WO2024250186A1 - 高熵氧化物掺杂包覆共修饰的正极材料、制备方法及应用 - Google Patents

高熵氧化物掺杂包覆共修饰的正极材料、制备方法及应用 Download PDF

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WO2024250186A1
WO2024250186A1 PCT/CN2023/098757 CN2023098757W WO2024250186A1 WO 2024250186 A1 WO2024250186 A1 WO 2024250186A1 CN 2023098757 W CN2023098757 W CN 2023098757W WO 2024250186 A1 WO2024250186 A1 WO 2024250186A1
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Prior art keywords
positive electrode
electrode material
entropy oxide
high entropy
coated
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English (en)
French (fr)
Inventor
程江辉
李长东
阮丁山
刘伟健
汪乾
黄耀良
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Priority to CN202380009340.8A priority Critical patent/CN117223124A/zh
Priority to PCT/CN2023/098757 priority patent/WO2024250186A1/zh
Publication of WO2024250186A1 publication Critical patent/WO2024250186A1/zh
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • the present disclosure relates to the technical field of positive electrode materials for sodium ion batteries, and in particular to a positive electrode material doped with a high entropy oxide and co-modified with a coating, and a preparation method and application thereof.
  • Sodium-ion batteries have attracted much attention in large-scale energy storage systems due to their low cost and abundant sodium resources.
  • O3-type layered transition metal oxide cathode materials have high theoretical capacity and simple structure, making them one of the best choices for cathode materials for sodium-ion batteries.
  • the transition metal layer is prone to relative slip and distortion, resulting in structural rearrangement and complex phase transitions, leading to low battery energy efficiency and poor cycle stability.
  • the purpose of the present disclosure is to provide a high entropy oxide doped, coated and co-modified positive electrode material, a preparation method and an application, so as to overcome the problem that the O3 type layered transition metal oxide positive electrode material is used in sodium ion batteries, and the battery energy efficiency is low and the cycle stability is poor.
  • the present disclosure provides a high entropy oxide doped and coated co-modified positive electrode material, comprising a substrate and a high entropy oxide, wherein part of the high entropy oxide is coated on the surface of the substrate to form a coating layer, and part of the high entropy oxide enters the surface layer of the substrate to form a doping layer;
  • said T is Fe.
  • the high entropy oxide is a nanoscale high entropy oxide.
  • the particle size of the high entropy oxide is less than 200 nm.
  • the mass fraction of the high entropy oxide in the positive electrode material is less than 5%.
  • the cathode material D50 is 5um-10um.
  • the present disclosure provides a method for preparing a high entropy oxide doped, coated and co-modified positive electrode material as described in any one of the aforementioned embodiments, comprising sintering a substrate having a high entropy oxide attached to the surface to obtain the high entropy oxide doped, coated and co-modified positive electrode material.
  • the method further includes preparing a substrate having a high entropy oxide attached to its surface: the method includes heating a mixed solution of a substrate, a metal salt and a solvent to obtain a substrate having a high entropy oxide attached to its surface.
  • the mass fraction of the substrate in the mixed solution is 25%-35%, and the mass fraction of the metal salt is 3.5%-4.5%.
  • the heating temperature is 60° C.-150° C.
  • the insulation time is 1 h-6 h.
  • the step of preparing the substrate with a high entropy oxide attached to the surface is carried out in a closed reactor.
  • the preparation process of the substrate having the high entropy oxide attached to the surface is accompanied by stirring.
  • the stirring speed is 100 rpm-500 rpm.
  • the stirring is performed by intermittent stirring.
  • stirring is performed for 50s-70s each time, with an interval of 8min-12min.
  • the metal salt is 5 or more of Li salts, Na salts, Mg salts, Ca salts, Al salts, Zn salts, Sc salts, Ti salts, V salts, Cr salts, Mn salts, Fe salts, Co salts, Y salts, Zr salts, Nb salts, Mo salts, Ga salts, Te salts, Sb salts, In salts, and Sn salts.
  • the metal salt is at least one of a nitrate and a chloride salt.
  • the solvent is ethanol, oleylamine and hexane in a ratio of 1:(0.9-1.1):(2.5-3.5).
  • reaction liquid is further subjected to solid-liquid separation, and the separated solid phase is dried.
  • the drying temperature is 75° C.-85° C., and the drying time is greater than 8 hours.
  • the temperature of the sintering step is 800° C.-1100° C., and the holding time is 4 h-15 h.
  • the temperature of the sintering step is 880° C.-980° C.
  • the holding time is 8 h-15 h.
  • the sintering atmosphere is air or oxygen.
  • the method further includes a step of preparing a substrate, comprising sintering a mixture of an oxide and a sodium source to obtain a substrate.
  • the oxide includes at least one of nickel oxide, manganese oxide, chromium oxide, iron oxide, vanadium oxide and titanium oxide.
  • the sodium source is one or more of sodium carbonate, sodium hydroxide, sodium oxide, and sodium peroxide.
  • the sintering temperature is 800° C.-1000° C.
  • the sintering time is 6 h-24 h.
  • the sintering temperature is 850° C.-950° C.
  • the holding time is 8 h-15 h.
  • the present disclosure provides an application of the positive electrode material described in any one of the aforementioned embodiments or the positive electrode material obtained by the method described in any one of the aforementioned embodiments in a sodium ion battery.
  • the present disclosure provides an electrode, comprising the positive electrode material described in any one of the aforementioned embodiments or the positive electrode material obtained by the method described in any one of the aforementioned embodiments.
  • the present disclosure provides a sodium ion battery comprising the electrode described in the aforementioned embodiment.
  • the present disclosure provides an electrical device comprising the sodium ion battery described in the aforementioned embodiment.
  • the high entropy oxide disclosed in the present invention is a single-phase solid solution material in which multiple metal elements share the same atomic site and the cations are randomly distributed. Due to the disorder of the metal layer, the metal elements tend to undergo redox reactions more randomly, which can inhibit Na + /vacancy order and charge order, delay or inhibit phase change, and improve the rate performance and cycle stability of the electrode material.
  • the presence of high entropy oxide in the coating layer disclosed in the present invention can react with part of the residual alkali and improve the conductivity. At the same time, the coating also has a certain electrochemical activity to ensure that the capacity is not lost.
  • the high entropy oxide itself has good structural stability and ionic conductivity, which is beneficial to improve the stability of the positive electrode material and reduce side reactions, while improving the transmission capacity of sodium ions.
