A high-conductivity nickel-based (copper) oxide composite material in the shape of a candied fruit on a stick, and preparation and application thereof

Abstract

This invention discloses a candied hawthorn-like highly conductive nickel-based (copper) oxide composite material, its preparation, and its application. A highly conductive linear material forms a candied hawthorn-like conductive network, uniformly interwoven on a hollow spherical nickel-based (copper) oxide matrix stacked with nanosheets. The nickel-based (copper) oxide is prepared by solvothermal reaction followed by high-temperature heat treatment, and then produced through a polyelectrolyte modification-ultrasonic-assisted stirring process. In this method, after charge modification, carriers carrying different charges and linear conductive agents automatically assemble based on charge affinity, resulting in the candied hawthorn-like highly conductive nickel-based (copper) oxide composite material. The composite material has advantages such as low cost, relatively simple process, batch stability, high conductivity, good thermal stability, and applicability to various battery systems.

Description

Technical Field

[0001] This invention belongs to the field of inorganic materials science and technology, specifically relating to a highly conductive nickel-based (copper) oxide composite material in the shape of candied hawthorn skewers and its preparation and application. Background Technology

[0002] With the transformation of the global energy structure and the rapid development of new energy technologies, high-performance, long-life, and highly safe electrochemical energy storage devices have become one of the key technologies driving the application of green energy. Among these electrochemical energy storage devices, the selection and optimization of electrode materials are one of the core factors determining their performance. Different types of battery electrochemical systems have different requirements for electrode materials. Developing electrode materials applicable to multiple battery systems requires comprehensive consideration of the specific requirements of different battery systems to achieve performance optimization and balance. For example, lithium-ion batteries require electrode materials with high energy density and long cycle life; thermal batteries require electrode materials with good high-temperature stability; and supercapacitors require electrode materials with high specific capacitance and fast charge / discharge capabilities. Currently, the preparation processes of major electrode materials often suffer from high energy consumption, high cost, environmental pollution, and narrow application systems, which are detrimental to environmental protection and sustainable development. Therefore, researching and developing low-cost, highly stable, relatively simple-process electrode materials applicable to multiple battery systems has extremely important scientific significance and practical value.

[0003] Currently, nickel-based (copper) oxides, as an important class of inorganic functional materials, have attracted much attention due to their abundant resources, good theoretical capacity, high environmental friendliness, and thermal stability. However, traditional nickel-based (copper) oxide materials face problems such as poor conductivity and limited electrochemical activity in practical applications, which seriously restricts their further application in high-performance electrochemical energy storage devices. In the current research, Zhang et al. (Zhang Y, Li Z, Gong L, et al. JEnergy Chem, 2023, 77: 561-571.) improved the conductivity of the material by introducing metallic Ag particles through in-situ reduction of AgCl. However, the material did not form a continuous electron transport channel, resulting in poor improvement in long-distance conductivity along the electrode thickness direction. At the same time, the reduction process is difficult to quantitatively control, and the addition of reducing agent easily introduces impurities. Xu et al. (Xu C, Jin C, Liu J, et al. J Energy Storage, 2021, 36:102394.) introduced carbon materials through mechanical grinding and mixing. However, on the one hand, the large specific surface area and aspect ratio of the carbon materials during the mixing process caused strong adsorption, agglomeration, and bridging effects. The entanglement and swirling of the carbon materials resulted in poor composite uniformity and bonding force on the surface of nickel-based (copper) oxides. On the other hand, the large differences in relative particle size and relative mass between carbon materials and nickel-based (copper) oxides made the mechanical grinding and mixing process prone to occupational health hazards such as dust, posing safety risks. Summary of the Invention

[0004] This invention addresses the problems of high energy consumption, high cost, environmental pollution, and limited application systems in the preparation processes of current main electrode materials. It provides a candied hawthorn-shaped, highly conductive nickel-based (copper) oxide composite material and its preparation and application. This invention optimizes the conductivity and structural stability of nickel-based (copper) oxides by uniformly interlacing a candied hawthorn-shaped conductive network composed of highly conductive linear materials onto a matrix. The specific surface area of ​​the composite material is increased through a hollow spherical structure design using stacked nanosheets, thereby increasing the number of reactive sites and improving electrochemical reaction and catalytic efficiency. Furthermore, multidimensional ion and electron transport channels are constructed by bridging nanosheets with highly conductive linear materials, reducing ion and electron transport barriers. This candied hawthorn-shaped, highly conductive nickel-based (copper) oxide composite material possesses advantages such as high conductivity, good thermal stability, high electrochemical reactivity, low synthesis energy consumption, low pollution, and applicability to various energy systems.

[0005] Specifically, in terms of the preparation process, this invention prepares nickel-based (copper) oxides through a solvothermal reaction followed by high-temperature heat treatment. The material is synthesized under high temperature and pressure using a gas as a template, and then nickel-based (copper) oxides are generated by the decomposition of nickel-based (copper) hydroxide through high-temperature heat treatment, exhibiting a unique nanosheet-stacking hollow spherical microstructure. Secondly, the excellent specific surface area increases the number of reactive sites, effectively reducing battery internal resistance and optimizing reaction conditions to improve the utilization rate of the catalytic material. Furthermore, the excellent specific surface area and unique nanopores increase the contact area with the electrolyte or electrolyte solution, providing additional ion transport channels, improving ion diffusion reaction kinetics, and shortening the lithium-ion transport and diffusion distance. Simultaneously, the unique three-dimensional hollow structure generally exhibits excellent lithium storage performance, enabling high lithium storage capacity and cycle stability as a lithium battery anode material. This invention prepares a candied hawthorn-shaped, highly conductive nickel-based (copper) oxide composite material through polyelectrolyte modification and ultrasonic-assisted stirring. Carriers and linear conductive agents with different electrical properties automatically assemble based on charge affinity, achieving uniform and compact loading and avoiding entanglement, agglomeration, and dust hazards caused by conventional mechanical mixing. Secondly, a highly conductive, high aspect ratio linear conductive agent is uniformly attached to the surface of the hollow spherical nickel-based (copper) oxide, forming a good electron transport channel and reducing electron transport barriers. Furthermore, the high aspect ratio linear conductive material can limit the volume expansion of the electrode material during cycling, improving the material's cycling stability. Simultaneously, the high aspect ratio linear conductive material can improve the structural stability and formability of powder-pressed electrodes for thermal batteries or high-temperature lithium batteries, playing a good role in powder fixation and bridging.

[0006] Specifically, the objective of this invention is achieved through the following technical solutions:

[0007] This invention provides a highly conductive nickel-based (copper) oxide composite material resembling a candied hawthorn stalk. The highly conductive nickel-based (copper) oxide comprises a candied hawthorn stalk structure composed of a nickel-based (copper) oxide carrier and a high aspect ratio linear conductive agent. The nickel-based (copper) oxide carrier is a hollow spherical structure formed by stacked nanosheets, and the highly conductive linear material forms a candied hawthorn-like conductive network, uniformly and interwoven on the surface of the nanosheet-stacked hollow spherical nickel-based (copper) oxide matrix. In this invention, the nickel-based (copper) oxide is the main active ingredient, participating in the electrochemical reaction. The highly conductive linear material is a performance-optimized modifying component that does not directly participate in the electrochemical reaction, significantly improving the conductivity and structural stability of the composite material and enhancing its cycle performance.

