technology. This invention uses a lithiophilic modified titanium nitride nanotube array and a solid electrolyte interface film to form a hybrid conductor with continuous ion and electron transport channels. This promotes uniform deposition and stripping of lithium within the nanotubes via a creep mechanism, effectively releasing stress and improving the battery's electrochemical performance. The titanium nitride nanotube array not only improves the overall conductivity of the electrode material but also adapts to the volume changes of the negative electrode during charge-discharge cycles. Furthermore, titanium nitride is stable for lithium, reducing side reactions during cycling.

Description

Technical Field

[0001] This invention belongs to the field of solid-state lithium metal battery technology, and particularly relates to a hybrid conductor with continuous ion and electron transport channels, its preparation method and application. Background Technology

[0002] With the development of electric vehicles and large-scale grid energy storage technologies, the demand for batteries with high energy density, long cycle life, and superior safety performance is increasing daily. However, traditional lithium-ion batteries suffer from serious safety issues, such as thermal runaway and flammability, and their energy density cannot meet the requirements of various advanced applications. Lithium metal anodes possess extremely high theoretical capacity (3860 mAh·g). -1 The theoretical capacity of traditional graphite anodes is 372 mAh·g. -1 Low electrochemical potential (-3.04 V, compared to the standard hydrogen electrode) and low density (0.53 g·cm³). -3 Solid electrolytes (SEs) possess excellent safety characteristics, and their high mechanical strength can suppress lithium dendrite growth, thereby improving battery cycle life and stability. Therefore, solid-state lithium metal batteries are considered one of the most promising energy storage devices and have attracted extensive research.

[0003] However, the practical application of solid-state lithium metal batteries is severely hampered by several key challenges, including the instability of the electrode-electrolyte interface, the accumulation of internal stress in lithium, and the growth of lithium dendrites. Specifically, during lithium deposition and stripping, significant volume changes occur, creating voids at the interface and triggering a sharp increase in polarization over time. Electrochemical reactions occurring during cycling generate enormous stress within the lithium metal (approximately 1 GPa of stress per 135 mV potential), which is then transferred to the electrolyte layer (SE). This immense stress can cause the SE to fracture and form channels for lithium dendrite penetration due to the "point effect," ultimately leading to a short circuit in the battery.

[0004] Faced with these challenges, researchers have made considerable efforts and achieved encouraging progress. One effective strategy is to create an artificial solid electrolyte interphase (SEI) film on the lithium metal anode. For example, porous organic polymers are integrated into polyethylene oxide (PEO)-based SEs to form lithium fluoride-rich SEIs, improving the uniformity of lithium deposition. Although such artificial SEI layers provide protection, they often fail under the large volume changes during lithium deposition and stripping processes. Another promising approach is to use three-dimensional electronic conductors as lithium metal hosts. This approach has several advantages: (1) the three-dimensional structure can buffer the volume changes during lithium plating or stripping, thereby enhancing the structural stability of the anode; (2) electronic conductors can accelerate electron transport and reduce battery polarization. For example, carbon cloth modified with MOF nanorod arrays is used as a lithium metal host, thereby reducing the local current density and enhancing the electrochemical deposition behavior of lithium. However, at high current densities, excessive operating current can cause lithium to deposit outside the framework, thus weakening its ability to control lithium deposition. Utilizing ionic conductors as lithium metal hosts is another effective strategy. When lithium ions are deposited within an ionic conductor, electron conduction is inhibited, causing lithium ions to deposit in a "bottom-up" manner. A typical example is using a three-dimensional garnet-type ionic conductor framework as a lithium metal host, guiding lithium deposition from the bottom and preventing dendrite formation. However, the insulation of the framework restricts electron transport, potentially leading to "dead lithium." Neither a single electron conductor nor a single ionic conductor can completely solve the challenges posed by solid-state lithium metal batteries. From a kinetic perspective, rapid transport of lithium ions and electrons is crucial to the performance of solid-state lithium metal batteries.