  • Fig. 1 is a flow chart of Example 1
  • FIG2 is a SEM of the dried material in step 3 of Example 1;
  • FIG3 is a SEM of the positive electrode substrate of Example 1;
  • FIG4 is a SEM of a positive electrode substrate coated with a high entropy oxide in Example 1.
  • Some embodiments of the present disclosure provide a high entropy oxide doped and coated co-modified positive electrode material, comprising a substrate and a high entropy oxide, wherein part of the high entropy oxide is coated on the surface of the substrate to form a coating layer, and part of the high entropy oxide enters the surface layer of the substrate to form a doping layer;
  • the high entropy oxide in this embodiment is a single-phase solid solution material in which multiple metal elements share the same atomic site and the cations are randomly distributed. Due to the disorder of the metal layer, the metal elements tend to undergo random redox reactions, which can inhibit Na + /vacancy order and charge order, delay or inhibit phase change, and improve the rate performance and cycle stability of the electrode material. In addition, there are five or more metal elements in the high entropy oxide, among which the doping amount of elements other than A, B, C, D, and E is relatively low, and a small amount of doping is more conducive to inhibiting Na + /vacancy order and charge order.
  • the presence of high entropy oxide in the coating layer can react with part of the residual alkali and improve the conductivity.
  • the coating also has a certain electrochemical activity to ensure that the capacity is not lost.
  • the high entropy oxide itself has good structural stability and ionic conductivity, which is beneficial to improve the stability of the positive electrode material and reduce side reactions, while improving the transmission capacity of sodium ions.
  • m 0.
  • the T is Fe.
  • the high entropy oxide is a nanoscale high entropy oxide.
  • Nanoscale high entropy oxide is more likely to partially enter the crystal surface of the substrate during high temperature reaction, which is beneficial to increase the content of high entropy oxide nanocrystals in the doping layer, and is also beneficial for the high entropy oxide to be uniformly coated on the surface of the positive electrode material.
  • Part of the high entropy oxide nanocrystals are doped into the bulk phase at high temperature, which is beneficial to improve the stability of the positive electrode material during the charge and discharge process.
  • the particle size of the high entropy oxide is less than 200 nm.
  • the mass fraction of the high entropy oxide in the positive electrode material is less than 5%.
  • the mass fraction of the high entropy oxide can be calculated based on the amount of metal salt and substrate added.
  • the low content of high entropy oxide has limited improvement on the rate capability and cycle stability of the material, but too high a content will also affect the capacity of the material.
  • the cathode material D50 is 5um-10um.
  • the present disclosure provides a method for preparing a high entropy oxide doped, coated and co-modified positive electrode material as described in any one of the aforementioned embodiments, comprising sintering a substrate having a high entropy oxide attached to the surface to obtain the high entropy oxide doped, coated and co-modified positive electrode material.
  • the preparation of a substrate with a high entropy oxide attached to the surface is also included: the mixed solution of the substrate, the metal salt and the solvent is heated to obtain a substrate with a high entropy oxide attached to the surface. It is difficult to achieve in-situ generation and uniform coating of the high entropy oxide in the solid phase method for preparing a substrate with a high entropy oxide attached to the surface, resulting in unsatisfactory improvement in the rate performance and cycle stability of the final product.
  • This embodiment generates a mixture of high entropy oxide and substrate by a solvothermal method.
  • the nanoscale high entropy oxide attached to the surface of the substrate is more uniform, which is more conducive to the nanoscale high entropy oxide entering the crystal surface during the high temperature reaction, and is also conducive to the uniform coating of the nanoscale high entropy oxide on the surface of the positive electrode material.
  • the mass fraction of the substrate in the mixed solution is 25%-35%, and the mass fraction of the metal salt is 3.5%-4.5%. If the concentration of the substrate and the metal salt in the mixed solution is too low, it is not conducive to improving the reaction efficiency. If the concentration is too high, it will affect the chemical equilibrium and the stable reaction, thereby affecting the uniformity of the high entropy oxide dispersion, thereby increasing the particle size of the high entropy oxide or reducing the uniformity of the particle size distribution of the high entropy oxide.
  • the heating temperature is 60°C-150°C
  • the holding time is 1h-6h.
  • the extension of the holding time and the heating temperature being too high or too low may cause the crystal size of the high entropy oxide to change, which is not conducive to the uniform doping and coating of the high entropy oxide.
  • the step of preparing the substrate with a high entropy oxide attached to the surface is carried out in a closed reactor, which may have a certain pressure under the elevated temperature conditions, which is conducive to the formation of high entropy oxide nanocrystals.
  • the preparation process of the substrate with a high entropy oxide attached to the surface is accompanied by stirring. Stirring can prevent the substrate from sinking to the bottom, and is conducive to relatively uniform dispersion of the substrate in the mixed solution, coordinating the uniformly dispersed nano high-entropy oxide, thereby promoting uniform coating of the generated high-entropy oxide.
  • the stirring speed is 100rpm-500rpm. If the stirring speed is too slow, the substrate and nano high-entropy oxide cannot be evenly dispersed in the mixed solution. If the stirring speed is too fast, it may affect the chemical equilibrium state of the solution, thereby affecting the combination of the high-entropy oxide and the substrate, which is not conducive to the uniform coating of the high-entropy oxide on the surface of the substrate.
  • the stirring is intermittent stirring. Long-term stirring will also affect the chemical equilibrium state of the solution, thereby affecting the combination of the high entropy oxide and the substrate, which is not conducive to the uniform coating of the high entropy oxide on the surface of the substrate.
  • stirring is performed for 50s-70s each time, with an interval of 8min-12min.
  • the metal salt is 5 or more of Li salts, Na salts, Mg salts, Ca salts, Al salts, Zn salts, Sc salts, Ti salts, V salts, Cr salts, Mn salts, Fe salts, Co salts, Y salts, Zr salts, Nb salts, Mo salts, Ga salts, Te salts, Sb salts, In salts, and Sn salts.
  • the metal salt is at least one of a nitrate and a chloride salt.
  • the solvent is ethanol, oleylamine and hexane in a ratio of 1:(0.9-1.1):(2.5-3.5).
  • the ethanol is used as a solvent
  • hexane is used as a solvent and dispersant, so that other solvents, substrates and generated high entropy oxide nanoparticles are evenly dispersed in the solvent
  • oleylamine is a stabilizer, which can slow down the reaction, maintain chemical balance, prevent nanoparticles from agglomerating, and make the nanoparticles evenly and slowly generated
  • ethanol, oleylamine and hexane are matched in proportion to obtain nanoscale high entropy oxides evenly dispersed in the solvent.
  • reaction liquid is further subjected to solid-liquid separation, and the separated solid phase is dried.