[0008] As one embodiment, the nickel-based (copper) oxide includes nickel oxide (NiO), a physical complex of nickel oxide and trace amounts of copper oxide (wt% NiO:CuO>90:10), and a nickel-copper oxide chemical complex NiO. X Cu 1-XAt least one of O (0.8 < x < 1.0). For example, nickel-based (copper) oxide can be nickel oxide (NiO), a mixture of nickel oxide and copper oxide (wt% NiO: CuO = 95:5), Ni 0.9 Cu 0.1 O, etc. Both nickel oxide and copper oxide can form a unique hollow spherical microstructure with stacked nanosheets by means of a gas template through a solvothermal method ( Figure 3 ). Their physical composite is the mixing of nickel oxide with this unique structure and copper oxide with this unique structure.

[0009] As an embodiment, the highly conductive linear material is one or both of a linear carbon material and a nano metal wire. The highly conductive linear material can play a good bridging role to accelerate the electron conduction between electrode active materials and between electrode active materials and current collectors, reduce the electron transport barrier, and at the same time limit the volume expansion during the cycling of electrode materials, improving the cycling stability of the materials.

[0010] As an embodiment, the linear carbon material includes a composite carbon material composed of one or more combinations of carbon fiber, carbon nanotube, and linear carbon.

[0011] As an embodiment, the nano metal wire includes a composite nano metal wire composed of one or more combinations of nano silver wire, nano gold wire, nano copper wire, and nano nickel wire.

[0012] As an embodiment, the aspect ratio range of the linear carbon material in the highly conductive linear material is 500 - 50000:1, and the aspect ratio range of the nano metal wire is 50 - 1000:1.

[0013] As an embodiment, the nickel-based (copper) oxide composite material is formed by stacking nanosheets with a thickness of 50 - 150 nm to form a hollow spherical structure, the diameter of the hollow cavity is 0.5 - 5 μm, and the outer diameter of the spherical particles is 1 - 10 μm. The nanosheets are rich in irregular nano pores, the specific surface area of the composite material is 25 - 70 m 2 / g, and the pore volume is 0.02 - 0.1 cm 3 / g; the hollow microspheres are interconnected through the bridging of nanosheets and highly conductive linear materials. Therefore, the composite material of the present invention has high conductivity and structural stability.

[0014] The present invention also relates to a preparation method of a wire-drawn candied haws-shaped highly conductive nickel-based (copper) oxide composite material. The method uses nickel-based (copper) oxide and a highly conductive linear material as raw materials and is prepared by a polyelectrolyte modification - ultrasonic assisted stirring process. The specific steps are as follows: S1. Pretreatment: The nickel-based (copper) oxide raw material is dried and sieved (to remove coarse particles), and the highly conductive linear material is transferred into a dispersant for pre-dispersion to form a suspension.

[0015] S2, Polyelectrolyte Modification: Nickel-based (copper) oxides were dispersed in an aqueous solution of a positive polyelectrolyte, and after continuous stirring, the mixture was washed and centrifuged. A suspension of highly conductive linear material was dispersed in an aqueous solution of a negative polyelectrolyte, and after continuous stirring, it was washed and centrifuged. Materials carrying different charges were obtained by vacuum drying. S3. Ingredients: The nickel-based (copper) oxide and the highly conductive linear material obtained from the dispersion in step S2 are successively transferred into the dispersant for ingredient preparation under continuous stirring; S4. Ultrasonic assisted stirring: The mixture obtained in step S3 is subjected to ultrasonic assisted stirring (to achieve uniform dispersion). After the material self-assembles, it is freeze-dried to obtain a candied hawthorn-shaped high-conductivity nickel-based (copper) oxide composite material.

[0016] A core aspect of this invention is the use of positive and negative polyelectrolytes to charge-modify a nickel-based (copper) oxide carrier and a highly conductive linear material, followed by automatic assembly of the materials carrying different charges under ultrasonic-assisted stirring. The principle of polyelectrolyte modification is based on the fact that the electrolyte dissociates in an aqueous solution, carrying different charges, and the carrier and conductive agent automatically assemble after soaking and stirring. Without the polyelectrolyte modification of this invention, directly mixing the nickel-based (copper) oxide carrier and the highly conductive linear material results in strong adsorption, aggregation, and bridging effects due to the large specific surface area and aspect ratio of the carbon materials during mixing. The entanglement and swirling of the carbon materials leads to poor uniformity and bonding strength on the nickel-based (copper) oxide surface. Figure 2 On the other hand, the relative particle size and relative mass of carbon materials and nickel-based (copper) oxides differ greatly, and the mechanical grinding and mixing process can easily cause occupational health hazards such as dust, posing safety risks.

[0017] As one implementation scheme, the polyelectrolyte described in step S2 can be classified into positive polyelectrolytes and negative polyelectrolytes according to the electrical properties exhibited after dissociation in distilled water. The positive polyelectrolyte is one of diethylene glycol diacrylate, polyethyleneimine, and polydimethyldiallyl ammonium chloride, preferably diethylene glycol diacrylate. The negative polyelectrolyte is one of poly(p-styrene sulfonic acid), polyvinyl sulfonic acid, and polymethacrylic acid, preferably poly(p-styrene sulfonic acid).

[0018] As one implementation scheme, the mass percentage concentration of the positive / negative polyelectrolyte aqueous solution in step S2 is 1% to 20%, preferably 2% to 10%. Using the polyelectrolyte aqueous solution to electrically modify the carrier and conductive agent, a mass percentage concentration below 1% may cause the material's electrical properties to not reverse or strengthen as expected when the amount of material added is large, resulting in weaker binding force during subsequent assembly relying on charge affinity. A concentration exceeding 20% ​​may result in high viscosity of the polyelectrolyte aqueous solution, making the powder material difficult to disperse, and increasing the amount used will also increase costs.

[0019] Another core aspect of this invention is the use of ultrasonic-assisted stirring. On one hand, this promotes the uniform dispersion of nickel-based (copper) oxides and highly conductive linear materials carrying different charges, forming a suspension that automatically assembles and achieves a tight, uniform bond based on charge affinity. On the other hand, it avoids damage to the material structure caused by the compression waves and shear forces generated by prolonged high-frequency sound waves. The dispersion process, which combines short-duration ultrasonic waves with long-duration stirring, ensures the uniform composite of the carrier and conductive agent, improving the problems of entanglement and agglomeration of aspect ratio conductive materials and the problem of powder flying during the grinding and mixing of lightweight carbon materials.

[0020] As one implementation scheme, the ultrasonic-assisted stirring process in step S4 involves alternating between short-duration (1-10 min) low-power ultrasonic stirring at 50-400 W and long-duration (0.5-1 h) high-speed stirring at 500-1200 rpm, repeating this process 1-5 times. This achieves uniform dispersion and material self-assembly. The dispersion process combining short-duration low-power ultrasonic stirring with long-duration high-speed stirring promotes the uniform dispersion of nickel-based (copper) oxides and highly conductive linear materials carrying different charges, forming a suspension. This improves the problems of entanglement and agglomeration of aspect ratio conductive materials and the flying of powder during grinding and mixing of lightweight carbon materials. Furthermore, it avoids the damage to the material structure caused by the compression waves and shear forces generated by long-duration high-frequency sound waves, promoting the automatic assembly of the carrier and conductive agent based on charge affinity to achieve a tight and uniform bond.

[0021] In one implementation scheme, the nickel-based (copper) oxide described in step S1 is obtained through a solvothermal reaction-high-temperature heat treatment process. The solvothermal reaction uses soluble nickel salts and / or soluble copper salts as reactants, CO2 and NH3 gases (provided by the decomposition of urea and ammonia) as templates, and a mixture of distilled water and alcohols as solvents (reacting at 100-180°C for 5-20 h) to synthesize a nickel (copper) hydroxide precursor, followed by heat treatment. In some embodiments, the materials are mixed evenly and transferred to a hydrothermal reactor lined with polytetrafluoroethylene, and reacted at 100-180°C for 5-20 h to obtain the nickel (copper) hydroxide precursor.