[0005] Therefore, it is necessary to provide a conductor material for solid-state lithium metal batteries that has a stable structure, good cycle performance, and excellent lithium-ion and electron transport properties. Summary of the Invention

[0006] To address the aforementioned technical problems, this invention proposes a hybrid conductor with continuous ion and electron transport channels, its preparation method, and its applications. The hybrid conductor with continuous ion and electron transport channels provided by this invention exhibits high lithiophilicity, excellent lithium-ion diffusion and electron transport capabilities, and can improve lithium metal deposition and stripping, thus possessing extremely high application value in the field of high-performance solid-state lithium metal batteries.

[0007] To achieve the above objectives, the present invention provides the following technical solution:

[0008] The present invention provides a hybrid conductor having continuous ion and electron transport channels, the hybrid conductor comprising a lithiophilic modified titanium nitride nanotube array and a solid electrolyte interface film deposited on the surface of the lithiophilic modified titanium nitride nanotube array.

[0009] Preferably, the diameter of the titanium nitride nanotubes in the lithiophilic modified titanium nitride nanotube array is 50-200 nm.

[0010] Preferably, the lithiophilic modified lithiophilic material includes one or more of the following: silver nanoparticles, gold nanoparticles, zinc nanoparticles, and silicon nanoparticles.

[0011] Preferably, the chemical composition of the solid electrolyte interface membrane includes one or more of lithium fluoride, lithium oxide, lithium carbonate, and lithium nitride.

[0012] Preferably, the solid electrolyte interface film is constructed by a pre-lithiation method; the pre-lithiation method includes electrochemical deposition or atomic layer deposition.

[0013] Preferably, the thickness of the solid electrolyte interface film is 5-50 nm.

[0014] Preferably, the method for preparing the titanium nitride nanotube array includes: annealing the titanium dioxide nanotube array in ammonia to obtain the titanium nitride nanotube array.

[0015] Preferably, the annealing temperature is 750-850℃, the annealing time is 0.5-5h, and the rate of heating to the annealing temperature is 1-5℃·min. -1 .

[0016] This invention provides a method for preparing the hybrid conductor with continuous ion and electron transport channels as described in the above technical solution, comprising the following steps:

[0017] (1) Lithophilic modification of titanium nitride nanotube arrays to obtain lithophilic modified titanium nitride nanotube arrays;

[0018] (2) A solid electrolyte interface film is constructed on the surface of the lithiophilic modified titanium nitride nanotube array obtained in step (1) to obtain the hybrid conductor with continuous ion and electron transport channels.

[0019] The present invention also provides the application of the hybrid conductor with continuous ion and electron transport channels described in the above technical solution in the preparation of battery electrode materials.

[0020] Compared with the prior art, the present invention has the following advantages and technical effects:

[0021] 1. This invention employs a lithium-loving modified titanium nitride nanotube array and a solid electrolyte interface film to form a hybrid conductor with continuous ion and electron transport channels. This can promote the uniform deposition and stripping of lithium within the nanotubes through a creep mechanism, which helps to improve the electrochemical stability of the electrode material. The titanium nitride nanotube array can not only improve the overall conductivity of the electrode material, but also adapt to the volume changes of the negative electrode during charge-discharge cycles. Furthermore, titanium nitride is stable for lithium, reducing side reactions during cycling.

[0022] 2. The solid electrolyte interphase (SEI) film with high lithiophilicity and high lithium-ion diffusion rate in the mixed conductor with continuous ion and electron transport channels provided by the present invention forms a continuous lithium-ion transport channel, which significantly improves the diffusion and transport capabilities of lithium ions; the titanium nitride nanotube array with excellent electronic conductivity and the SEI together form a continuous lithium-ion and electron transport channel, which is beneficial to the uniform deposition and stripping of lithium metal.