  • the drying temperature is 75°C-85°C, and the drying time is greater than 8 hours.
  • rotary vacuum drying or normal pressure drying is used, but negative pressure is conducive to quickly removing moisture to prepare for subsequent sintering.
  • the temperature of the sintering step is 800° C.-1100° C.
  • the holding time is 4 h-15 h.
  • the temperature of the sintering step is 880° C.-980° C.
  • the holding time is 8 h-15 h.
  • the sintering atmosphere is air or oxygen.
  • the method further includes a step of preparing a substrate, including sintering a mixture of an oxide and a sodium source to obtain a substrate.
  • the oxide includes at least one of nickel oxide, manganese oxide, chromium oxide, iron oxide, vanadium oxide and titanium oxide.
  • the sodium source is one or more of sodium carbonate, sodium hydroxide, sodium oxide, and sodium peroxide.
  • the sintering temperature is 800° C.-1000° C.
  • the sintering time is 6 h-24 h.
  • the sintering temperature is 850° C.-950° C.
  • the holding time is 8 h-15 h.
  • the present disclosure provides an application of the positive electrode material described in any one of the aforementioned embodiments or the positive electrode material obtained by the method described in any one of the aforementioned embodiments in a sodium ion battery.
  • the present disclosure provides an electrode, comprising the positive electrode material described in any one of the aforementioned embodiments or the positive electrode material obtained by the method described in any one of the aforementioned embodiments.
  • the present disclosure provides a sodium ion battery comprising the electrode described in the aforementioned embodiment.
  • the present disclosure provides an electrical device comprising the sodium ion battery described in the aforementioned embodiment.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • This embodiment provides a method for doping and coating a high entropy oxide to co-modify a sodium ion positive electrode material, as shown in FIG1 , comprising the following steps:
  • Step 1 nickel oxide, manganese trioxide, zinc oxide and sodium carbonate are mixed in a molar ratio of Ni, Mn, Zn and Na of 0.20:0.7:0.1:0.95, which is recorded as mixture A;
  • Step 2 Sinter at 880°C for 12 hours in air atmosphere to obtain substrate B, the morphology of which is shown in FIG3 .
  • Step 3 Add copper nitrate trihydrate, zinc nitrate hexahydrate, iron nitrate nonahydrate, cerium nitrate hexahydrate, and zirconium chloride into a conical flat-bottom beaker, wherein the molar ratio of copper, zinc, iron, cerium, and zirconium elements is approximately 1:1:1:1:1, and then add 30g of substrate B so that the theoretical maximum mass fraction of high entropy oxide in the positive electrode material is 5%, and then add 100ml of ethanol, oleylamine, and hexane in a volume ratio of 1:1:3, put in a magnet, seal the beaker, place it on a ceramic heating table, react at 100°C for 120min, stir at a speed of 150rpm, stir for 1min, stir once every 10min, filter after the reaction, and perform rotary vacuum drying on the solid phase at a drying temperature of 80°C and a rotation speed of 200rpm to obtain material C, the morphology of which is shown in
  • Step 4 Material C is sintered at 900°C for 10 hours in an air atmosphere to obtain a positive electrode material with a high entropy coating, the morphology of which is shown in FIG4 .
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • This embodiment provides a method for high entropy oxide doping, coating and co-modifying a sodium ion positive electrode material, comprising the following steps:
  • Step 1 nickel oxide, manganese trioxide, zinc oxide and sodium carbonate are mixed in a molar ratio of Ni, Mn, Zn and Na of 0.20:0.7:0.1:0.95, which is recorded as mixture A;
  • Step 2 Sinter at 880°C for 12 hours in an air atmosphere to obtain substrate B.
  • Step 3 Add copper nitrate trihydrate, zinc nitrate hexahydrate, cerium nitrate hexahydrate, zirconium chloride, and nickel chloride hexahydrate into a conical flat-bottomed beaker, wherein the molar ratio of copper, zinc, cerium, zirconium, and nickel elements is approximately 1:1:1:1:1, and then add 30 g of substrate B so that the theoretical maximum mass fraction of high entropy oxide in the positive electrode material is 5%, and then add 100 ml of ethanol, oleylamine, and hexane in a volume ratio of 1:1:3, put in a magnet, seal the beaker, place it on a ceramic heating table, react at 100°C for 120 min, stir at a speed of 150 rpm, stir for 1 min, stir once every 10 min, filter after the reaction, and perform rotary vacuum drying on the solid phase at a drying temperature of 80°C and a rotation speed of 200 rpm to obtain material C.
  • Step 4 Sinter material C at 900°C for 10 hours in an air atmosphere to obtain a positive electrode material with a high entropy coating.
  • Embodiment 3 is a diagrammatic representation of Embodiment 3
  • This embodiment provides a method for doping and coating high entropy oxides to co-modify sodium ion positive electrode materials.
  • the only difference from Embodiment 1 is that in step 3, ethanol, oleylamine and hexane are added in a volume ratio of 1:0.9:2.5.
  • Embodiment 4 is a diagrammatic representation of Embodiment 4:
  • This embodiment provides a method for doping and coating a high entropy oxide to co-modify a sodium ion positive electrode material.
  • the only difference from Embodiment 1 is that in step 3, ethanol, oleylamine and hexane are added in a volume ratio of 1:1.1:3.5.
  • Embodiment 5 is a diagrammatic representation of Embodiment 5:
  • This embodiment provides a method for high entropy oxide doping, coating and co-modification of sodium ion positive electrode materials, which is different from Embodiment 1 only in that, in step 3, stirring is continued at a speed of 150 rpm.
  • Embodiment 6 is a diagrammatic representation of Embodiment 6
  • This embodiment provides a method for doping and coating high entropy oxides to co-modify sodium ion positive electrode materials.
  • the only difference from Embodiment 1 is that in step 3, the stirring speed is 500 rpm.
  • Embodiment 7 is a diagrammatic representation of Embodiment 7:
  • This embodiment provides a method for doping and coating high entropy oxides to co-modify sodium ion positive electrode materials.
  • the only difference from Embodiment 1 is that in step 3, the stirring speed is 100 rpm.
  • Embodiment 8 is a diagrammatic representation of Embodiment 8
  • This embodiment provides a method for doping and coating high entropy oxides to co-modify sodium ion positive electrode materials.
  • the only difference from Embodiment 1 is that in step 3, the stirring time is 50 seconds, and the stirring is performed every 12 minutes.
  • Embodiment 9 is a diagrammatic representation of Embodiment 9:
  • This embodiment provides a method for doping and coating high entropy oxides to co-modify sodium ion positive electrode materials.
