Solid-state battery material for humanoid robot and manufacturing process of solid-state battery material
By designing composite cathode materials, sulfide-based electrolytes, and modified anode materials, the chemical stability and cycle performance issues of solid-state batteries in humanoid robot applications were solved, achieving high energy density and safe and reliable battery performance.
Patent Information
- Application Number
- CN202512024068.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-30
- Publication Date
- 2026-04-07
AI Technical Summary
Existing solid-state battery materials suffer from problems such as poor chemical stability, severe interfacial reactions, degradation of cycle performance, and insufficient energy density in humanoid robot applications, making it difficult to meet the requirements for long battery life and safety and reliability.
A high-performance solid-state battery is formed by using composite cathode materials, sulfide-based composite solid electrolytes, and modified anode materials. The lithium-rich manganese-based material is stabilized by a Li2ZrO3 coating layer, the electrolyte is enhanced by Li3PO4-Al2O3 composite nanoparticles, and the anode is improved by Si-C composite particles and TiN conductive layer. Combined with cold pressing process and strict water and oxygen control, a high-performance solid-state battery is formed.
It significantly improves the ionic conductivity, cycle stability and safety performance of solid-state batteries, increases energy density and first charge/discharge efficiency, and ensures the reliability and safety of batteries under complex operating conditions.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of solid-state battery technology, specifically to a solid-state battery material for humanoid robots and its manufacturing process. Background Technology
[0002] As a new generation of intelligent equipment, humanoid robots are developing towards human-like movement capabilities, long-duration battery life, and high safety and reliability. This places performance requirements on their power sources far exceeding those of traditional lithium-ion batteries. Traditional liquid lithium-ion batteries suffer from safety hazards such as electrolyte leakage, flammability, and thermal runaway, and their energy density is generally below 350Wh / kg, making them unsuitable for the complex working conditions of humanoid robots. Solid-state batteries, which replace traditional liquid electrolytes and separators with solid electrolytes, offer significant advantages such as high energy density, good safety, and long cycle life, and are considered the core development direction for next-generation power batteries.
[0003] Currently, research on solid-state batteries focuses on two core issues: solid-state electrolyte materials and electrode-electrolyte interface compatibility. Solid-state electrolytes mainly include three categories: sulfides, oxides, and polymers. Polymer electrolytes have low ionic conductivity at room temperature, making them unsuitable for high-current charge-discharge requirements; oxide electrolytes, while chemically stable, are brittle, have high interfacial impedance, and poor compatibility with electrode materials; sulfide electrolytes possess high ionic conductivity and good processing performance, making them one of the most promising solid-state electrolyte systems for current applications. However, sulfide electrolytes such as Li7P3S... 11 It readily reacts with water and oxygen in the air to produce H2S gas, exhibiting poor chemical stability. Furthermore, it is prone to interfacial reactions when in contact with positive electrode materials, leading to a decline in battery cycle performance.
[0004] In terms of cathode materials, the energy density of traditional ternary materials and lithium iron phosphate materials has approached its theoretical limit, making it difficult to support the long-endurance requirements of humanoid robots. Lithium-rich manganese-based materials, due to their ultra-high theoretical specific capacity, have become a research hotspot for next-generation high-energy-density cathode materials. However, lithium-rich manganese-based materials suffer from problems such as low initial charge-discharge efficiency, severe voltage decay during cycling, and vigorous reactions at the electrolyte interface, limiting their application in solid-state batteries.
[0005] In terms of anode materials, silicon-based materials boast a theoretical specific capacity of up to 4200 mAh / g, more than 10 times that of traditional graphite anodes, making them crucial for improving battery energy density. However, silicon-based materials experience a volume expansion rate exceeding 300% during charge and discharge, easily leading to electrode structure pulverization and active material shedding. Furthermore, an unstable solid electrolyte interface film readily forms on the surface, severely impacting battery cycle life. In addition, the poor conductivity of silicon-based materials also limits their electrochemical performance.
[0006] Therefore, developing a solid electrolyte material with high ionic conductivity and good chemical stability, as well as positive and negative electrode materials with excellent compatibility, high capacity, and long cycle life, and matching them with an efficient manufacturing process, is of great significance for promoting the application of solid-state batteries in humanoid robots. Summary of the Invention
[0007] The purpose of this invention is to provide a solid-state battery material for humanoid robots and its manufacturing process, so as to solve the problems mentioned in the background art.
[0008] To achieve the above objectives, the present invention provides the following technical solution: a solid-state battery material for humanoid robots, comprising a composite positive electrode material, a sulfide-based composite solid electrolyte, and a modified negative electrode material, wherein the mass ratio of each component is: 45-55% composite positive electrode material, 8-12% sulfide-based composite solid electrolyte, and 35-45% modified negative electrode material.