[0023] 3. When the hybrid conductor with continuous ion and electron transport channels provided by the present invention is applied to solid-state lithium metal electrode materials, the assembled solid-state lithium metal battery exhibits characteristics such as high specific capacity, good rate performance, and strong cycle stability, indicating that the hybrid conductor provided by the present invention has important application prospects in the field of high-performance solid-state lithium metal batteries.

[0024] 4. The method for preparing a hybrid conductor with continuous ion and electron transport channels provided by the present invention has the advantages of being simple, efficient, easy to operate, and low in cost, and is suitable for further promotion. Attached Figure Description

[0025] The accompanying drawings, which form part of this application, are used to provide a further understanding of this application. The illustrative embodiments and descriptions of this application are used to explain this application and do not constitute an undue limitation of this application. In the drawings:

[0026] Figure 1 SEM image of the titanium nitride nanotube array prepared in Example 1;

[0027] Figure 2 X-ray diffraction pattern of the titanium nitride nanotube array prepared in Example 1;

[0028] Figure 3 HRTEM image of the hybrid conductor with continuous ion and electron transport channels prepared in Example 1;

[0029] Figure 4 Mapping diagram of the hybrid conductor with continuous ion and electron transport channels prepared in Example 1;

[0030] Figure 5 The graph shows the electrochemical performance of the solid-state lithium metal full cell in Application Example 1.

[0031] Figure 6 The graph shows the electrochemical performance of the solid lithium metal half-cells in Application Example 2 and Comparative Application Examples 1-3. Detailed Implementation

[0032] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0033] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.

[0034] This invention provides a hybrid conductor with continuous ion and electron transport channels, the hybrid conductor comprising a lithiophilic modified titanium nitride nanotube array and a solid electrolyte interface film deposited on the surface of the lithiophilic modified titanium nitride nanotube array.

[0035] This invention employs a lithium-loving modified titanium nitride nanotube array and a solid electrolyte interface film to form a hybrid conductor with continuous ion and electron transport channels. This promotes the uniform deposition and stripping of lithium within the nanotubes via a creep mechanism, which helps improve the electrochemical stability of the electrode material. The titanium nitride nanotube array not only improves the overall conductivity of the electrode material but also adapts to the volume changes of the negative electrode during charge-discharge cycles. Furthermore, titanium nitride is stable for lithium, reducing side reactions during cycling.

[0036] In a preferred embodiment, the diameter of the titanium nitride nanotubes in the lithiophilic modified titanium nitride nanotube array is 50-200 nm, more preferably 100-200 nm. This invention uses titanium nitride nanotube arrays with diameters within the above range. Lithium metal diffusion in the nanotubes primarily utilizes Coble creep, which effectively releases stress and promotes uniform lithium deposition. Excessively large diameter titanium nitride nanotubes will result in significant dislocation creep, a hybrid diffusion-displacement mechanism, leading to stress accumulation and jeopardizing battery safety performance.

[0037] In a preferred embodiment, the lithiophilic modified material includes one or more of silver nanoparticles, gold nanoparticles, zinc nanoparticles, and silicon nanoparticles. This invention improves the lithiophilicity of titanium nitride nanotube arrays by modifying them with lithiophilic agents, thereby promoting uniform lithium deposition and slowing down lithium dendrite growth.

[0038] In a preferred embodiment, the method for preparing the titanium nitride nanotube array includes: annealing the titanium dioxide nanotube array in ammonia to obtain the titanium nitride nanotube array.

[0039] In a preferred embodiment, the titanium dioxide nanotube array is prepared by a template method, a hydrothermal method, or anodizing, more preferably by anodizing. The titanium dioxide nanotube array obtained by anodizing has a more uniform size, which is beneficial to improving its electrochemical stability.

[0040] In a preferred embodiment, the annealing temperature is 750-850℃, the annealing time is 0.5-5h, and the rate of heating to the annealing temperature is 1-5℃·min. -1 The annealing process described above is beneficial for obtaining a titanium nitride nanotube array that is stable to lithium metal.