  • the only difference from Embodiment 1 is that in step 3, the stirring time is 70 seconds, and the stirring is performed every 8 minutes.
  • Embodiment 10 is a diagrammatic representation of Embodiment 10:
  • This embodiment provides a method for high entropy oxide doping, coating and co-modification of sodium ion positive electrode materials.
  • the only difference from Embodiment 1 is that in step 3, the beaker is sealed and placed on a ceramic heating table to react at 60° C. for 120 minutes.
  • Embodiment 11 is a diagrammatic representation of Embodiment 11:
  • This embodiment provides a method for high entropy oxide doping, coating and co-modification of sodium ion positive electrode materials.
  • the only difference from Embodiment 1 is that in step 3, the beaker is sealed and placed on a ceramic heating table to react at 150° C. for 120 minutes.
  • Embodiment 12 is a diagrammatic representation of Embodiment 12
  • This embodiment provides a method for high entropy oxide doping, coating and co-modification of sodium ion positive electrode materials.
  • the only difference from Embodiment 1 is that in step 3, the beaker is sealed and placed on a ceramic heating table to react at 100° C. for 6 hours.
  • Embodiment 13 is a diagrammatic representation of Embodiment 13:
  • the present embodiment provides a method for doping, coating and co-modifying a sodium ion positive electrode material with a high entropy oxide.
  • the only difference from Example 1 is that in step 3, copper nitrate, zinc nitrate, iron nitrate, cerium nitrate, zirconium chloride and nickel chloride are added to a conical flat-bottomed beaker in an element molar ratio of 1:1:1:1:1:1 (the total molar amount of metal elements is equal to that in Example 1).
  • Embodiment 14 is a diagrammatic representation of Embodiment 14:
  • the present embodiment provides a method for doping, coating and co-modifying a sodium ion positive electrode material with a high entropy oxide.
  • the only difference from Example 1 is that in step 3, copper nitrate, zinc nitrate, iron nitrate, cerium nitrate, zirconium chloride and nickel chloride are added to a conical flat-bottomed beaker at an element molar ratio of 1:1:1:1:1:0.015 (the total molar amount of metal elements is the same as that in Example 1).
  • Embodiment 15 is a diagrammatic representation of Embodiment 15:
  • This embodiment provides a method for high entropy oxide doping, coating and co-modification of sodium ion positive electrode materials.
  • the only difference from Embodiment 1 is that in step 3, the beaker is sealed and placed on a ceramic heating table to react at 100° C. for 1 hour.
  • Embodiment 16 is a diagrammatic representation of Embodiment 16:
  • This embodiment provides a method for high entropy oxide doping, coating and co-modification of sodium ion positive electrode materials, which is different from Embodiment 1 only in that in step 4, the sintering temperature is 1100°C.
  • Embodiment 17 is a diagrammatic representation of Embodiment 17:
  • This embodiment provides a method for high entropy oxide doping, coating and co-modification of sodium ion positive electrode materials, which is different from Embodiment 1 only in that, in step 4, the sintering temperature is 800°C.
  • Embodiment 18 is a diagrammatic representation of Embodiment 18:
  • This embodiment provides a method for doping and coating a high entropy oxide to co-modify a sodium ion positive electrode material.
  • the difference from Embodiment 1 is that in step 3, copper nitrate, zinc nitrate, iron nitrate, cerium nitrate, and zirconium chloride are mixed at an element molar ratio of 0.25: 0.25:0.25:0.15:0.15 were added into a conical flat-bottom beaker (the total molar amount of metal elements is equal to that in Example 1).
  • Embodiment 19 is a diagrammatic representation of Embodiment 19:
  • This embodiment provides a method for doping, coating and co-modifying a sodium ion positive electrode material with a high entropy oxide.
  • the only difference from Example 1 is that in step 3, copper nitrate, zinc nitrate, iron nitrate, cerium nitrate and zirconium chloride are added to a conical flat-bottomed beaker according to an element molar ratio of 0.15:0.15:0.25:0.25:0.25 (the total molar amount of metal elements is equal to that in Example 1).
  • Embodiment 20 is a diagrammatic representation of Embodiment 20.
  • the present embodiment provides a method for doping and coating a high entropy oxide to co-modify a sodium ion positive electrode material.
  • the method differs from the embodiment 1 only in that, in step 1, the composition of the mixed material A is adjusted so that in step 2, Na 0.9 Ni 0.2 Mn 0.6 Fe 0.2 O 2 and Na 0.73 Ni 0.6 Co 0.05 Mn 0.35 O 2 are obtained respectively; or, in step 3, Cu 0.125 Zn 0.125 Fe 0.125 Ce 0.125 Zr 0.125 Ni 0.125 Co 0.125 Cr 0.125 O 2 and Mg 0.2 Al 0.2 Ni 0.2 Zn 0.2 Ti 0.2 O 2 are obtained respectively.
  • the 1C/0.1C is improved to a certain extent compared with the substrate, and the capacity retention rate after 100 cycles of 1C is increased by more than 5%.
  • This comparative example provides a method for doping and coating a high entropy oxide to co-modify a sodium ion positive electrode material, comprising the following steps:
  • Step 1 nickel oxide, manganese trioxide, zinc oxide and sodium carbonate are mixed in a molar ratio of Ni, Mn, Zn and Na of 0.20:0.7:0.1:0.95, which is recorded as mixture A;
  • Step 2 Sinter at 880°C for 12 hours in an air atmosphere to obtain substrate B.
  • Step 3 Add 2.02g zinc nitrate hexahydrate and 1.58g zirconium chloride into a conical flat-bottom beaker, add 30g substrate B, so that the theoretical maximum mass fraction of the high entropy oxide in the positive electrode material is 5%, then add 100ml of ethanol, oleylamine and hexane in a volume ratio of 1:1:3, put in a magnet, seal the beaker, place it on a ceramic heating table, react at 100°C for 120min, stir at a speed of 150rpm, stir for 1min, stir once every 10min, filter and dry after the reaction to obtain material C.
  • Step 4 Sinter material C at 900°C for 10 hours in an air atmosphere to obtain a positive electrode material with a high entropy coating.
  • This comparative example provides a method for doping and coating a high entropy oxide to co-modify a sodium ion positive electrode material, comprising the following steps:
  • Step 1 nickel oxide, manganese trioxide, zinc oxide and sodium carbonate are mixed in a molar ratio of Ni, Mn, Zn and Na of 0.20:0.7:0.1:0.95, which is recorded as mixture A;
  • Step 2 Sinter at 880°C for 12 hours in an air atmosphere to obtain substrate B.