[0009] The composite cathode material is composed of the following components by mass percentage: 80-85% lithium-rich manganese-based active material, 2-5% Li₂ZrO₃ coating layer, and Li₇P₃S. 11 Electrolyte particles 10-15%; the chemical formula of the lithium-rich manganese-based active material is Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O2, with a particle size of 1-3 μm;
[0010] The sulfide-based composite solid electrolyte is composed of the following components in mass percentage: Li7P3S 11 The matrix comprises 90-95% and Li3PO4-Al2O3 composite nanoparticles comprise 5-10%; the mass ratio of Li3PO4 to Al2O3 in the Li3PO4-Al2O3 composite nanoparticles is 1:2-3 and the particle size is 50-100 nm.
[0011] The modified negative electrode material is composed of Si-C composite particles and a TiN conductive layer, the thickness of which is 50-100 nm; the mass percentage of Si in the Si-C composite particles is 40-50%, and the particle size is 200-500 nm.
[0012] Preferably, the specific surface area of the lithium-rich manganese-based active material is 1.2-1.8 m². 2 / g, tap density is 2.8-3.2g / cm³ 3 .
[0013] Preferably, the Li7P3S 11 The matrix has a purity of ≥99.5%, a particle size of 100-200 nm, and a room temperature ionic conductivity of ≥8×10⁻⁶. -4S / cm.
[0014] Preferably, the C in the Si-C composite particles is amorphous carbon with a porous structure on its surface and a porosity of 15-20%.
[0015] A manufacturing process for solid-state battery materials for humanoid robots includes the following steps:
[0016] Step S1: Preparation of composite cathode material
[0017] S11: Mix LiOH·H2O, Mn(CH3COO)2·4H2O, Ni(CH3COO)2·4H2O, and Co(CH3COO)2·4H2O in stoichiometric ratios. 1.2 Mn 0.54 Ni 0.13 Co 0.13 O2 is dissolved in deionized water, and citric acid is added as a chelating agent. The molar ratio of citric acid to metal ions is 1.2:1. The pH value is adjusted to 7-8, and the mixture is stirred at 60-70℃ for 2-3 hours to form a sol.
[0018] S12: Dry the sol at 120-130℃ for 12-15h to obtain a dry gel. Heat the dry gel to 450-500℃ in air at a heating rate of 5℃ / min and hold for 3-4h. Then continue to heat to 850-900℃ and hold for 6-8h. After natural cooling, ball mill to a particle size of 1-3μm to obtain a lithium-rich manganese-based active material.
[0019] S13: Dissolve Zr(NO3)4·5H2O and LiNO3 in ethanol according to the stoichiometric ratio of Li2ZrO3, add polyvinylpyrrolidone as a dispersant, the mass of polyvinylpyrrolidone is 5-8% of the total mass of Zr(NO3)4·5H2O and LiNO3, and ultrasonically disperse for 30-40 min to obtain the coating solution.
[0020] S14: Add lithium-rich manganese-based active material to the coating solution, stir at 50-60℃ for 3-4h, then dry at 100-110℃ for 8-10h, raise the temperature to 600-650℃ in air at a heating rate of 3℃ / min, and keep at the temperature for 2-3h to obtain lithium-rich manganese-based material coated with Li2ZrO3.
[0021] S15: Lithium-rich manganese-based materials coated with Li2ZrO3 and Li7P3S 11 Electrolyte particles are mixed at a mass ratio of 85:15-80:20, anhydrous ethanol is added as a dispersion medium, ball milling is performed for 2-3 hours, and vacuum drying is carried out at 80-90℃ for 4-5 hours to obtain composite cathode material;
[0022] Step S2: Preparation of sulfide-based composite solid electrolyte
[0023] S21: Mix Li2S and P2S5 in a stoichiometric ratio of Li7P3S 11 The mixture was combined with anhydrous acetonitrile as the ball milling medium at a ball-to-material ratio of 20:1. The mixture was then ball-milled at a high-energy speed of 400-500 r / min for 20-24 h under inert gas protection to obtain amorphous Li7P3S. 11 Precursor;
[0024] S22: Mix Li3PO4 and Al2O3 at a mass ratio of 1:2-3, add anhydrous ethanol, ball mill for 10-12 h, and vacuum dry at 100-110℃ for 6-8 h to obtain Li3PO4-Al2O3 composite nanoparticles with a particle size of 50-100 nm.