[0022] As one embodiment, the soluble nickel salt is one of nickel acetate, nickel chloride, nickel nitrate, and nickel sulfate. The soluble copper salt is one of copper chloride, copper sulfate, and copper nitrate.

[0023] As one embodiment, the heat treatment involves heating the nickel (copper) hydroxide precursor to 300-600°C at a heating rate of 5-30°C / min and holding it at that temperature for 0.5-6 hours, followed by furnace cooling to 50-60°C. The resulting nickel-based (copper) oxide has a hollow spherical or near-spherical structure.

[0024] As one implementation scheme, the pretreatment drying and sieving process described in step S1 is mainly aimed at facilitating rapid and uniform dispersion in the polyelectrolyte solution. The nickel-based (copper) oxide powder is spread out to a thickness of 1-20 mm for drying; a thickness less than 1 mm results in low production efficiency, while a thickness greater than 20 mm leads to long drying times. After spreading, it is placed in a forced-air drying oven at 50-100℃ for 1-10 hours and then sieved through a 100-200 mesh sieve. The drying process removes moisture from the reactants to prevent them from clumping due to dampness; therefore, both vacuum drying and freeze drying are applicable, and the choice depends on laboratory conditions and the process flow. The sieving process removes large particles to avoid affecting the uniformity of dispersion due to difficulties in dissolution.

[0025] As one implementation, the highly conductive linear material mentioned in step S1 is one or a mixture of two of the following: linear carbon materials or nanomaterials with a high aspect ratio. The linear carbon material includes composite carbon materials composed of one or more combinations of carbon fibers, carbon nanotubes, and linear carbon. The nanomaterials include composite nanomaterials composed of one or more combinations of silver nanowires, gold nanowires, copper nanowires, and nickel nanowires.

[0026] As one implementation scheme, the pre-dispersion of the highly conductive linear material in step S1 uses one or more of the following dispersants: distilled water, anhydrous ethanol, anhydrous toluene, anhydrous methanol, and anhydrous n-hexane. During continuous stirring, the highly conductive linear material is slowly added to the dispersant, preferably one or more of the following: distilled water, anhydrous ethanol, anhydrous toluene, anhydrous methanol, and anhydrous n-hexane. The dispersant to the mixture dispersion solid ratio is 5-20. After continuous stirring for 0.5-3 hours, a uniformly dispersed suspension is obtained.

[0027] As one implementation scheme, in the batching process described in step S3, the nickel-based (copper) oxide obtained in step S2 is first added during continuous stirring, and after being dispersed evenly, the highly conductive linear material obtained in step S2 is added in a certain proportion. The mass ratio of the highly conductive linear material in the mixture of nickel-based (copper) oxide and highly conductive linear material is 1% to 10%, preferably 2% to 8%. The mass of the highly conductive linear material can be adjusted according to the specific power system and application of the composite material. When the content is less than 1%, it cannot fully play the role of improving conductivity. When the content is greater than 10%, on the one hand, the conductivity improvement effect tends to saturate, and further increasing the proportion of conductive agent will not significantly improve the effect. On the other hand, increasing the proportion of conductive agent will lead to a decrease in the proportion of active material, thereby affecting the specific capacity and cycle performance of the electrode material.

[0028] As one implementation, the dispersant in step S3 is selected from one or more of distilled water, anhydrous ethanol, anhydrous toluene, anhydrous methanol, and anhydrous n-hexane.

[0029] As one implementation, the freeze-drying temperature in step S4 is -80 ~ -60℃, and the freezing time is 18 ~ 24 h.

[0030] This invention also relates to the application of a highly conductive nickel-based (copper) oxide composite material in the shape of a candied hawthorn stalk. This highly conductive nickel-based (copper) oxide composite material can be used as a negative electrode active material for lithium batteries, a positive electrode active material for thermal batteries, an additive for the positive electrode of thermal batteries, an electrode active material for supercapacitors, or a catalyst. For example, the highly conductive nickel oxide composite material, as a negative electrode active material for lithium batteries, has high theoretical specific capacity and cycle stability, promoting the insertion and extraction of lithium ions to achieve rapid charging and discharging of the battery. For example, the highly conductive nickel oxide and copper oxide composite material, as a positive electrode active material for thermal batteries, has high thermal stability and theoretical capacity. It can be prepared into a thermal battery powder electrode through a powder pressing process and assembled with a molten salt electrolyte, separator, negative electrode, heating element, and current collector to form a single cell. For example, the hollow highly conductive nickel oxide composite material, as a catalyst, can promote reactions such as hydrogenation, oxygenation, oxidation, and dehydrogenation, playing an important role in oil refining, ammonia synthesis, organic synthesis, and petrochemical fields.

[0031] Compared with the prior art, the present invention has the following beneficial effects: 1) The nickel-based (copper) oxide raw material prepared by this invention is obtained through a solvothermal reaction-high temperature heat treatment process. It has a unique nanosheet stacked hollow spherical microstructure, excellent thermal stability and high product purity, ensuring the reliability of product quality.

[0032] 2) The highly conductive nickel-based (copper) oxide composite material prepared by the present invention is obtained by polyelectrolyte modification-ultrasonic assisted stirring process, and the conductive agent is uniformly dispersed and loaded on the carrier surface and has good binding force.

[0033] 3) In the high conductivity nickel-based (copper) oxide composite material prepared by this invention, the linear conductive agent plays a good bridging role, which can accelerate the electron conduction between electrode active materials and between electrode active materials and current collectors, reduce the electron transport barrier, and limit the volume expansion of electrode materials during cycling, thereby improving the cycling stability of the material.

[0034] 4) The high conductivity nickel-based (copper) oxide composite material prepared by this invention has a unique hollow structure and specific surface area, which increases the number of reactive sites and the wetting area with electrolyte or electrolyte solution, effectively reducing the internal resistance of the battery, improving the ion diffusion reaction kinetics, and exhibiting excellent lithium storage performance.

[0035] 5) The highly conductive nickel-based (copper) oxide composite material prepared by this invention has a wide range of applications and can be used as a lithium battery anode, a thermal battery cathode, an additive for thermal battery cathodes, a supercapacitor electrode, a catalyst, etc. Attached Figure Description

[0036] Other features, objects, and advantages of the present invention will become more apparent from the following detailed description of non-limiting embodiments with reference to the accompanying drawings: Figure 1 This is a flowchart of the material preparation process; Figure 2 This is due to particle agglomeration and uneven adhesion caused by conventional ball milling. Figure 3 Detailed image of the unique pore structure of nanosheets; Figure 4 Here is a SEM image of nickel oxide from Example 1; Figure 5 This is a SEM image of the silver nanowires from Example 1; Figure 6 SEM images of the highly conductive nickel-based (copper) oxide composite materials from Examples 1, 2, 4, and 5; Figure 7 The material XRD pattern for Example 1; Figure 8 TEM image of the material in Example 1; Figure 9 The material BET diagram for Example 1; Figure 10 This is a thermal analysis diagram of the material in Example 1; Figure 11 The diagram shows the electrical conductivity of the powder material in Example 1. Figure 12 The battery discharge curves are for Examples 1, 4, Comparative Examples 1, 2 and commercial nickel oxide. Figure 13 The figures show the discharge curves of the battery in Example 2 and the commercial FeS2 material. Figure 14 The graphs show the charge-discharge curves of the batteries containing nickel oxide synthesized in Example 3, Comparative Example 3, and commercial nickel oxide. Figure 15 The electrolytic cell chronopotential curves are for Example 5, Comparative Example 4, and commercial nickel oxide. Detailed Implementation

[0037] The present invention will be described in detail below with reference to embodiments. These embodiments will help those skilled in the art to further understand the present invention, but do not limit the invention in any way. It should be noted that those skilled in the art can make several adjustments and improvements without departing from the concept of the present invention. These all fall within the protection scope of the present invention.