  • Step 3 Mix B evenly using a mixer, sinter at 900°C for 10 hours in an air atmosphere to obtain Na 0.95 Ni 0.2 Zn 0.1 Mn 0.7 O 2 positive electrode material.
  • This comparative example provides a method for doping and coating a high entropy oxide to co-modify a sodium ion positive electrode material, comprising the following steps:
  • Step 1 nickel oxide, manganese trioxide, zinc oxide and sodium carbonate are mixed in a molar ratio of Ni, Mn, Zn and Na of 0.20:0.7:0.1:0.95, which is recorded as mixture A;
  • Step 2 Sinter at 880°C for 12 hours in an air atmosphere to obtain substrate B.
  • Step 3 Add 30 g of substrate B into a conical flat-bottom beaker, add substrate B, and then add 100 ml of ethanol, oleylamine and hexane in a volume ratio of 1:1:3, seal the beaker, place it on a heating table and react at 100°C for 120 minutes. After the reaction is complete, filter and dry to obtain material C.
  • Step 4 Sinter material C at 900°C in an air atmosphere for 10 hours to obtain an uncoated positive electrode material.
  • This comparative example provides a method for doping and coating high entropy oxides to co-modify sodium ion positive electrode materials.
  • the only difference from Example 1 is that in step 3, cerium nitrate, zirconium chloride, and nickel chloride are added to a conical flat-bottomed beaker in an element molar ratio of 1:1:1 (the total molar amount of metal elements is equal to that in Example 1).
  • This comparative example provides a method for doping and coating high-entropy oxides to co-modify sodium ion positive electrode materials.
  • the only difference from Example 1 is that in step 3, copper nitrate, zinc nitrate, iron nitrate, and cerium nitrate are added to a conical flat-bottomed beaker according to an element molar ratio of 1:1:1:1 (the total molar amount of metal elements is equal to that in Example 1).
  • This comparative example provides a method for doping and coating a high entropy oxide to co-modify a sodium ion positive electrode material.
  • the difference from Example 1 is that in step 3, ethanol, oleylamine and hexane are added in a volume ratio of 1:0.5:4.
  • This comparative example provides a method for doping and coating a high entropy oxide to co-modify a sodium ion positive electrode material.
  • the difference from Example 1 is that in step 3, ethanol, oleylamine and hexane are added in a volume ratio of 1:1.5:2.
  • This comparative example provides a method for doping and coating high entropy oxides to co-modify sodium ion positive electrode materials.
  • the only difference from comparative example 1 is that in step 3, the stirring speed is 1000 rpm.
  • This comparative example provides a method for high entropy oxide doping, coating and co-modification of sodium ion positive electrode materials.
  • the only difference from comparative example 1 is that in step 3, the beaker is sealed and placed on a ceramic heating table to react at 100° C. for 10 hours.
  • This comparative example provides a method for high entropy oxide doping, coating and co-modification of sodium ion positive electrode materials.
  • the only difference from comparative example 1 is that in step 3, the beaker is sealed and placed on a ceramic heating table to react at 30° C. for 120 minutes.
  • This comparative example provides a method for high entropy oxide doping, coating and co-modification of sodium ion positive electrode materials.
  • the only difference from comparative example 1 is that in step 3, the beaker is sealed and placed on a ceramic heating table to react at 180° C. for 120 minutes.
  • This comparative example provides a method for doping and coating high entropy oxides to co-modify sodium ion positive electrode materials.
  • the only difference from Example 1 is that in step 3, the stirring time is 30 seconds, and the stirring is performed once every 15 minutes.
  • This comparative example provides a method for doping and coating high entropy oxides to co-modify sodium ion positive electrode materials.
  • the only difference from Example 1 is that in step 3, the stirring time is 90 seconds, and the stirring is performed every 5 minutes.
  • the positive electrode materials obtained in the above embodiments and comparative examples are prepared into button batteries, specifically including: 1 preparing slurry, weighing materials and conductive agents, and mixing binders, wherein the mass ratio of materials: conductive agents: binders is 8:1:1, the binder used is PVDF, and the conductive agent is conductive carbon; 2 coating, using a scraper to coat on aluminum foil; 3 drying, drying the coated electrode in a vacuum drying oven, the drying temperature is 120°C, and the drying time is 4h; 4 pressing, pressing the dried electrode using a roller machine; 5 assembling the positive electrode, negative electrode, diaphragm, electrolyte and other battery parts into button batteries. Then the electrical performance of the battery is tested, the test voltage is 1.5-4.2V, and the test temperature is 25°C, and Table 1 is obtained.
  • Table 1 shows the electrical properties of the batteries prepared by the implementation cases and comparative examples. It can be seen from Examples 1-2 and Comparative Example 2 that the results show that the high-entropy oxide modification of the sodium ion positive electrode material has a beneficial effect, especially for the rate performance and cycle performance. It can be seen from Example 1 and Comparative Examples 1-2 that the high-entropy material has a more obvious effect on the performance improvement than the direct coating of the oxide, which may be due to the more stable structure of the high-entropy oxide and the better ion conductivity.
  • the present invention utilizes high entropy oxide to coat and dope the substrate.
  • the presence of high entropy oxide can react with part of the residual alkali and improve the conductivity.
  • the coating also has a certain electrochemical activity to ensure that the capacity is not lost.
  • the high entropy oxide itself has good structural stability and ionic conductivity, which is beneficial to improve the stability of the positive electrode material and reduce side reactions, while improving the transmission capacity of sodium ions, thereby improving the rate and cycle performance of the positive electrode material.
  • the preparation method is simple, the equipment requirements are low, and it is convenient for industrial application.