[0025] S23: Amorphous Li7P3S 11 The precursor and Li3PO4-Al2O3 composite nanoparticles were mixed at a mass ratio of 95:5-90:10 and transferred into a mold under inert gas protection. The mixture was then subjected to hot pressing sintering at a temperature of 200-220℃ and a pressure of 25-30MPa for 2-3 hours. After natural cooling to room temperature, a sulfide-based composite solid electrolyte sheet with a thickness of 50-80μm was obtained.
[0026] Step S3: Preparation of modified anode material
[0027] S31: Mix Si powder and phenolic resin at a mass ratio of 4:6-5:5, add anhydrous ethanol, ball mill for 4-5 hours, dry at 120-130℃ for 8-10 hours, and then heat to 800-850℃ at a heating rate of 5℃ / min in an inert gas atmosphere and hold for 4-5 hours. The phenolic resin carbonizes to form amorphous carbon, thus obtaining Si-C composite particles.
[0028] S32: Si-C composite particles are uniformly spread on a magnetron sputtering target tray. Ti is used as the target material, and magnetron sputtering is performed in a mixed atmosphere of argon and nitrogen. The volume ratio of argon to nitrogen is 4:1, the sputtering power is 150-200W, the sputtering pressure is 0.3-0.5Pa, and the sputtering time is 30-60min. A TiN conductive layer is formed on the surface of the Si-C composite particles to obtain the modified anode material.
[0029] Step S4: Assembly of the full battery
[0030] S41: The composite cathode material and polyvinylidene fluoride are mixed at a mass ratio of 95:5, and N-methylpyrrolidone is added as a solvent. The mixture is stirred to form a cathode slurry. The cathode slurry is coated onto an aluminum foil current collector and vacuum dried at 120-130℃ for 12-15 hours. Then, it is rolled to obtain a cathode sheet with an areal density of 15-20 mg / cm³. 2 ;
[0031] S42: The modified negative electrode material is mixed with sodium carboxymethyl cellulose at a mass ratio of 98:2, and deionized water is added as a solvent. The mixture is stirred to prepare a negative electrode slurry. The negative electrode slurry is coated onto a copper foil current collector and vacuum dried at 100-110℃ for 10-12 hours. Then, it is rolled to obtain a negative electrode sheet with an areal density of 8-10 mg / cm³. 2 ;
[0032] S43: In an inert gas-protected glove box, the positive electrode sheet, sulfide-based composite solid electrolyte sheet, and negative electrode sheet are stacked in the order of "positive electrode sheet - sulfide-based composite solid electrolyte sheet - negative electrode sheet". The cold pressing process is adopted, with a cold pressing pressure of 15-20 MPa and a holding time of 10-15 min. Then, it is encapsulated in an aluminum-plastic film to obtain a solid battery for humanoid robots.
[0033] Preferably, the TiN conductive layer has a polycrystalline structure with a grain size of 5-20 nm and a volume resistivity ≤5×10⁻⁶. -7 Ω·m.
[0034] Preferably, in step S11, the pH value is adjusted using ammonia water, and the mass concentration of the ammonia water is 25-28%.
[0035] Preferably, the inert gas in steps S21 and S23 is argon with a purity ≥ 99.999%.
[0036] Preferably, the inert gas in step S31 is nitrogen with a purity ≥ 99.99%.
[0037] Preferably, the water and oxygen content in the glove box during step S43 is ≤0.1ppm.
[0038] Compared with the prior art, the beneficial effects of the present invention are:
[0039] 1. This invention significantly improves the overall performance of solid-state batteries for humanoid robots by using composite cathode materials, sulfide-based composite solid electrolytes, and modified anode materials. In the composite cathode material, the high specific capacity of the lithium-rich manganese-based active material, combined with the interfacial stabilizing effect of the Li₂ZrO₃ coating layer, effectively suppresses voltage decay and interfacial side reactions during cycling; Li₇P₃S 11 The introduction of electrolyte particles creates a three-dimensional ion transport network, which improves the ion diffusion rate of the cathode material.
[0040] 2. The sulfide-based composite solid electrolyte of the present invention, through the doping of Li3PO4-Al2O3 composite nanoparticles, significantly enhances the mechanical strength and chemical stability of the electrolyte while maintaining high ionic conductivity, thus solving the problem that traditional sulfide electrolytes are prone to interfacial reactions with cathode materials.
[0041] 3. In the modified anode material of this invention, the porous carbon structure of the Si-C composite particles provides a buffer space for the volume expansion of silicon, avoiding the pulverization of the electrode structure; the introduction of the TiN conductive layer greatly improves the electronic conductivity of the anode material and reduces the polarization effect; the cold pressing process and strict water and oxygen control ensure close contact between the electrode and electrolyte interface and reduce the interface impedance. Detailed Implementation
[0042] The technical solutions in the embodiments of the present invention will be clearly and completely described below. 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.