[0041] In a preferred embodiment, the solid electrolyte interface membrane has a chemical composition comprising one or more of lithium fluoride, lithium oxide, lithium carbonate, and lithium nitride. The solid electrolyte interface membrane of this invention exhibits high lithiophilicity and a high lithium-ion diffusion rate, improving lithium metal deposition and stripping.

[0042] In a preferred embodiment, the solid electrolyte interface film is constructed using a pre-lithiation method; the pre-lithiation method includes electrochemical deposition or atomic layer deposition; the electrolyte used in the electrochemical deposition method is prepared from an organic solvent, a lithium salt, and additives, wherein the concentration of the lithium salt in the electrolyte is 0.8-1.5 mol / L, and the mass concentration of the additives is 2%; the organic solvent includes one or more of ethylene carbonate (EC), propylene carbonate (PC), diethyl carbonate (DEC), dimethyl ether (DME), and 1,3-dioxolane (DOL); the lithium salt includes one or more of lithium bis(trifluoromethanesulfonylimide) (LiTFSI), lithium perchlorate (LiClO4), and lithium hexafluorophosphate (LiPF6); the additives include one or more of lithium nitrate (LiNO3), triphenyl phosphate (TPP), and dimethyl methylphosphonate (DMMP).

[0043] In a preferred embodiment, the thickness of the solid electrolyte interface film is 5-50 nm. This invention controls the thickness of the solid electrolyte interface film within this range, offering the advantages of continuous and rapid lithium-ion transport. An excessively thin solid electrolyte interface film cannot guarantee its mechanical stability and lithium-ion transport capability, while an excessively thick film increases the internal resistance of the battery and reduces its charge / discharge efficiency.

[0044] This invention provides a method for preparing the hybrid conductor with continuous ion and electron transport channels as described in the above technical solution, comprising the following steps:

[0045] (1) Lithophilic modification of titanium nitride nanotube arrays to obtain lithophilic modified titanium nitride nanotube arrays;

[0046] (2) A solid electrolyte interface film is constructed on the surface of the lithiophilic modified titanium nitride nanotube array obtained in step (1) to obtain the hybrid conductor with continuous ion and electron transport channels.

[0047] In a preferred embodiment, in step (1), the lithiophilic modification specifically involves: using a titanium nitride nanotube array as the cathode, a titanium sheet as the anode, and a lithiophilic material precursor solution as the electrolyte, performing electrolysis to obtain a pretreated titanium nitride nanotube array; and calcining the pretreated titanium nitride nanotube array to obtain a lithiophilically modified titanium nitride nanotube array.

[0048] In a preferred embodiment, the solvent of the lithiophilic material precursor solution is water and ethylene glycol; the ratio of the lithiophilic material precursor, water and ethylene glycol in the lithiophilic material precursor solution is (2.0-3.6) g: 10 mL: 240 mL; the lithiophilic material precursor includes silver nitrate, gold chloride or zinc sulfate.

[0049] In a preferred embodiment, the electrolysis current is a constant current of 15mA, the electrolysis time is 1min, and the electrolysis is performed twice.

[0050] In a preferred embodiment, the calcination temperature is 400°C, the calcination time is 3 hours, and the rate of heating to the calcination temperature is 2°C·min. -1 The calcination atmosphere is a nitrogen atmosphere.

[0051] In a preferred embodiment, in step (2), the process parameters for constructing the solid electrolyte interface membrane include: room temperature, voltage of 0-1V, and current density of 0.01-2mA·cm⁻¹. -1 .

[0052] The present invention also provides the application of the hybrid conductor with continuous ion and electron transport channels described in the above technical solution in the preparation of battery electrode materials.

[0053] In this embodiment of the invention, room temperature refers to "25±2℃".

[0054] Unless otherwise specified, all raw materials used in the embodiments of this invention were purchased through commercial channels.