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Abstract

本公开公开了高熵氧化物掺杂包覆共修饰的正极材料、制备方法及应用，其中正极材料包括基材和高熵氧化物，部分所述高熵氧化物包覆在基材表面形成包覆层，部分所述高熵氧化物进入所述基材的表层形成掺杂层，所述基材为O3型层状过渡金属氧化物。本公开利用高熵氧化物包覆基材，对钠离子电池正极材料的倍率和循环性能具有较优异效果。

Description

高熵氧化物掺杂包覆共修饰的正极材料、制备方法及应用 技术领域
本公开涉及钠离子电池正极材料技术领域，具体而言，涉及高熵氧化物掺杂包覆共修饰的正极材料、制备方法及应用。
背景技术
钠离子电池(SIB)因低成本及钠资源丰富等优势在大规模储能系统中备受关注，O3型层状过渡金属氧化物正极材料理论容量高、结构简单，成为钠离子电池正极材料的最佳选择之一。然而充放电过程中，过渡金属层容易发生相对滑移和畸变，导致结构重排并产生复杂相变，导致电池能量效率低，循环稳定性差等问题。
鉴于此，特提出本公开。
发明内容
本公开的目的在于提供高熵氧化物掺杂包覆共修饰的正极材料、制备方法及应用，克服O3型层状过渡金属氧化物正极材料应用于钠离子电池中，电池能量效率较低，循环稳定性较差的问题。
本公开是这样实现的：
第一方面，本公开提供一种高熵氧化物掺杂包覆共修饰的正极材料，包括基材和高熵氧化物，部分所述高熵氧化物包覆在基材表面形成包覆层，部分所述高熵氧化物进入所述基材的表层形成掺杂层；
所述基材为O3型层状过渡金属氧化物，所述高熵氧化物结构式为AaBbCcDdEe(M)mO2，其中0.15<a<0.25，0.15<b<0.25，0.15<c<0.25，0.15<d<0.25，0.15<e<0.25，m<0.1，a+b+c+d+e+m＝1，所述A、B、C、D、E选自Li、Na、Mg、Ca、Al、Zn、Sc、Ti、V、Cr、Mn、Fe、Co、Y、Zr、Nb、Mo、Ga、Te、Sb、In、Ce和Sn中的五种，M选自Li、Na、Mg、Ca、Al、Zn、Sc、Ti、V、Cr、Mn、Fe、Co、Y、Zr、Nb、Mo、Ga、Te、Sb、In、Ce和Sn中的至少一种。
在可选的实施方式中，m＞0。
在可选的实施方式中，所述基材结构式为NaxNiyMnz(T)tO2，T为Cu、Cr、Fe、Zn、Ti和V中的至少一种，其中0.8<x<1，0≤y≤0.5，0≤z≤1.0，0≤t≤0.2，且y+z+t＝1。
在可选的实施方式中，所述T为Fe。
在可选的实施方式中，所述高熵氧化物为纳米级的高熵氧化物。
在可选的实施方式中，所述高熵氧化物的粒径小于200nm。
在可选的实施方式中，所述正极材料中高熵氧化物的质量分数小于5％。
在可选的实施方式中，所述正极材料D50为5um-10um。
第二方面，本公开提供一种前述实施方式任意一项所述高熵氧化物掺杂包覆共修饰的正极材料的制备方法，包括对表面附着有高熵氧化物的基材进行烧结，得到所述高熵氧化物掺杂包覆共修饰的正极材料。
在可选的实施方式中，还包括表面附着有高熵氧化物的基材的制备：包括对基材、金属盐和溶剂的混合溶液进行加热，得到表面附着有高熵氧化物的基材。
在可选的实施方式中，所述表面附着有高熵氧化物的基材的制备步骤中，所述混合溶液中基材的质量分数为25％-35％，所述金属盐的质量分数为3.5％-4.5％。
在可选的实施方式中，所述表面附着有高熵氧化物的基材的制备步骤中，加热温度为60℃-150℃，保温时间1h-6h。
在可选的实施方式中，所述表面附着有高熵氧化物的基材的制备步骤在密闭反应器中进行。
在可选的实施方式中，所述表面附着有高熵氧化物的基材的制备过程伴随搅拌。
在可选的实施方式中，搅拌转速为100rpm-500rpm。
在可选的实施方式中，搅拌采用间歇式搅拌。
在可选的实施方式中，所述表面附着有高熵氧化物的基材的制备步骤中，每次搅拌50s-70s，间隔8min-12min搅拌一次。
在可选的实施方式中，所述表面附着有高熵氧化物的基材的制备步骤中，金属盐为Li盐、Na盐、Mg盐、Ca盐、Al盐、Zn盐、Sc盐、Ti盐、V盐、Cr盐、Mn盐、Fe盐、Co盐、Y盐、Zr盐、Nb盐、Mo盐、Ga盐、Te盐、Sb盐、In盐、Sn盐中的5种或5种以上。
在可选的实施方式中，所述金属盐为硝酸盐、氯盐中的至少一种。
在可选的实施方式中，所述溶剂为乙醇、油胺和己烷，比例为1:(0.9-1.1):(2.5-3.5)。
在可选的实施方式中，加热完成后还对反应液进行固液分离，并对分离出的固相进行烘干。
在可选的实施方式中，所述烘干温度为75℃-85℃，烘干时间大于8h。
在可选的实施方式中，所述烧结步骤的温度为烧结温度为800℃-1100℃，保温时间4h-15h。
在可选的实施方式中，所述烧结步骤的温度为880℃-980℃，保温时间为8h-15h。
在可选的实施方式中，烧结气氛为空气或氧气。
在可选的实施方式中，还包括基材的制备步骤：包括对氧化物和钠源的混合物进行烧结，得到基材。
在可选的实施方式中，所述氧化物包括氧化镍、氧化锰、氧化铬、氧化铁、氧化钒和氧化钛中的至少一种。
在可选的实施方式中，所述钠源为碳酸钠、氢氧化钠、氧化钠、过氧化钠中的一种或多种。
在可选的实施方式中，基材的制备步骤中，烧结温度为800℃-1000℃，烧结时间6h-24h。
在可选的实施方式中，基材的制备步骤中，烧结的温度为850℃-950℃，保温时间为8h-15h。
第三方面，本公开提供一种前述实施方式任意一项所述的正极材料或前述实施方式任意一项所述方法得到的正极材料在钠离子电池中的应用。
第四方面，本公开提供一种电极，包括前述实施方式任意一项所述的正极材料或前述实施方式任意一项所述方法得到的正极材料。
第五方面，本公开提供一种钠离子电池，包括前述实施方式所述的电极。
第六方面，本公开提供一种用电设备，包括前述实施方式所述的钠离子电池。
本公开具有以下有益效果：
本公开中的高熵氧化物作为一种多种金属元素共享相同的原子位点，阳离子无序分布的单相固溶体材料，因金属层无序化，金属元素更趋于随机发生氧化还原反应，可抑制Na+/空位有序和电荷有序，延缓或抑制相变，提高电极材料的倍率性能和循环稳定性。
本公开中包覆层中高熵氧化物的存在能够反应掉部分残碱，提升导电性，同时包覆物也具有一定的电化学活性，保证容量不损失；且高熵氧化物本身具有良好的结构稳定性和离子导电性，有利于提高正极材料的稳定性并减少副反应，同时提高钠离子的传输能力。
附图说明