[0038] Example 1 A highly conductive nickel-based (copper) oxide composite material resembling candied hawthorn berries, the preparation process of which is as follows: Figure 1 As shown, nickel oxide ( Figure 4 SEM image) and conductive agent of silver nanowires ( Figure 5 SEM image) shows a self-assembled structure resembling a candied hawthorn skewer. Figure 6 SEM image), the product has high purity and is free of impurities. Figure 7 XRD pattern), in which silver nanowires are uniformly dispersed and wound around the surface of a hollow nickel oxide support ( Figure 8 TEM image). The composite material has a good specific surface area ( Figure 9 BET diagram) and thermal stability ( Figure 10 Thermal analysis diagram), the conductivity of the composite material is greatly improved after the addition of linear conductive agent ( Figure 11 Powder conductivity diagram). As a cathode material for thermal batteries, it exhibits a stable discharge curve and high discharge specific capacity. Figure 12 (Discharge curve diagram). The specific implementation steps are as follows: A solvothermal reaction-high-temperature heat treatment process was adopted. A mixture of 10 ml distilled water and 15 ml ethanol was used as the solvent to dissolve 1 mmol of nickel chloride. Then, 0.01 mol of urea and 3 ml of ammonia were added. Using a gas as a template, the reaction was carried out at 120 °C for 10 h to obtain a nickel hydroxide precursor. The nickel hydroxide precursor was placed in a muffle furnace and heated to 500 °C at a heating rate of 5 °C / min and held at that temperature for 3 h. The furnace was then cooled to 50 °C to obtain nickel oxide raw material.

[0039] S1. Pretreatment: Dry the nickel oxide raw material. Spread the material to a thickness of 10 mm and place it in a forced-air drying oven at 60℃ for 5 h. Then, pass it through a 200-mesh sieve for later use. Transfer the silver nanowires into anhydrous ethanol at a liquid-to-solid ratio of 15 and stir for 1 h to pre-disperse and form a suspension for later use.

[0040] S2. Polyelectrolyte modification: Nickel oxide was dispersed in a 10% (w / w) aqueous solution of diethylene glycol diacrylate phthalate, stirred for 1 h, washed alternately with distilled water and anhydrous ethanol, centrifuged, and then vacuum dried at 60°C for 5 h to obtain positively charged nickel oxide; a suspension of silver nanowires was dispersed in a 10% (w / w) aqueous solution of poly(p-styrene sulfonic acid), stirred for 1 h, washed alternately with distilled water and anhydrous ethanol, centrifuged, and then vacuum dried at 60°C for 5 h to obtain negatively charged silver nanowires.

[0041] S3. Ingredients: Weigh the positively charged nickel oxide and negatively charged silver nanowires obtained in step S2 at a mass ratio of 98:2. After dispersing the positively charged nickel oxide evenly in anhydrous ethanol at a liquid-to-solid ratio of 10, add the weighed negatively charged silver nanowires.

[0042] S4. Ultrasonic-assisted stirring: The mixture obtained in step S3 was subjected to alternating short-term (5 min) ultrasonic stirring at 200W and long-term (0.5 h) stirring at 600 rpm, repeated twice to achieve uniform dispersion and material self-assembly. After freeze-drying at -60℃ for 20 h, a candied hawthorn-like high-conductivity nickel oxide composite material was obtained. Figure 6 ).

[0043] The prepared material was used as the positive electrode active material of the thermal battery. A positive electrode sheet with a diameter of Ф26 mm and a thickness of approximately 1.5 mm was prepared by powder pressing after mixing a highly conductive nickel oxide composite material (shaped like a candied hawthorn stalk), magnesium oxide, and a ternary molten salt electrolyte (LiCl-LiBr-LiF) in a weight ratio of 80:2:18. This positive electrode sheet was then assembled with a separator (wt% LiCl-LiF-LiBr ternary electrolyte: wt% magnesium oxide = 70:30, Ф26 mm, approximately 1 mm thick) and a lithium boron alloy negative electrode sheet (LiB64, Yichang Yilong Electronic Materials Co., Ltd., Ф18 mm, approximately 0.4 mm thick). Electrical performance discharge tests were conducted at 550℃. The battery discharged normally, with a stable discharge voltage and a high specific capacity. Figure 12 The commercial nickel oxide was purchased from Tianjin Xiens Opd Technology Co., Ltd. (99%), and the same electrical performance testing conditions were used.

[0044] Example 2 A highly conductive nickel-based (copper) oxide composite material resembling a candied hawthorn skewer is disclosed. The nickel-based (copper) oxide and a linear conductive agent self-assemble to form the candied hawthorn skewer structure. Its composition is Ni. 0.9 Cu 0.1 O2 and carbon fiber mixture, wherein the carbon fiber is uniformly dispersed, wound and loaded in hollow Ni 0.9 Cu 0.1 O2 carrier surface. The composite material possesses good specific surface area and thermal stability; the conductivity of the composite material is significantly improved after the addition of a linear conductive agent. As an auxiliary additive for FeS2 cathode material in thermal batteries, it exhibits a stable discharge curve, increases high-temperature discharge time, and reduces battery internal resistance. Specific implementation steps are as follows: A solvothermal reaction-high-temperature heat treatment process was employed. A mixture of 25 ml distilled water and 30 ml ethanol was used as the solvent to dissolve 1.8 mmol of nickel chloride and 0.2 mmol of copper chloride. Then, 0.03 mol of urea and 6 ml of ammonia were added. Using a gas as a template, the reaction was carried out at 150 °C for 8 h to obtain a nickel-copper hydroxide precursor. The nickel-copper hydroxide precursor was placed in a muffle furnace and heated to 450 °C at a heating rate of 5 °C / min and held for 4 h. After furnace cooling to 50 °C, Ni was obtained. 0.9 Cu 0.1 O2 raw materials.

[0045] S1. Pretreatment: Ni 0.9 Cu 0.1 The O2 raw material is dried, and after being spread out to a thickness of 5 mm, it is placed in a forced-air drying oven and dried at 60°C for 5 hours. After drying, it is passed through a 100-mesh sieve and set aside for use. The carbon fiber is transferred into distilled water at a liquid-to-solid ratio of 10 and stirred for 2 hours to pre-disperse and form a suspension for use.

[0046] S2, Polyelectrolyte Modification: Ni 0.9 Cu 0.1 O2 was dispersed in an 8% (w / w) aqueous solution of diethylene glycol diacrylate phthalate. After soaking and stirring for 2 h, the mixture was washed alternately with distilled water and anhydrous ethanol, centrifuged, and then vacuum dried at 60 °C for 5 h to obtain positively charged Ni. 0.9 Cu 0.1 O2; The carbon fiber suspension was dispersed in an 8% (w / w) aqueous solution of polyvinyl sulfonic acid, soaked and stirred for 2 h, then washed alternately with distilled water and anhydrous ethanol, centrifuged, and vacuum dried at 60 °C for 5 h to obtain carbon fibers carrying negative charges.