[0055] Example 1

[0056] A hybrid conductor with continuous ion and electron transport channels is composed of an array of titanium nitride nanotubes modified with silver nanoparticles and a solid electrolyte interface film deposited on the surface of the array of titanium nitride nanotubes modified with silver nanoparticles. The diameter of the titanium nitride nanotubes in the array of titanium nitride nanotubes modified with silver nanoparticles is 100 nm. The chemical composition of the solid electrolyte interface film includes lithium fluoride, lithium oxide, lithium carbonate and lithium nitride. The thickness of the solid electrolyte interface film is 5-50 nm.

[0057] The preparation process is as follows:

[0058] (1) Add 2.75g of ammonium fluoride to 15mL of deionized water and stir until homogeneous to obtain solution A; add solution A to 500mL of ethylene glycol and stir until homogeneous to obtain solution B;

[0059] (2) Using a rectangular titanium sheet of 1×7cm as the anode and cathode, and the solution B obtained in step (1) as the electrolyte, electrolyze for 2 hours at a constant voltage of 60V to form a titanium dioxide nanotube array at the anode.

[0060] (3) The titanium dioxide nanotube array obtained in step (2) is placed in a tube furnace and heated at 5 °C·min under an ammonia atmosphere. -1 The temperature was increased to 750℃ at a certain rate and annealed for 1 hour to obtain a titanium nitride nanotube array.

[0061] (4) Dissolve 2.1g of silver nitrate in 10mL of deionized water, then add 240mL of ethylene glycol and stir until homogeneous to obtain solution C; using the titanium nitride nanotube array obtained in step (3) as the cathode, the titanium sheet as the anode, and solution C as the electrolyte, electrolyze at a constant current of 15mA for 1min, then clean the titanium nitride nanotube array with anhydrous ethanol, repeat the above electrolysis process once to obtain a pretreated titanium nitride nanotube array; place the above pretreated titanium nitride nanotube array in a tube furnace, and heat it at 2℃·min under a nitrogen atmosphere. -1 The temperature was increased at a rate of 400℃ and held at 400℃ for 3 hours to obtain a titanium nitride nanotube array modified with silver nanoparticles.

[0062] (5) Using the titanium nitride nanotube array modified with silver nanoparticles obtained in step (4) as the working electrode and lithium metal as the counter electrode, electrochemical deposition was performed in an electrolyte prepared with DOL, DME, LiTFSI and LiNO3 (the concentration of LiTFSI in the electrolyte was 1.0 mol / L, the mass concentration of LiNO3 was 2.0%, and the volume ratio of DOL and DME was 1:1) to obtain a mixed conductor with continuous ion and electron transport channels; the process parameters for electrochemical deposition were: temperature 25℃, voltage 0-1V, current density 0.1mA·cm -1 .

[0063] Figure 1This is a SEM image of the titanium nitride nanotube array prepared in Example 1. Figure 1 As can be seen, in the titanium nitride nanotube array prepared in Example 1, the titanium nitride nanotubes are arranged vertically and have a diameter of about 100 nm.

[0064] Figure 2 The image shows the X-ray diffraction pattern of the titanium nitride nanotube array prepared in Example 1. Figure 2 It can be seen that the chemical composition of the obtained titanium nitride nanotube array is pure titanium nitride.

[0065] Figure 3 HRTEM image of the hybrid conductor with continuous ion and electron transport channels prepared in Example 1. Figure 3 It can be seen that an SEI layer is deposited on the surface of titanium nitride nanotubes.

[0066] Figure 4 Mapping image of the hybrid conductor with continuous ion and electron transport channels prepared in Example 1. From Figure 4 As can be seen, C, N, O, F and Ag elements are uniformly distributed on the surface of titanium nitride nanotubes.

[0067] Example 2

[0068] A hybrid conductor with continuous ion and electron transport channels is composed of a titanium nitride nanotube array modified with gold nanoparticles and a solid electrolyte interface film deposited on the surface of the titanium nitride nanotube array modified with gold nanoparticles; the diameter of the titanium nitride nanotubes in the titanium nitride nanotube array modified with gold nanoparticles is 100 nm, the chemical composition of the solid electrolyte interface film includes lithium fluoride, lithium oxide, lithium carbonate and lithium nitride, and the thickness of the solid electrolyte interface film is 5-50 nm.