为了更清楚地说明本公开实施例的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，应当理解，以下附图仅示出了本公开的某些实施例，因此不应被看作是对范围的限定，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他相关的附图。
图1为实施例1为流程图；
图2为实施例1步骤3中烘干料的SEM；
图3为实施例1正极基材SEM；
图4为实施例1高熵氧化物包覆正极基材SEM。
具体实施方式
为使本公开实施例的目的、技术方案和优点更加清楚，下面将对本公开实施例中的技术方案进行清楚、完整地描述。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
本公开的一些实施方式提供一种高熵氧化物掺杂包覆共修饰的正极材料，包括基材和高熵氧化物，部分所述高熵氧化物包覆在基材表面形成包覆层，部分所述高熵氧化物进入所述基材的表层形成掺杂层；
所述基材为O3型层状过渡金属氧化物，所述高熵氧化物结构式为AaBbCcDdEe(M)mO2，其中0.15<a<0.25，0.15<b<0.25，0.15<c<0.25，0.15<d<0.25，0.15<e<0.25，m<0.1，a+b+c+d+e+m＝1，所述A、B、C、D、E选自Li、Na、Mg、Ca、Al、Zn、Sc、Ti、V、Cr、Mn、Fe、Co、Y、Zr、Nb、Mo、Ga、Te、Sb、In、Ce和Sn中的五种，M选自Li、Na、Mg、Ca、Al、Zn、Sc、Ti、V、Cr、Mn、Fe、Co、Y、Zr、Nb、Mo、Ga、Te、Sb、In、Ce和Sn中的至少一种。
本实施方式中的高熵氧化物作为一种多种金属元素共享相同的原子位点，阳离子无序分布的单相固溶体材料，因金属层无序化，金属元素更趋于随机发生氧化还原反应，可抑制Na+/空位有序和电荷有序，延缓或抑制相变，提高电极材料的倍率性能和循环稳定性。另外，高熵氧化物中金属元素为五种或五种以上，其中A、B、C、D、E以外的元素掺杂量较低，少量掺杂更有利于抑制Na+/空位有序和电荷有序。
本实施方式中包覆层中高熵氧化物的存在能够反应掉部分残碱，提升导电性，同时包覆物也具有一定的电化学活性，保证容量不损失；且高熵氧化物本身具有良好的结构稳定性和离子导电性，有利于提高正极材料的稳定性并减少副反应，同时提高钠离子的传输能力。
在一些可选的实施方式中，m＞0。
在一些可选的实施方式中，所述基材结构式为NaxNiyMnz(T)tO2，T为Cu、Cr、Fe、Zn、Ti和V中的至少一种，其中0.8<x<1，0≤y≤0.5，0≤z≤1.0，0≤t≤0.2，且y+z+t＝1。
在一些可选的实施方式中，所述T为Fe。
在一些可选的实施方式中，所述高熵氧化物为纳米级的高熵氧化物。纳米级高熵氧化物，更易于在高温反应中部分进入基材的晶体表层，有利于提高掺杂层中高熵氧化物纳米晶体含量，同时有利于高熵氧化物均匀包覆在正极材料表面，部分高熵氧化物纳米晶体在高温下掺杂至体相利于提高正极材料充放电过程中的稳定性。
在可选的实施方式中，。
在一些可选的实施方式中，所述高熵氧化物的粒径小于200nm。
在一些可选的实施方式中，所述正极材料中高熵氧化物的质量分数小于5％，正极材料制备过程中，以金属盐和基材的加入量计算高熵氧化物的质量分数即可，高熵氧化物的含量较低，对材料的倍率性和循环稳定性的提升有限，但含量过高也会影响材料的容量。
在一些可选的实施方式中，所述正极材料D50为5um-10um。
第二方面，本公开提供一种前述实施方式任意一项所述高熵氧化物掺杂包覆共修饰的正极材料的制备方法，包括对表面附着有高熵氧化物的基材进行烧结，得到所述高熵氧化物掺杂包覆共修饰的正极材料。
在一些可选的实施方式中，还包括表面附着有高熵氧化物的基材的制备：包括对基材、金属盐和溶剂的混合溶液进行加热，得到表面附着有高熵氧化物的基材。固相法制备表面附着有高熵氧化物的基材很难实现高熵氧化物原位生成和均匀包覆，导致最终得到产品的倍率性和循环稳定性提升效果不理想，本实施方式通过溶剂热法生成高熵氧化物与基材的混合物，相比于固相法，在基材表面附着的纳米级高熵氧化物更加均匀，更利于纳米级高熵氧化物在高温反应中进入晶体表层，同时有利于纳米级高熵氧化物均匀包覆在正极材料表面。
在一些可选的实施方式中，所述表面附着有高熵氧化物的基材的制备步骤中，所述混合溶液中基材的质量分数为25％-35％，所述金属盐的质量分数为3.5％-4.5％。混合液中基材和金属盐的浓度过低，不利于反应效率的提升，浓度过高会影响化学平衡以及反应的稳定进行，从而影响高熵氧化物分散的均匀性，进而会增加高熵氧化物的粒径或降低高熵氧化物粒径分布的均匀性。
在一些可选的实施方式中，所述表面附着有高熵氧化物的基材的制备步骤中，加热温度为60℃-150℃，保温时间1h-6h，所述保温时间的延长以及加热温度过高或过低，都可能会使得高熵氧化物的晶体尺寸的变化，从而不利于高熵氧化物均匀的掺杂和包覆。
在一些可选的实施方式中，所述表面附着有高熵氧化物的基材的制备步骤在密闭反应器中进行，升温条件下可具有一定的压力，有利于高熵氧化物纳米晶的形成。
在一些可选的实施方式中，所述表面附着有高熵氧化物的基材的制备过程伴随搅拌， 搅拌能够防止基材沉底，有利于基材相对均匀的分散在混合溶液中，协同均匀分散的纳米高熵氧化物，从而促使生成的高熵氧化物均匀包覆。
在一些可选的实施方式中，搅拌转速为100rpm-500rpm，搅拌速度过慢无法起到使基材和纳米高熵氧化物均匀分散于混合溶液的作用，搅拌速度过快可能会影响溶液化学平衡状态，从而影响高熵氧化物和基材的结合，进而不利于高熵氧化物均匀包覆在基材表面。
在一些可选的实施方式中，搅拌采用间歇式搅拌，长时间搅拌也会影响溶液化学平衡状态，从而影响高熵氧化物和基材的结合，进而不利于高熵氧化物均匀包覆在基材表面。
在一些可选的实施方式中，所述表面附着有高熵氧化物的基材的制备步骤中，每次搅拌50s-70s，间隔8min-12min搅拌一次。
在一些可选的实施方式中，所述表面附着有高熵氧化物的基材的制备步骤中，金属盐为Li盐、Na盐、Mg盐、Ca盐、Al盐、Zn盐、Sc盐、Ti盐、V盐、Cr盐、Mn盐、Fe盐、Co盐、Y盐、Zr盐、Nb盐、Mo盐、Ga盐、Te盐、Sb盐、In盐、Sn盐中的5种或5种以上。
在一些可选的实施方式中，所述金属盐为硝酸盐、氯盐中的至少一种。
在一些可选的实施方式中，所述溶剂为乙醇、油胺和己烷，比例为1:(0.9-1.1):(2.5-3.5)。