[0043] Example 1
[0044] A solid-state battery material for humanoid robots has the following mass ratio: 50% composite positive electrode material, 10% sulfide-based composite solid electrolyte, and 40% modified negative electrode material.
[0045] The composite cathode material is composed of the following components by mass percentage: lithium-rich manganese-based Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O2 83%, Li2ZrO3 coating 3%, Li7P3S 11 Electrolyte particles: 14%; Lithium-rich manganese-based material: particle size: 2 μm, specific surface area: 1.5 m². 2 / g, tap density is 3.0g / cm³ 3 .
[0046] The sulfide-based composite solid electrolyte is composed of the following components by mass percentage: Li7P3S 11 The matrix comprises 93% Li3PO4-Al2O3 composite nanoparticles, with a mass ratio of Li3PO4 to Al2O3 of 1:2.5 and a particle size of 80 nm; Li7P3S 11 The matrix has a purity of 99.6%, a particle size of 150 nm, and a room temperature ionic conductivity of 9 × 10⁻⁶. -4 S / cm.
[0047] The modified anode material consists of Si-C composite particles and a TiN conductive layer with a thickness of 80 nm. The Si-C composite particles contain 45% Si by mass, with a particle size of 350 nm. The C is amorphous carbon with a surface porosity of 18%.
[0048] The manufacturing process of the above-mentioned solid-state battery materials includes the following steps:
[0049] Step S1: Preparation of composite cathode material
[0050] S11: Mix LiOH·H2O, Mn(CH3COO)2·4H2O, Ni(CH3COO)2·4H2O, and Co(CH3COO)2·4H2O in stoichiometric ratios. 1.2 Mn 0.54 Ni 0.13 Co 0.13 O2 is dissolved in deionized water, and citric acid is added as a chelating agent. The molar ratio of citric acid to metal ions is 1.2:1. The pH value is adjusted to 7.5 using 26% ammonia water. The mixture is stirred at 65°C for 2.5 hours to form a sol.
[0051] S12: The sol was dried at 125℃ for 13h to obtain a dry gel. The dry gel was heated to 480℃ in air at a heating rate of 5℃ / min and held for 3.5h. Then the temperature was further increased to 880℃ and held for 7h. After natural cooling, the gel was ball-milled to a particle size of 2μm to obtain a lithium-rich manganese-based active material.
[0052] S13: Dissolve Zr(NO3)4·5H2O and LiNO3 in ethanol according to the stoichiometric ratio of Li2ZrO3, add polyvinylpyrrolidone as a dispersant, the mass of polyvinylpyrrolidone is 6% of the total mass of Zr(NO3)4·5H2O and LiNO3, and ultrasonically disperse for 35 min to obtain the coating solution.
[0053] S14: Add lithium-rich manganese-based active material to the coating solution, stir at 55℃ for 3.5h, then dry at 105℃ for 9h, raise the temperature to 620℃ in air at a heating rate of 3℃ / min, and hold for 2.5h to obtain lithium-rich manganese-based material coated with Li2ZrO3.
[0054] S15: Lithium-rich manganese-based materials coated with Li2ZrO3 and Li7P3S 11 Electrolyte particles were mixed at a mass ratio of 86:14, anhydrous ethanol was added as a dispersion medium, ball milled for 2.5 h, and vacuum dried at 85 °C for 4.5 h to obtain the composite cathode material.
[0055] Step S2: Preparation of sulfide-based composite solid electrolyte
[0056] S21: Mix Li2S and P2S5 in a stoichiometric ratio of Li7P3S 11 The mixture was combined with anhydrous acetonitrile as the ball milling medium at a ball-to-material ratio of 20:1. The mixture was then ball-milled at 450 r / min for 22 h under argon gas protection (99.999% purity) to obtain amorphous Li7P3S. 11 Precursor;
[0057] S22: Li ＝ PO4 and Al2O3 were mixed at a mass ratio of 1:2.5, anhydrous ethanol was added, the mixture was ball-milled for 11 h, and then vacuum dried at 105 °C for 7 h to obtain Li3PO4-Al2O3 composite nanoparticles with a particle size of 80 nm.
[0058] S23: Amorphous Li7P3S 11 The precursor and Li3PO4-Al2O3 composite nanoparticles were mixed at a mass ratio of 93:7 and transferred into a mold under the protection of 99.999% pure argon gas. The mixture was then subjected to a hot pressing sintering process at a temperature of 210℃ and a sintering pressure of 28MPa for 2.5 hours. After natural cooling to room temperature, a sulfide-based composite solid electrolyte sheet with a thickness of 65μm was obtained.