[0069] The preparation process is as follows:

[0070] (1) Add 2.5g of ammonium fluoride to 15mL of deionized water and stir until homogeneous to obtain solution A; add solution A to 500mL of ethylene glycol and stir until homogeneous to obtain solution B;

[0071] (2) Using a rectangular titanium sheet of 1×7cm as the anode and cathode, and the solution B obtained in step (1) as the electrolyte, electrolyze for 2 hours at a constant voltage of 60V to form a titanium dioxide nanotube array at the anode.

[0072] (3) The titanium dioxide nanotube array obtained in step (2) is placed in a tube furnace and heated at 5 °C·min under an ammonia atmosphere. -1 The temperature was increased to 750℃ at a certain rate and annealed for 1 hour to obtain a titanium nitride nanotube array.

[0073] (4) Dissolve 3.6g of gold chloride in 10mL of deionized water, then add 240mL of ethylene glycol and stir until homogeneous to obtain solution C; using the titanium nitride nanotube array obtained in step (3) as the cathode, the titanium sheet as the anode, and solution C as the electrolyte, electrolyze at a constant current of 15mA for 1min, then clean the titanium nitride nanotube array with anhydrous ethanol, repeat the above electrolysis process once to obtain a pretreated titanium nitride nanotube array; place the above pretreated titanium nitride nanotube array in a tube furnace, and heat it at 2℃·min under a nitrogen atmosphere. -1 The temperature was increased at a rate of 400℃ and held at 400℃ for 3 hours to obtain a titanium nitride nanotube array modified with gold nanoparticles.

[0074] (5) Using the titanium nitride nanotube array modified with gold nanoparticles obtained in step (4) as the working electrode and lithium metal as the counter electrode, electrochemical deposition was performed in an electrolyte prepared with DOL, DME, LiTFSI and LiNO3 (the concentration of LiTFSI in the electrolyte was 1.5 mol / L, the mass concentration of LiNO3 was 2.0%, and the volume ratio of DOL and DME was 1:1) to obtain a mixed conductor with continuous ion and electron transport channels; the process parameters for electrochemical deposition were: temperature 25℃, voltage 0-1V, current density 0.2mA·cm -1 .

[0075] Example 3

[0076] A hybrid conductor with continuous ion and electron transport channels is composed of an array of titanium nitride nanotubes modified with zinc nanoparticles and a solid electrolyte interface film deposited on the surface of the array of titanium nitride nanotubes modified with zinc nanoparticles. The diameter of the titanium nitride nanotubes in the array of titanium nitride nanotubes modified with zinc nanoparticles is 100 nm. The chemical composition of the solid electrolyte interface film includes lithium fluoride, lithium oxide, lithium carbonate and lithium nitride. The thickness of the solid electrolyte interface film is 5-50 nm.

[0077] The preparation process is as follows:

[0078] (1) Add 2.8g of ammonium fluoride to 15mL of deionized water and stir until homogeneous to obtain solution A; add solution A to 500mL of ethylene glycol and stir until homogeneous to obtain solution B;

[0079] (2) Using a rectangular titanium sheet of 1.5×7cm as the anode and cathode, and using solution B obtained in step (1) as the electrolyte, electrolyze for 2 hours at a constant voltage of 60V to form a titanium dioxide nanotube array at the anode.

[0080] (3) The titanium dioxide nanotube array obtained in step (2) is placed in a tube furnace and heated at 3°C·min under an ammonia atmosphere. -1 The temperature was increased to 750℃ at a certain rate and annealed for 1 hour to obtain a titanium nitride nanotube array.