[0047] S3, Ingredients: The positively charged Ni obtained in step S2 is added... 0.9 Cu 0.1 O2 and negatively charged carbon fibers were weighed at a mass ratio of 92:8, and positively charged Ni was added at a liquid-to-solid ratio of 10. 0.9 Cu 0.1After O2 is transferred into anhydrous ethanol and dispersed evenly, the weighed negatively charged carbon fibers are added.

[0048] S4. Ultrasonic-assisted stirring: The mixture obtained in step S3 was subjected to alternating short-term (7 min) ultrasonic stirring at 300 W and long-term (1 h) stirring at 900 rpm, repeated 3 times to achieve uniform dispersion and material self-assembly. After freeze-drying at -60℃ for 24 h, a high-conductivity Ni with a candied fruit-like appearance was obtained. 0.9 Cu 0.1 O2 composite material ( Figure 6 ).

[0049] The prepared material was used as an auxiliary additive for the positive electrode material of FeS2 (Saidiga Shandong Technology Co., Ltd., 99%) in thermal batteries. FeS2: Candied Hawthorn-like High Conductivity Ni 0.9 Cu 0.1 O2 composite material: magnesium oxide: LiCl-LiBr-LiF ternary molten salt electrolyte was mixed in a weight ratio of 75:5:2:18 and then prepared into a positive electrode sheet with a diameter of Ф26mm and a thickness of approximately 1.5mm by powder pressing. This positive electrode sheet was then assembled with a separator (wt% LiCl-LiF-LiBr ternary electrolyte: wt% magnesium oxide = 70:30, Ф26mm, thickness approximately 1mm) and a lithium-boron alloy negative electrode sheet (LiB64, Yichang Yilong Electronic Materials Co., Ltd., Ф18mm, thickness approximately 0.4mm). Electrical performance discharge tests were conducted at 550℃. The battery discharged normally with a stable discharge voltage. The high-temperature discharge time increased, and the battery internal resistance decreased. Figure 13 ).

[0050] Example 3 A highly conductive nickel-based (copper) oxide composite material resembling a candied hawthorn skewer is disclosed. The nickel-based (copper) oxide and a linear conductive agent self-assemble to form this candied hawthorn skewer structure. The composite material is a mixture of nickel oxide and gold nanowires, with the gold nanowires uniformly dispersed and wound around the surface of a hollow nickel oxide carrier. The composite material exhibits good specific surface area and thermal stability. The addition of the linear conductive agent significantly improves the conductivity of the composite material. As a positive electrode material for lithium-ion batteries, it demonstrates high cycle stability and discharge specific capacity. The specific implementation steps are as follows: A solvothermal reaction-high-temperature heat treatment process was adopted. A mixture of 25 ml distilled water and 30 ml ethanol was used as the solvent to dissolve 3 mmol of nickel chloride. Then, 0.04 mol of urea and 10 ml of ammonia were added. Using a gas as a template, the reaction was carried out at 150 °C for 12 h to obtain a nickel hydroxide precursor. The nickel hydroxide precursor was placed in a muffle furnace and heated to 450 °C at a heating rate of 5 °C / min and held at that temperature for 4 h. The furnace was then cooled to obtain nickel oxide raw material.

[0051] S1. Pretreatment: Dry the nickel oxide raw material. After spreading the material to a thickness of 8 mm, place it in a forced-air drying oven at 60℃ for 6 hours and then pass it through a 150-mesh sieve for later use. Transfer the gold nanowires into anhydrous ethanol at a liquid-to-solid ratio of 15 and stir for 1 hour to pre-disperse them into a suspension for later use.

[0052] S2. Polyelectrolyte modification: Nickel oxide was dispersed in a 5% (w / w) aqueous solution of diethylene glycol diacrylate phthalate. After soaking and stirring for 2 h, it was washed alternately with distilled water and anhydrous ethanol, centrifuged, and then vacuum dried at 60℃ for 5 h to obtain positively charged nickel oxide. The suspension of gold nanowires was dispersed in a 5% (w / w) aqueous solution of poly(p-styrene sulfonic acid). After soaking and stirring for 2 h, it was washed alternately with distilled water and anhydrous ethanol, centrifuged, and then vacuum dried at 60℃ for 5 h to obtain negatively charged gold nanowires.

[0053] S3. Ingredients: Weigh the positively charged nickel oxide and negatively charged gold nanowires obtained in step S2 at a mass ratio of 97:3. After dispersing the positively charged nickel oxide evenly in anhydrous ethanol at a liquid-to-solid ratio of 15, add the weighed negatively charged gold nanowires.

[0054] S4. Ultrasonic-assisted stirring: The mixture obtained in step S3 is subjected to alternating short-term (8 min) ultrasonic stirring at 200W and long-term (1 h) stirring at 800rpm. This process is repeated twice to achieve uniform dispersion and material self-assembly. After freeze-drying at -60℃ for 18 h, a high-conductivity nickel oxide composite material in the shape of candied hawthorn is obtained.

[0055] The prepared material was used as the negative electrode active material for lithium batteries. The active material, acetylene black, and PVDF were weighed at a mass ratio of 7:2:1, ground finely in a mortar, and then NMP was added at a liquid-to-solid ratio of 7:3 for further grinding to obtain a uniform slurry. This slurry was then coated onto copper foil, vacuum dried, and cut into uniform circular electrode sheets with a diameter of Ф12mm. Finally, lithium metal was used as the counter electrode and assembled with a PP separator, gasket, and spring sheet in a glove box. Electrolyte (LiPF6 / EC:DEC (1:1 wt%)) was injected to assemble a CR2032 coin cell. The battery could be charged and discharged normally. Figure 14 The commercial nickel oxide was purchased from Tianjin Xiens Opd Technology Co., Ltd. (99%), and the same electrical performance testing conditions were used.

[0056] Example 4 A highly conductive nickel-based (copper) oxide composite material resembling a candied hawthorn skewer is disclosed. The nickel-based (copper) oxide and a linear conductive agent self-assemble to form this candied hawthorn skewer structure. The composite material is composed of a mixture of nickel oxide and copper oxide with carbon nanotubes, wherein the carbon nanotubes are uniformly dispersed and wound around the surface of a hollow nickel oxide and copper oxide mixture carrier. The composite material exhibits good specific surface area and thermal stability. The addition of the linear conductive agent significantly improves the conductivity of the composite material. As a positive electrode material for thermal batteries, it shows a stable discharge curve and high discharge specific capacity. The specific implementation steps are as follows: A solvothermal reaction-high-temperature heat treatment process was employed. Using a mixture of 12 ml distilled water and 16 ml ethanol as the solvent, 1 mmol of nickel chloride was dissolved, followed by the addition of 0.01 mol urea and 3 ml ammonia. Using a gas as a template, the reaction was carried out at 120 °C for 10 h to obtain a nickel hydroxide precursor. The nickel hydroxide precursor was placed in a muffle furnace and heated to 500 °C at a rate of 5 °C / min, held at that temperature for 3 h, and then cooled with the furnace to obtain nickel oxide raw material. Copper oxide raw material was prepared using the same method and then mixed with nickel oxide at a ratio of wt% NiO:CuO = 95:5 to obtain a nickel oxide and copper oxide mixture.

[0057] S1. Pretreatment: The mixture of nickel oxide and copper oxide is dried. After the material is spread out to a thickness of 10 mm, it is placed in a forced-air drying oven and dried at 60℃ for 5 h. After drying, it is passed through a 150-mesh sieve and set aside for use. Carbon nanotubes are transferred into anhydrous ethanol at a liquid-to-solid ratio of 12 and stirred for 1 h to pre-disperse and form a suspension for use.