[0059] Step S3: Preparation of modified anode material
[0060] S31: Si powder and phenolic resin are mixed at a mass ratio of 45:55, anhydrous ethanol is added, ball milling is performed for 4.5 h, drying is carried out at 125 ℃ for 9 h, and then the temperature is raised to 820 ℃ at a heating rate of 5 ℃ / min in a nitrogen atmosphere with a purity of 99.99%, and held for 4.5 h. The phenolic resin is carbonized to form amorphous carbon, thus obtaining Si-C composite particles.
[0061] S32: Si-C composite particles are uniformly spread on a magnetron sputtering target tray. Ti is used as the target material. Magnetron sputtering is performed in a mixed atmosphere of argon and nitrogen. The volume ratio of argon to nitrogen is 4:1, the sputtering power is 180W, the sputtering pressure is 0.4Pa, and the sputtering time is 45min. A TiN conductive layer is formed on the surface of the Si-C composite particles to obtain the modified anode material.
[0062] Step S4: Assembly of the full battery
[0063] S41: The composite cathode material and polyvinylidene fluoride are mixed at a mass ratio of 95:5, N-methylpyrrolidone is added as a solvent, and the mixture is stirred to prepare a cathode slurry. The cathode slurry is coated onto an aluminum foil current collector, vacuum dried at 125°C for 13 hours, and then rolled to obtain a cathode sheet with an areal density of 18 mg / cm³. 2 ;
[0064] S42: The modified negative electrode material and sodium carboxymethyl cellulose were mixed at a mass ratio of 98:2, and deionized water was added as a solvent. The mixture was stirred to prepare a negative electrode slurry. The negative electrode slurry was coated onto a copper foil current collector and vacuum dried at 105℃ for 11 hours. Then, it was rolled to obtain a negative electrode sheet with an areal density of 9 mg / cm³. 2 ;
[0065] S43: In an argon glove box with water and oxygen content ≤0.1ppm, the electrodes are stacked in the order of “positive electrode - sulfide-based composite solid electrolyte sheet - negative electrode sheet”, and a cold pressing process is adopted. The cold pressing pressure is 18MPa and the holding time is 12min. Then, it is encapsulated in an aluminum-plastic film to obtain a solid battery for humanoid robots.
[0066] Example 2
[0067] A solid-state battery material for humanoid robots has the following mass ratio: 45% composite positive electrode material, 8% sulfide-based composite solid electrolyte, and 47% modified negative electrode material.
[0068] The composite cathode material is composed of the following components by mass percentage: lithium-rich manganese-based Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O2 85%, Li2ZrO3 coating 2%, Li7P3S 11 Electrolyte particles account for 13%; the lithium-rich manganese-based material has a particle size of 1 μm and a specific surface area of 1.2 m². 2 / g, tap density is 2.8g / cm³ 3 .
[0069] The sulfide-based composite solid electrolyte is composed of the following components by mass percentage: Li7P3S 11 95% matrix, 5% Li3PO4-Al2O3 composite nanoparticles; Li3PO4 to Al2O3 mass ratio 1:2, particle size 50nm; Li7P3S 11 The matrix has a purity of 99.5%, a particle size of 100 nm, and a room temperature ionic conductivity of 8 × 10⁻⁶. -4 S / cm.
[0070] The modified anode material consists of Si-C composite particles and a TiN conductive layer with a thickness of 50 nm. The Si-C composite particles contain 40% Si by mass, with a particle size of 200 nm. The C is amorphous carbon with a surface porosity of 15%.
[0071] The manufacturing process of the above solid-state battery material is the same as that in Example 1, except for the following parameters:
[0072] Step S11: Adjust the pH value to 7, the reaction temperature to 60℃, and the reaction time to 2 hours;
[0073] Step S12: Drying temperature 120℃, drying time 12h, pre-firing temperature 450℃, pre-firing time 3h, final firing temperature 850℃, final firing time 6h.
[0074] Step S23: Sintering temperature 200℃, sintering pressure 25MPa, holding time 2h, electrolyte sheet thickness 50μm;
[0075] Step S32: Sputtering power 150W, sputtering pressure 0.3Pa, sputtering time 30min;
[0076] Step S43: Cold pressing pressure 15MPa, holding time 10min.
[0077] Example 3
[0078] A solid-state battery material for humanoid robots has the following mass ratio: 55% composite positive electrode material, 12% sulfide-based composite solid electrolyte, and 33% modified negative electrode material.