[0081] (4) Dissolve 2g of zinc sulfate in 10mL of deionized water, then add 240mL of ethylene glycol and stir until homogeneous to obtain solution C; using the titanium nitride nanotube array obtained in step (3) as the cathode, the titanium sheet as the anode, and solution C as the electrolyte, electrolyze at a constant current of 15mA for 1min, then clean the titanium nitride nanotube array with anhydrous ethanol, repeat the above electrolysis process once to obtain a pretreated titanium nitride nanotube array; place the above pretreated titanium nitride nanotube array in a tube furnace, and heat it at 2℃·min under a nitrogen atmosphere. -1 The temperature was increased at a rate of 400℃ and held at 400℃ for 3 hours to obtain a titanium nitride nanotube array modified with zinc nanoparticles.

[0082] (5) Using the titanium nitride nanotube array modified with zinc nanoparticles obtained in step (4) as the working electrode and lithium metal as the counter electrode, electrochemical deposition was performed in an electrolyte prepared with DOL, DME, LiTFSI and LiNO3 (the concentration of LiTFSI in the electrolyte was 0.8 mol / L, the mass concentration of LiNO3 was 2.0%, and the volume ratio of DOL and DME was 1:1) to obtain a mixed conductor with continuous ion and electron transport channels; the process parameters for electrochemical deposition were: temperature 25℃, voltage 0-1V, current density 0.3mA·cm -1 .

[0083] Comparative Example 1

[0084] The only difference from Example 1 is that steps (4) and (5) are omitted.

[0085] Comparative Example 2

[0086] The only difference from Example 1 is that step (5) is omitted.

[0087] Comparative Example 3

[0088] The only difference from Example 1 is that step (4) is omitted.

[0089] Application Example 1

[0090] A solid-state lithium metal full battery consists of a working electrode, a counter electrode, and a solid electrolyte; the working electrode is a hybrid conductor with continuous ion and electron transport channels as described in Example 1.

[0091] The preparation method of solid-state lithium metal full cells includes the following steps:

[0092] (1) Lithium iron phosphate powder, super P, polyethylene oxide PEO, and lithium bis(trifluoromethanesulfonyl)imide LiTFSI were mixed in acetonitrile at a weight ratio of 6:1:2:1 to obtain lithium iron phosphate slurry. The obtained lithium iron phosphate slurry was then coated on carbon-coated aluminum foil and vacuum dried at 70°C for 12 h to obtain lithium iron phosphate cathode material.

[0093] (2) 686 mg of polyethylene oxide (PEO, Mw≈600000, purchased from Sigma), 343 mg of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and 36 mg of lithium titanium aluminum phosphate (LATP) were added to 15 mL of anhydrous acetonitrile and stirred for 12 h. The resulting solution was then poured into a mold and a Celgard diaphragm was added. The solution was dried at 60 °C for 24 h to obtain a polymer composite electrolyte. All of the above processes were carried out in a glove box filled with Ar, with O2 and H2O below 0.1 ppm.

[0094] (3) Using the mixed conductor with continuous ion and electron transport channels in Example 1 as the working electrode, the lithium iron phosphate cathode material obtained in step (1) as the counter electrode, and the polymer composite electrolyte obtained in step (2) as the solid electrolyte, a full cell is assembled.

[0095] The electrochemical performance of Application Example 1 was tested at 60°C, and the results are shown in [Figure Number]. Figure 5 . Figure 5 The graph shows the electrochemical performance of the solid-state lithium metal full cell in Application Example 1. (From...) Figure 5 It can be seen that when the hybrid conductor with continuous ion and electron transport channels in Example 1 is used as the negative electrode and lithium iron phosphate is used as the positive electrode to assemble a full battery, it can stably cycle 300 times and the capacity decay rate is 0.2% when the charge and discharge performance is tested at 1C rate.

[0096] Application Example 2 and Comparative Examples 1-3

[0097] A solid lithium metal half-cell consists of a working electrode, a counter electrode, and a solid electrolyte; the working electrode is a hybrid conductor as described in Example 1 or Comparative Examples 1-3.