[0058] S2. Polyelectrolyte modification: A mixture of nickel oxide and copper oxide was dispersed in a 10% (w / w) aqueous solution of diethylene glycol diacrylate phthalate. After soaking and stirring for 1 h, the mixture was washed alternately with distilled water and anhydrous ethanol, centrifuged, and then vacuum dried at 60°C for 4 h to obtain a positively charged mixture of nickel oxide and copper oxide. A carbon nanotube suspension was dispersed in a 5% (w / w) aqueous solution of poly(p-styrene sulfonic acid). After soaking and stirring for 2 h, the suspension was washed alternately with distilled water and anhydrous ethanol, centrifuged, and then vacuum dried at 60°C for 5 h to obtain negatively charged carbon nanotubes.

[0059] S3. Ingredients: Weigh the positively charged nickel oxide and copper oxide mixture obtained in step S2 with the negatively charged carbon nanotubes at a mass ratio of 96:4. After dispersing the positively charged nickel oxide and copper oxide mixture evenly in anhydrous ethanol at a liquid-to-solid ratio of 15, add the weighed negatively charged carbon nanotubes.

[0060] S4. Ultrasonic-assisted stirring: The mixture obtained in step S3 was subjected to alternating short-term (8 min) ultrasonic stirring at 200W and long-term (0.5 h) stirring at 1000 rpm, repeated 3 times to achieve uniform dispersion and material self-assembly. The mixture was then freeze-dried at -80℃ for 15 h to obtain a candied hawthorn-like high-conductivity nickel oxide and copper oxide composite material. Figure 6 ).

[0061] The prepared material was used as the positive electrode active material of the thermal battery. A composite material of highly conductive nickel oxide and copper oxide in the shape of candied hawthorn berries, magnesium oxide, and LiCl-LiBr-LiF ternary molten salt electrolyte were mixed in a weight ratio of 80:2:18 and then prepared into a positive electrode sheet with a diameter of 30 mm and a thickness of approximately 1.5 mm by powder pressing. This positive electrode sheet was then assembled with a separator (wt% LiCl-LiF-LiBr ternary electrolyte: wt% magnesium oxide = 70:30, diameter 30 mm, thickness approximately 1 mm) and a lithium-boron alloy negative electrode sheet (LiB64, Yichang Yilong Electronic Materials Co., Ltd., diameter 26 mm, thickness approximately 0.4 mm). Electrical performance discharge tests were conducted at 500℃. The battery discharged normally with a stable discharge voltage. Figure 12 ).

[0062] Example 5 A highly conductive nickel-based (copper) oxide composite material resembling a candied hawthorn skewer is disclosed. The nickel-based (copper) oxide and a linear conductive agent self-assemble to form the candied hawthorn skewer structure. Its composition is Ni. 0.95 Cu 0.05 A mixture of O2 and carbon nanotubes, wherein the carbon nanotubes are uniformly dispersed and wound around a hollow Ni 0.95 Cu 0.05 O2 carrier surface. The composite material possesses good specific surface area and thermal stability, and its conductivity is significantly improved after the addition of a linear conductive agent. As an anode catalyst for water electrolysis to produce hydrogen, it exhibits conductivity at 20 mA / cm². 2 At the specified current density, the electrolytic cell can operate stably for over 90 hours. The specific implementation steps are as follows: A solvothermal reaction-high-temperature heat treatment process was employed. A mixture of 30 ml distilled water and 30 ml ethanol was used as the solvent to dissolve 1.9 mmol of nickel chloride and 0.1 mmol of copper chloride. Then, 0.04 mol of urea and 8 ml of ammonia were added. Using a gas as a template, the reaction was carried out at 120 °C for 10 h to obtain a nickel-copper hydroxide precursor. The nickel-copper hydroxide precursor was placed in a muffle furnace and heated to 500 °C at a heating rate of 5 °C / min and held at that temperature for 3 h. After furnace cooling, Ni was obtained. 0.95 Cu 0.05 O2 raw materials.

[0063] S1. Pretreatment: Ni 0.95 Cu0.05 The O2 raw material was dried, and the material was spread out to a thickness of 10 mm and then placed in a forced-air drying oven at 60°C for 5 hours. After drying, it was passed through a 200-mesh sieve and set aside for use. The carbon nanotubes were transferred into anhydrous ethanol at a liquid-to-solid ratio of 18 and stirred for 1 hour to pre-disperse and form a suspension for use.

[0064] S2, Polyelectrolyte Modification: Ni 0.95 Cu 0.05 O2 was dispersed in a 9% (w / w) aqueous solution of diethylene glycol diacrylate phthalate. After soaking and stirring for 1 h, the mixture was washed alternately with distilled water and anhydrous ethanol, centrifuged, and then vacuum dried at 60 °C for 5 h to obtain positively charged Ni. 0.95 Cu 0.05 O2; The carbon nanotube suspension was dispersed in a 5% (w / w) aqueous solution of poly(p-styrene)sulfonic acid, soaked and stirred for 2 h, then washed alternately with distilled water and anhydrous ethanol, centrifuged, and vacuum dried at 60 °C for 5 h to obtain negatively charged carbon nanotubes.

[0065] S3, Ingredients: The positively charged Ni obtained in step S2 is added... 0.95 Cu 0.05 O2 and negatively charged carbon nanotubes were weighed at a mass ratio of 95:5, and positively charged Ni was added at a liquid-to-solid ratio of 15. 0.95 Cu 0.05 After O2 is transferred into anhydrous ethanol and dispersed evenly, weighed negatively charged carbon nanotubes are added.

[0066] S4. Ultrasonic-assisted stirring: The mixture obtained in step S3 was subjected to alternating short-term (5 min) ultrasonic stirring at 400W and long-term (1 h) stirring at 600rpm, repeated twice to achieve uniform dispersion and material self-assembly. After freeze-drying at -60℃ for 18 h, a high-conductivity Ni with a candied fruit-like appearance was obtained. 0.95 Cu 0.05 O2 composite material ( Figure 6 ).

[0067] The prepared material was used as the anode catalyst for hydrogen production via water electrolysis, and the highly conductive Ni in the shape of a candied hawthorn was used. 0.95 Cu 0.05 An O2 composite catalyst mixture was used as the anode catalyst, and a commercial platinum-carbon (Pt / C) catalyst was used as the cathode catalyst. A loading of 3 mg / cm³ was applied. 2 High conductivity Ni 0.95 Cu 0.05 O2 and loading of 0.5 mg / cm 2Commercially available Pt / C catalyst was sprayed onto nickel foam. The catalyst-coated nickel foam was then placed on both sides of an FFA-3-50 membrane, forming a membrane electrode together with the gas diffusion layer. Potassium hydroxide was used as the electrolyte. At 20 mA / cm²... 2 At a current density of [value missing], the electrolytic cell can operate stably for more than 90 hours. Figure 15 The commercial nickel oxide was purchased from Tianjin Xiens Opd Technology Co., Ltd. (99%), and the same electrical performance testing conditions were used.

[0068] Comparative Example 1 Compared with Example 1, Comparative Example 1 did not add a conductive agent. After synthesis through a solvothermal reaction-high temperature heat treatment process, its electrical performance was directly tested. The specific implementation steps are as follows: A solvothermal reaction-high-temperature heat treatment process was adopted. A mixture of 10 ml distilled water and 15 ml ethanol was used as the solvent to dissolve 1 mmol of nickel chloride. Then, 0.01 mol of urea and 3 ml of ammonia were added. Using a gas as a template, the reaction was carried out at 120 °C for 10 h to obtain a nickel hydroxide precursor. The nickel hydroxide precursor was placed in a muffle furnace and heated to 500 °C at a heating rate of 5 °C / min and held at that temperature for 3 h. The furnace was then cooled to 50 °C to obtain nickel oxide raw material.