[0079] The composite cathode material is composed of the following components by mass percentage: lithium-rich manganese-based Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O2 80%, Li2ZrO3 coating 5%, Li7P3S 11 Electrolyte particles 15%; lithium-rich manganese-based material with a particle size of 3 μm and a specific surface area of 1.8 m². 2 / g, tap density is 3.2g / cm³ 3 .
[0080] The sulfide-based composite solid electrolyte is composed of the following components by mass percentage: Li7P3S 11 90% matrix, 10% Li3PO4-Al2O3 composite nanoparticles; Li3PO4 to Al2O3 mass ratio 1:3, particle size 100nm; Li7P3S 11 The matrix has a purity of 99.7%, a particle size of 200 nm, and a room temperature ionic conductivity of 10 × 10⁻⁶. -4 S / cm.
[0081] The modified anode material consists of Si-C composite particles and a TiN conductive layer with a thickness of 100 nm. The Si-C composite particles contain 50% Si by mass, with a particle size of 500 nm, and C is amorphous carbon with a surface porosity of 20%.
[0082] The manufacturing process of the above solid-state battery material is the same as that in Example 1, except for the following parameters:
[0083] Step S11: Adjust the pH value to 8, the reaction temperature to 70℃, and the reaction time to 3 hours;
[0084] Step S12: Drying temperature 130℃, drying time 15h, pre-firing temperature 500℃, pre-firing time 4h, final firing temperature 900℃, final firing time 8h.
[0085] Step S23: Sintering temperature 220℃, sintering pressure 30MPa, holding time 3h, electrolyte sheet thickness 80μm;
[0086] Step S32: Sputtering power 200W, sputtering pressure 0.5Pa, sputtering time 60min;
[0087] Step S43: Cold pressing pressure 20MPa, holding time 15min.
[0088] Comparative Example 1
[0089] A solid-state battery material, whose composition and manufacturing process are basically the same as those in Example 1, except that the composite cathode material is not coated with Li2ZrO3.
[0090] Comparative Example 2
[0091] A solid-state battery material, whose composition and manufacturing process are basically the same as those in Example 1, except that the sulfide-based composite solid electrolyte is not doped with Li3PO4-Al2O3 composite nanoparticles.
[0092] Comparative Example 3
[0093] A solid-state battery material, whose composition and manufacturing process are basically the same as those in Example 1, except that the modified negative electrode material is not sputtered with a TiN conductive layer.
[0094] Test method:
[0095] (1) Ionic conductivity test: AC impedance method was used, with a frequency range of 10⁻¹⁰. 6 The test temperature was room temperature (25°C). The sulfide-based composite solid electrolyte sheet was sandwiched between two stainless steel electrodes to assemble a symmetrical cell for testing.
[0096] (2) Electrochemical performance test: The battery test system was used to conduct the first charge and discharge test at room temperature at a rate of 0.1C, with a voltage range of 2.0-4.8V; the cycle performance test was conducted at a rate of 0.5C, with 500 cycles.
[0097] (3) Safety performance testing: Needle penetration, compression, and thermal shock tests were conducted according to GB / T31485-2015 standard. The needle penetration test used a 3mm diameter steel needle to pierce the battery at a speed of 10mm / s; the compression test used a flat plate to compress the battery at a pressure of 100kN for 1 minute; the thermal shock test placed the battery in an oven at 130℃ for 30 minutes.
[0098] Test results:
[0099] The test results for each embodiment and comparative example are shown in Table 1.
[0100]
[0101]
[0102] Results analysis:
[0103] As shown in Table 1, the solid-state battery materials prepared in Examples 1-3 of this invention exhibit excellent overall performance. Among them, Example 1 demonstrates the best performance, with its sulfide-based composite solid electrolyte achieving a room-temperature ionic conductivity of 1.2 × 10⁻⁶. -3 The energy density is 492Wh / kg, with an initial charge / discharge efficiency of 89%, a 0.1C discharge specific capacity of 256mAh / g, a capacity retention rate of 93% after 500 cycles, and an energy density of 492Wh / kg, which is far higher than that of other parallel ratios.
[0104] In Comparative Example 1, the composite cathode material was not coated with Li2ZrO3, resulting in a violent interfacial reaction between the lithium-rich manganese-based material and the sulfide electrolyte, leading to a reduced initial charge-discharge efficiency and a cycle capacity retention rate of only 75%. Slight bulging was observed during the thermal shock test. In Comparative Example 2, the sulfide electrolyte was not doped with Li3PO4-Al2O3 composite nanoparticles, resulting in decreased ionic conductivity and chemical stability of the electrolyte, and lower cycle capacity retention rate and energy density compared to the example. In Comparative Example 3, the anode material was not sputtered with a TiN conductive layer, resulting in poor conductivity and interfacial compatibility, which reduced the battery's discharge specific capacity and cycle stability.