[0098] The preparation method of solid-state lithium metal half-cells includes the following steps:

[0099] (1) 686 mg of polyethylene oxide (PEO, Mw≈600000, purchased from Sigma), 343 mg of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and 36 mg of lithium titanium aluminum phosphate (LATP) were added to 15 mL of anhydrous acetonitrile and stirred for 12 h. The resulting solution was then poured into a mold and a Celgard diaphragm was added. The solution was dried at 60 °C for 24 h to obtain a polymer composite electrolyte. All of the above processes were carried out in a glove box filled with Ar, with O2 and H2O below 0.1 ppm.

[0100] (2) Using the mixed conductor in Example 1 or Comparative Examples 1-3 as the working electrode, the lithium metal sheet as the counter electrode, and the polymer composite electrolyte obtained in step (1) as the solid electrolyte, a half cell is assembled.

[0101] The electrochemical performance of Application Example 2 and Comparative Examples 1-3 was tested at 60°C, and the results are shown in [Figure number missing]. Figure 6 . Figure 6 The graphs show the electrochemical performance of the solid-state lithium metal half-cells used in Application Example 2 and Comparative Application Examples 1-3. (Source: [Insert Source Here]) Figure 6 It can be seen that at 0.2 mA·cm -1 0.2mAh·cm -1 Under the cycling conditions, the half-cell made of the composite material in Example 1 has a cycle performance of 450h, the half-cell made of the composite material in Comparative Example 1 has a cycle performance of 100h, the half-cell made of the composite material in Comparative Example 2 has a cycle performance of 185h, and the half-cell made of the composite material in Comparative Example 3 has a cycle performance of 210h.

[0102] The above are merely preferred embodiments of this application, but the scope of protection of this application is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this application should be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.

Claims

1. A hybrid conductor having continuous ion and electron transport channels, characterized in that, The hybrid conductor comprises a lithiophilic modified titanium nitride nanotube array and a solid electrolyte interface film deposited on the surface of the lithiophilic modified titanium nitride nanotube array. The lithiophilic modified material is one or more of the following: silver nanoparticles, zinc nanoparticles, and silicon nanoparticles. The solid electrolyte interface membrane has a chemical composition of one or more of lithium fluoride, lithium oxide, lithium carbonate, and lithium nitride; the solid electrolyte interface membrane is constructed by a pre-lithiation method; the pre-lithiation method is electrochemical deposition or atomic layer deposition.

2. The hybrid conductor with continuous ion and electron transport channels according to claim 1, characterized in that, The diameter of the titanium nitride nanotubes in the lithiophilic modified titanium nitride nanotube array is 50-200 nm.

3. The hybrid conductor with continuous ion and electron transport channels according to claim 1, characterized in that, The thickness of the solid electrolyte interface film is 5-50 nm.

4. The hybrid conductor with continuous ion and electron transport channels according to claim 1, characterized in that, The method for preparing the titanium nitride nanotube array includes: annealing the titanium dioxide nanotube array in ammonia to obtain the titanium nitride nanotube array.

5. The hybrid conductor with continuous ion and electron transport channels according to claim 4, characterized in that, The annealing temperature is 750-850℃, the annealing time is 0.5-5 hours, and the heating rate to the annealing temperature is 1-5℃·min. -1 .

6. The method for preparing the hybrid conductor having continuous ion and electron transport channels as described in any one of claims 1-5, characterized in that, Includes the following steps: (1) Lithophilic modification of titanium nitride nanotube arrays to obtain lithophilic modified titanium nitride nanotube arrays; (2) A solid electrolyte interface film is constructed on the surface of the lithiophilic modified titanium nitride nanotube array obtained in step (1) to obtain the hybrid conductor with continuous ion and electron transport channels.

7. The use of the hybrid conductor with continuous ion and electron transport channels as described in any one of claims 1-5 in the preparation of battery electrode materials.

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