[0069] The prepared material was used as the positive electrode active material of the thermal battery. Nickel oxide raw material: magnesium oxide: LiCl-LiBr-LiF ternary molten salt electrolyte was mixed in a weight ratio of 80:2:18 and then prepared into a positive electrode sheet with a diameter of Ф26 mm and a thickness of approximately 1.5 mm by powder pressing. This positive electrode sheet was then assembled with a separator (wt% LiCl-LiF-LiBr ternary electrolyte: wt% magnesium oxide = 70:30, Ф26 mm, thickness approximately 1 mm) and a lithium boron alloy negative electrode sheet (LiB64, Yichang Yilong Electronic Materials Co., Ltd., Ф18 mm, thickness approximately 0.4 mm). Electrical performance discharge tests were conducted at 550°C. The battery could discharge normally, but compared to Example 1, the discharge voltage and specific capacity were significantly reduced. Figure 12 ).

[0070] Comparative Example 2 Compared to Example 1, Comparative Example 2 did not involve polyelectrolyte modification-ultrasonic stirring. It used the same nickel oxide and silver nanowire material ratio as Example 1, directly transferring the nickel oxide into anhydrous ethanol for uniform dispersion, and then adding the silver nanowires to achieve mixing. The specific implementation steps are as follows: A solvothermal reaction-high-temperature heat treatment process was adopted. A mixture of 10 ml distilled water and 15 ml ethanol was used as the solvent to dissolve 1 mmol of nickel chloride. Then, 0.01 mol of urea and 3 ml of ammonia were added. Using a gas as a template, the reaction was carried out at 120 °C for 10 h to obtain a nickel hydroxide precursor. The nickel hydroxide precursor was placed in a muffle furnace and heated to 500 °C at a heating rate of 5 °C / min and held at that temperature for 3 h. The furnace was then cooled to 50 °C to obtain nickel oxide raw material.

[0071] S1. Pretreatment: Dry the nickel oxide raw material. Spread the material to a thickness of 10 mm and place it in a forced-air drying oven at 60℃ for 5 h. Then, pass it through a 200-mesh sieve for later use. Transfer the silver nanowires into anhydrous ethanol at a liquid-to-solid ratio of 15 and stir for 1 h to pre-disperse and form a suspension for later use.

[0072] S2. Ingredients: Weigh the nickel oxide and silver nanowires obtained in step S1 at a mass ratio of 98:2. After dispersing the nickel oxide in anhydrous ethanol at a liquid-to-solid ratio of 10, add the weighed silver nanowires.

[0073] S3. Freeze-drying: The mixture obtained in step S2 is freeze-dried at -60℃ for 20 hours to obtain a conductive nickel oxide composite material.

[0074] The prepared material was used as the positive electrode active material of the thermal battery. A positive electrode sheet with a diameter of Ф26 mm and a thickness of approximately 1.5 mm was prepared by powder pressing after mixing conductive nickel oxide composite material, magnesium oxide, and LiCl-LiBr-LiF ternary molten salt electrolyte in a weight ratio of 80:2:18. This positive electrode sheet was then assembled with a separator (wt% LiCl-LiF-LiBr ternary electrolyte: wt% magnesium oxide = 70:30, Ф26 mm, approximately 1 mm thick) and a lithium boron alloy negative electrode sheet (LiB64, Yichang Yilong Electronic Materials Co., Ltd., Ф18 mm, approximately 0.4 mm thick). Electrical performance discharge tests were conducted at 550°C. The battery discharged normally, but compared to Example 1, the discharge voltage fluctuated and the specific capacity decreased. Figure 12 ).

[0075] Comparative Example 3 Compared to Example 3, Comparative Example 3 did not undergo polyelectrolyte modification-ultrasonic stirring. It used the same nickel oxide and gold nanowire material ratio as Example 3, directly transferring the nickel oxide into anhydrous ethanol for uniform dispersion, and then adding the gold nanowires to achieve mixing. The specific implementation steps are as follows: A solvothermal reaction-high-temperature heat treatment process was adopted. A mixture of 25 ml distilled water and 30 ml ethanol was used as the solvent to dissolve 3 mmol of nickel chloride. Then, 0.04 mol of urea and 10 ml of ammonia were added. Using a gas as a template, the reaction was carried out at 150 °C for 12 h to obtain a nickel hydroxide precursor. The nickel hydroxide precursor was placed in a muffle furnace and heated to 450 °C at a heating rate of 5 °C / min and held at that temperature for 4 h. The furnace was then cooled to obtain nickel oxide raw material.

[0076] S1. Pretreatment: Dry the nickel oxide raw material. After spreading the material to a thickness of 8 mm, place it in a forced-air drying oven at 60℃ for 6 hours and then pass it through a 150-mesh sieve for later use. Transfer the gold nanowires into anhydrous ethanol at a liquid-to-solid ratio of 15 and stir for 1 hour to pre-disperse them into a suspension for later use.

[0077] S2. Ingredients: Weigh the nickel oxide and gold nanowires obtained in step S1 at a mass ratio of 97:3. After dispersing the nickel oxide evenly in anhydrous ethanol at a liquid-to-solid ratio of 15, add the weighed gold nanowires.

[0078] S3. Freeze-drying: The mixture obtained in step S2 is freeze-dried at -60℃ for 18 hours to obtain a conductive nickel oxide composite material.

[0079] The prepared material was used as the negative electrode active material for lithium batteries. The active material, acetylene black, and PVDF were weighed at a mass ratio of 7:2:1, ground finely in a mortar, and then NMP was added at a liquid-to-solid ratio of 7:3 for further grinding to obtain a uniform slurry. This slurry was then coated onto copper foil, vacuum dried, and cut into uniform circular electrode sheets with a diameter of Ф12mm. Finally, lithium metal was used as the counter electrode and assembled with a PP separator, gasket, and spring sheet in a glove box. Electrolyte (LiPF6 / EC:DEC (1:1 wt%)) was injected to assemble a CR2032 coin cell. Compared to Example 3, the battery capacity decreased (…). Figure 14 ).

[0080] Comparative Example 4 Compared to Example 5, Comparative Example 4 did not undergo polyelectrolyte modification-ultrasonic stirring, and used the same Ni as in Example 5. 0.95 Cu 0.05 The ratio of O2 to carbon nanotube materials directly affects Ni 0.95 Cu 0.05 After O2 is transferred to anhydrous ethanol and dispersed evenly, carbon nanotubes are added to mix the two. The specific implementation steps are as follows: A solvothermal reaction-high-temperature heat treatment process was employed. A mixture of 30 ml distilled water and 30 ml ethanol was used as the solvent to dissolve 1.9 mmol of nickel chloride and 0.1 mmol of copper chloride. Then, 0.04 mol of urea and 8 ml of ammonia were added. Using a gas as a template, the reaction was carried out at 120 °C for 10 h to obtain a nickel-copper hydroxide precursor. The nickel-copper hydroxide precursor was placed in a muffle furnace and heated to 500 °C at a heating rate of 5 °C / min and held at that temperature for 3 h. After furnace cooling, Ni was obtained. 0.95 Cu 0.05 O2 raw materials.

[0081] S1. Pretreatment: Ni 0.95 Cu 0.05 The O2 raw material was dried, and the material was spread out to a thickness of 10 mm and then placed in a forced-air drying oven at 60°C for 5 hours. After drying, it was passed through a 200-mesh sieve and set aside for use. The carbon nanotubes were transferred into anhydrous ethanol at a liquid-to-solid ratio of 18 and stirred for 1 hour to pre-disperse and form a suspension for use.