[0105] Safety test results of the various embodiments and comparative examples show that the solid-state batteries prepared by this invention, due to their all-solid-state structure, passed the needle penetration and extrusion tests without any fire or explosion. Examples 1-3 and Comparative Example 3 showed stability in the thermal shock test, while Comparative Examples 1 and 2 exhibited slight bulging due to the relatively intense interfacial reaction between the electrolyte and electrode during the thermal shock test. This further demonstrates the importance of the composite positive electrode material coating treatment, sulfide electrolyte doping with composite nanoparticles, and the sputtering of a conductive layer on the negative electrode material in improving the overall performance of the solid-state batteries. In summary, the solid-state battery material and manufacturing process for humanoid robots provided by this invention demonstrate significant advantages in multiple key indicators such as ionic conductivity, charge / discharge efficiency, cycle stability, energy density, and safety performance, and have broad application prospects and market value.
[0106] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.
[0107] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.
Claims
1. A solid-state battery material for humanoid robots, characterized in that, It includes composite cathode material, sulfide-based composite solid electrolyte and modified anode material, with the following mass ratio: composite cathode material 45-55%, sulfide-based composite solid electrolyte 8-12%, and modified anode material 35-45%. The composite cathode material is composed of the following components by mass percentage: 80-85% lithium-rich manganese-based active material, 2-5% Li₂ZrO₃ coating layer, and Li₇P₃S. 11 Electrolyte particles 10-15%, the chemical formula of the lithium-rich manganese-based active material is Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O2, with a particle size of 1-3 μm; The sulfide-based composite solid electrolyte is composed of the following components in mass percentage: Li7P3S 11 The matrix comprises 90-95% and Li3PO4-Al2O3 composite nanoparticles comprise 5-10%, wherein the mass ratio of Li3PO4 to Al2O3 in the Li3PO4-Al2O3 composite nanoparticles is 1:2-3 and the particle size is 50-100nm. The modified negative electrode material is composed of Si-C composite particles and a TiN conductive layer, wherein the thickness of the TiN conductive layer is 50-100 nm; the mass percentage of Si in the Si-C composite particles is 40-50%, and the particle size is 200-500 nm.
2. The solid-state battery material for humanoid robots according to claim 1, characterized in that: The specific surface area of the lithium-rich manganese-based active material is 1.2-1.8 m². 2 / g, tap density is 2.8-3.2g / cm³ 3 .
3. The solid-state battery material for humanoid robots according to claim 2, characterized in that: The Li7P3S 11 The matrix has a purity of ≥99.5%, a particle size of 100-200 nm, and a room temperature ionic conductivity of ≥8×10⁻⁶. -4 S / cm.
4. The solid-state battery material for humanoid robots according to claim 3, characterized in that: The C in the Si-C composite particles is amorphous carbon with a porous structure on its surface and a porosity of 15-20%.
5. A manufacturing process for a solid-state battery material for humanoid robots as described in any one of claims 1-4, characterized in that, Includes the following steps: Step S1: Preparation of composite cathode material S11: Mix LiOH·H2O, Mn(CH3COO)2·4H2O, Ni(CH3COO)2·4H2O, and Co(CH3COO)2·4H2O in stoichiometric ratios. 1.2 Mn 0.54 Ni 0.13 Co 0.13 O2 is dissolved in deionized water, and citric acid is added as a chelating agent. The molar ratio of citric acid to metal ions is 1.2:
1. The pH value is adjusted to 7-8, and the mixture is stirred at 60-70℃ for 2-3 hours to form a sol. S12: Dry the sol at 120-130℃ for 12-15h to obtain a dry gel. Heat the dry gel to 450-500℃ in air at a heating rate of 5℃ / min and hold for 3-4h. Then continue to heat to 850-900℃ and hold for 6-8h. After natural cooling, ball mill to a particle size of 1-3μm to obtain a lithium-rich manganese-based active material. S13: Dissolve Zr(NO3)4·5H2O and LiNO3 in ethanol according to the stoichiometric ratio of Li2ZrO3, add polyvinylpyrrolidone as a dispersant, the mass of polyvinylpyrrolidone is 5-8% of the total mass of Zr(NO3)4·5H2O and LiNO3, and ultrasonically disperse for 30-40 min to obtain the coating solution. S14: Add lithium-rich manganese-based active material to the coating solution, stir at 50-60℃ for 3-4h, then dry at 100-110℃ for 8-10h, raise the temperature to 600-650℃ in air at a heating rate of 3℃ / min, and keep at the temperature for 2-3h to obtain lithium-rich manganese-based material coated with Li2ZrO3. S15: Lithium-rich manganese-based materials coated with Li2ZrO3 and Li7P3S 11 Electrolyte particles are mixed at a mass ratio of 85:15-80:20, anhydrous ethanol is added as a dispersion medium, ball milling is performed for 2-3 hours, and vacuum drying is carried out at 80-90℃ for 4-5 hours to obtain composite cathode material; Step S2: Preparation of sulfide-based composite solid electrolyte S21: Mix Li2S and P2S5 in a stoichiometric ratio of Li7P3S 11 The mixture was combined with anhydrous acetonitrile as the ball milling medium at a ball-to-material ratio of 20:
1. The mixture was then ball-milled at a high-energy speed of 400-500 r / min for 20-24 h under inert gas protection to obtain amorphous Li7P3S. 11 Precursor; S22: Mix Li3PO4 and Al2O3 at a mass ratio of 1:2-3, add anhydrous ethanol, ball mill for 10-12 h, and vacuum dry at 100-110℃ for 6-8 h to obtain Li3PO4-Al2O3 composite nanoparticles with a particle size of 50-100 nm. S23: Amorphous Li7P3S 11 The precursor and Li3PO4-Al2O3 composite nanoparticles were mixed at a mass ratio of 95:5-90:10 and transferred into a mold under inert gas protection. The mixture was then subjected to hot pressing sintering at a temperature of 200-220℃ and a pressure of 25-30MPa for 2-3 hours. After natural cooling to room temperature, a sulfide-based composite solid electrolyte sheet with a thickness of 50-80μm was obtained. Step S3: Preparation of modified anode material S31: Mix Si powder and phenolic resin at a mass ratio of 4:6-5:5, add anhydrous ethanol, ball mill for 4-5 hours, dry at 120-130℃ for 8-10 hours, and then heat to 800-850℃ at a heating rate of 5℃ / min in an inert gas atmosphere and hold for 4-5 hours. The phenolic resin carbonizes to form amorphous carbon, thus obtaining Si-C composite particles. S32: Si-C composite particles are uniformly spread on a magnetron sputtering target tray. Ti is used as the target material, and magnetron sputtering is performed in a mixed atmosphere of argon and nitrogen. The volume ratio of argon to nitrogen is 4:1, the sputtering power is 150-200W, the sputtering pressure is 0.3-0.5Pa, and the sputtering time is 30-60min. A TiN conductive layer is formed on the surface of the Si-C composite particles to obtain the modified anode material. Step S4: Assembly of the full battery S41: The composite cathode material and polyvinylidene fluoride are mixed at a mass ratio of 95:5, and N-methylpyrrolidone is added as a solvent. The mixture is stirred to form a cathode slurry. The cathode slurry is coated onto an aluminum foil current collector and vacuum dried at 120-130℃ for 12-15 hours. Then, it is rolled to obtain a cathode sheet with an areal density of 15-20 mg / cm³. 2 ; S42: The modified negative electrode material is mixed with sodium carboxymethyl cellulose at a mass ratio of 98:2, and deionized water is added as a solvent. The mixture is stirred to prepare a negative electrode slurry. The negative electrode slurry is coated onto a copper foil current collector and vacuum dried at 100-110℃ for 10-12 hours. Then, it is rolled to obtain a negative electrode sheet with an areal density of 8-10 mg / cm³. 2 ; S43: In an inert gas-protected glove box, the positive electrode sheet, sulfide-based composite solid electrolyte sheet, and negative electrode sheet are stacked in the order of "positive electrode sheet - sulfide-based composite solid electrolyte sheet - negative electrode sheet". The cold pressing process is adopted, with a cold pressing pressure of 15-20 MPa and a holding time of 10-15 min. Then, it is encapsulated in an aluminum-plastic film to obtain a solid-state battery for humanoid robots.
6. The manufacturing process of the solid-state battery material for humanoid robots according to claim 5, characterized in that: The TiN conductive layer has a polycrystalline structure with a grain size of 5-20 nm and a volume resistivity of ≤5×10⁻⁶. -7 Ω·m.
7. The manufacturing process of the solid-state battery material for humanoid robots according to claim 6, characterized in that: In step S11, the pH value is adjusted using ammonia water with a mass concentration of 25-28%.
8. The manufacturing process of the solid-state battery material for humanoid robots according to claim 7, characterized in that: The inert gas used in steps S21 and S23 is argon.
9. The manufacturing process of the solid-state battery material for humanoid robots according to claim 8, characterized in that: The inert gas in step S31 is nitrogen.
10. The manufacturing process of the solid-state battery material for humanoid robots according to claim 9, characterized in that: In step S43, the water and oxygen content in the glove box is ≤0.1ppm.