[0082] S2, Ingredients: The Ni obtained in step S2 is... 0.95 Cu 0.05 O2 and carbon nanotubes were weighed at a mass ratio of 95:5, and Ni was added at a liquid-to-solid ratio of 15. 0.95 Cu 0.05 After O2 is transferred into anhydrous ethanol and dispersed evenly, the weighed carbon nanotubes are added.

[0083] S3. Freeze-drying: The mixture obtained in step S2 is freeze-dried at -60℃ for 18 hours to obtain conductive Ni. 0.95 Cu 0.05 O2 composite material.

[0084] The prepared material was used as an anode catalyst for hydrogen production via water electrolysis, with conductive Ni... 0.95 Cu 0.05 An O2 composite catalyst mixture was used as the anode catalyst, and a commercial platinum-carbon (Pt / C) catalyst was used as the cathode catalyst. A loading of 3 mg / cm³ was applied. 2 conductive Ni 0.95 Cu 0.05 O2 and loading of 0.5 mg / cm 2 Commercially available Pt / C catalyst was sprayed onto nickel foam. The catalyst-coated nickel foam was then placed on both sides of an FFA-3-50 membrane, forming a membrane electrode together with the gas diffusion layer. Potassium hydroxide was used as the electrolyte. At 20 mA / cm²... 2 At the current density, compared with Example 5, the stable operating time of the electrolytic cell is shortened ( Figure 15 The commercial nickel oxide was purchased from Tianjin Xiens Opd Technology Co., Ltd. (99%), and the same electrical performance testing conditions were used.

[0085] The specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the specific embodiments described above, and those skilled in the art can make various modifications or variations within the scope of the claims, which do not affect the essence of the present invention.

Claims

1. A highly conductive nickel-based (copper) oxide composite material in the shape of candied hawthorn skewers, characterized in that, In the nickel-based (copper) oxide composite material, a highly conductive linear material forms a wire-drawing-like conductive network, which uniformly and交错缠绕于纳米片堆积中空球形镍基(铜)氧化物基体上;镍基(铜)氧化物为氧化镍、氧化镍和微量氧化铜的物理复合物、镍铜氧化学复合物Ni X Cu 1-X O (0.8 < x < 1.0), or at least one of them; the highly conductive linear material is one or both of linear carbon materials and nano metal wires. It should be noted that the Chinese part "交错缠绕于纳米片堆积中空球形镍基(铜)氧化物基体上" seems to be incomplete or inaccurate in expression. You may want to check and correct it for a more precise translation.

2. The composite material according to claim 1, characterized in that, The linear carbon material includes one or more of carbon fiber, carbon nanotubes, and linear carbon. And / or, the nanometal wires include one or more of the following: silver nanowires, gold nanowires, copper nanowires, and nickel nanowires; And / or, the aspect ratio of the linear carbon material in the highly conductive linear material ranges from 500 to 50000:1, and the aspect ratio of the nano-metal wire ranges from 50 to 1000:

1.

3. The composite material according to claim 1, characterized in that, The nickel-based (copper) oxide composite material is formed by stacking nanosheets with a thickness of 50 to 150 nm to form a hollow spherical structure, with a hollow cavity diameter of 0.5 to 5 μm and an outer diameter of 1 to 10 μm. The nanosheets are rich in irregular nanopores, and the composite material has a specific surface area of ​​25~70 m². 2 / g, pore volume is 0.02 ~ 0.1 cm³ 3 / g; Hollow microspheres are interconnected through nanosheet piling and bridging with highly conductive linear materials.

4. A method for preparing the composite material according to claim 1, characterized in that, The method includes the following steps: S1. Pretreatment: The nickel-based (copper) oxide raw material is dried and sieved; the highly conductive linear material is transferred into a dispersant for pre-dispersion to form a suspension; S2, Polyelectrolyte Modification: Nickel-based (copper) oxides were dispersed in an aqueous solution of a positive polyelectrolyte, and after continuous stirring, the mixture was washed and centrifuged. A suspension of highly conductive linear material was dispersed in an aqueous solution of a negative polyelectrolyte, and after continuous stirring, it was washed and centrifuged. Materials carrying different charges were obtained by vacuum drying. S3. Ingredients: The nickel-based (copper) oxide and the highly conductive linear material obtained in step S2 are successively transferred into the dispersant for batching under continuous stirring; S4. Ultrasonic assisted stirring: The mixture obtained from the dispersion in step S3 is subjected to ultrasonic assisted stirring. After the material self-assembles, it is freeze-dried to obtain a high-conductivity nickel-based (copper) oxide composite material in the shape of candied hawthorn.

5. The preparation method according to claim 4, characterized in that, The nickel-based (copper) oxide raw material is obtained by a solvothermal reaction-high temperature heat treatment process, using soluble nickel salt and / or soluble copper salt as reaction raw materials, gas as template, and a mixture of distilled water and alcohol as solvent to synthesize a nickel (copper) hydroxide precursor, which is then subjected to heat treatment.

6. The preparation method according to claim 5, characterized in that, Includes at least one of the following technical features: A1. The soluble nickel salt is one of nickel acetate, nickel chloride, nickel nitrate, and nickel sulfate; A2. The soluble copper salt is one of copper chloride, copper sulfate, and copper nitrate; A3. The gas template is provided by the decomposition of urea and ammonia. A4. Using a mixture of distilled water and alcohol as a solvent, react at 100-180℃ for 5-20 h to obtain nickel (copper) hydroxide precursors; A5. The heat treatment involves heating the material to 300-600°C at a heating rate of 5-30°C / min and holding it at that temperature for 0.5-6 hours, followed by furnace cooling to 50-60°C.

7. The preparation method according to claim 4, characterized in that, The dispersants in steps S1 and S3 are selected from one or more of distilled water, anhydrous ethanol, anhydrous toluene, anhydrous methanol, and anhydrous n-hexane, respectively. And / or, in step S2, the positive polyelectrolyte is one of diethylene glycol diacrylate, polyethyleneimine, and polydimethyldiallyl ammonium chloride; And / or, the mass percentage concentration of the positive polyelectrolyte aqueous solution is 1% to 20%; And / or, in step S2, the negative polyelectrolyte is one of poly(p-styrene sulfonic acid), poly(poly(ethylene sulfonic acid), and poly(methacrylic acid); And / or, the mass percentage concentration of the negative polyelectrolyte aqueous solution is 1% to 20%.

8. The preparation method according to claim 4, characterized in that, In step S3, the mass ratio of the high-conductivity linear material in the nickel-based (copper) oxide and high-conductivity linear material mixture is 1wt% to 10wt%; the dispersion liquid-solid ratio after the dispersant and mixture are mixed is 5 to 20.

9. The preparation method according to claim 4, characterized in that, In step S4, the ultrasonic-assisted stirring treatment is performed by alternating between short-duration (1-10 min) low-power ultrasound (50-400 W) and long-duration (30-60 min) high-speed stirring (500-1200 rpm), and repeated 1-5 times. And / or, the freeze-drying temperature is -80 ~ -60℃, and the freezing time is 18 ~ 24 h.

10. Use of a composite material according to any one of claims 1-3, or a composite material prepared by the method according to any one of claims 4-9, characterized in that, The composite material is used as a negative electrode active material for lithium batteries, a positive electrode active material for thermal batteries, an additive for the positive electrode of thermal batteries, an electrode active material for supercapacitors, or a catalyst.

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