其中，所述乙醇作为溶剂；己烷作为溶剂和分散剂，使其它溶剂、基材和生成的高熵氧化物纳米粒子在溶剂中均匀分散；油氨为稳定剂，可以减慢反应、保持化学平衡，防止纳米粒子团聚，使得纳米粒子均匀缓慢生成；其中乙醇、油胺和己烷按比例配合，能够得到在溶剂中均匀分散的纳米级高熵氧化物。
在一些可选的实施方式中，加热完成后还对反应液进行固液分离，并对分离出的固相进行烘干。
在一些可选的实施方式中，所述烘干的温度为75℃-85℃，烘干时间大于8h，一些实施例中采用旋转真空烘干或常压烘干，但负压有利于快速去除水分，为接下来的烧结做准备。
在一些可选的实施方式中，所述烧结步骤的温度为烧结温度为800℃-1100℃，保温时间4h-15h。
在一些可选的实施方式中，所述烧结步骤的温度为880℃-980℃，保温时间为8h-15h。
在一些可选的实施方式中，烧结气氛为空气或氧气。
在一些可选的实施方式中，还包括基材的制备步骤：包括对氧化物和钠源的混合物进行烧结，得到基材。
在一些可选的实施方式中，所述氧化物包括氧化镍、氧化锰、氧化铬、氧化铁、氧化钒和氧化钛中的至少一种。
在一些可选的实施方式中，所述钠源为碳酸钠、氢氧化钠、氧化钠、过氧化钠中的一种或多种。
在一些可选的实施方式中，基材的制备步骤中，烧结温度为800℃-1000℃，烧结时间6h-24h。
在一些可选的实施方式中，基材的制备步骤中，烧结的温度为850℃-950℃，保温时间为8h-15h。
第三方面，本公开提供一种前述实施方式任意一项所述的正极材料或前述实施方式任意一项所述方法得到的正极材料在钠离子电池中的应用。
第四方面，本公开提供一种电极，包括前述实施方式任意一项所述的正极材料或前述实施方式任意一项所述方法得到的正极材料。
第五方面，本公开提供一种钠离子电池，包括前述实施方式所述的电极。
第六方面，本公开提供一种用电设备，包括前述实施方式所述的钠离子电池。
以下结合实施例对本公开的特征和性能作进一步的详细描述。
实施例1：
本实施例提供一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，如图1所示，包括以下步骤：
步骤1：将氧化镍，三氧化二锰，氧化锌和碳酸钠按照Ni、Mn、Zn、Na元素的摩尔比例为0.20:0.7:0.1:0.95的比例混合，记为混料A；
步骤2：在空气气氛下880℃烧结保温12h，得到基材B，形貌如图3所示。
步骤3：将三水硝酸铜，六水硝酸锌，九水硝酸铁，六水硝酸铈，氯化锆加入锥形平底烧杯中，其中铜、锌、铁、铈、锆元素摩尔比约1:1:1:1:1，再加入30g基材B，使得正极材料中高熵氧化物理论上的最大质量分数为5％，再加入体积比为1:1:3的乙醇、油胺和己烷共100ml，放入磁子，对烧杯进行密封，放在陶瓷加热台上以100℃反应120min，搅拌速度150rpm，搅拌时间1min，间隔10min搅拌一次，反应完后过滤，对固相进行旋转真空烘干，烘干温度80℃，转速200rpm，得到材料C，形貌如图2所示。
步骤4：将材料C在空气气氛下900℃烧结保温10h，得到具有高熵包覆的正极材料，形貌如图4所示。
实施例2：
本实施例提供一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，包括以下步骤：
步骤1：将氧化镍，三氧化二锰，氧化锌和碳酸钠按照Ni、Mn、Zn、Na元素的摩尔比例为0.20:0.7:0.1:0.95的比例混合，记为混料A；
步骤2：在空气气氛下880℃烧结保温12h，得到基材B。
步骤3：将三水硝酸铜，六水硝酸锌，六水硝酸铈，氯化锆，六水氯化镍加入锥形平底烧杯中，其中铜、锌、铈、锆、镍元素摩尔比约1:1:1:1:1，再加入30g基材B，使得正极材料中高熵氧化物理论上的最大质量分数为5％，再加入体积比为1:1:3的乙醇、油胺和己烷共100ml，放入磁子，对烧杯进行密封，放在陶瓷加热台上以100℃反应120min，搅拌速度150rpm，搅拌时间1min，间隔10min搅拌一次，反应完后过滤，对固相进行旋转真空烘干，烘干温度80℃，转速200rpm，得到材料C。
步骤4：将材料C在空气气氛下900℃烧结保温10h，得到具有高熵包覆的正极材料。
实施例3：
本实施例提供一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，与实施例1的区别仅在于，步骤3中，加入体积比为1:0.9:2.5的乙醇、油胺和己烷。
实施例4：
本实施例提供一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，与实施例1的区别仅在于，步骤3中，加入体积比为1:1.1:3.5的乙醇、油胺和己烷。
实施例5：
本实施例提供一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，与实施例1的区别仅在于，步骤3中，以150rpm的速度持续搅拌。
实施例6：
本实施例提供一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，与实施例1的区别仅在于，步骤3中，搅拌时搅拌速度为500rpm。
实施例7：
本实施例提供一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，与实施例1的区别仅在于，步骤3中，搅拌时搅拌速度为100rpm。
实施例8：
本实施例提供一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，与实施例1的区别仅在于，步骤3中，搅拌时间50s，间隔12min搅拌一次。
实施例9：
本实施例提供一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，与实施例1的区别仅在于，步骤3中，搅拌时间70s，间隔8min搅拌一次。
实施例10：
本实施例提供一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，与实施例1的区别仅在于，步骤3中，对烧杯进行密封，放在陶瓷加热台上以60℃反应120min。
实施例11：
本实施例提供一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，与实施例1的区别仅在于，步骤3中，对烧杯进行密封，放在陶瓷加热台上以150℃反应120min。
实施例12：
本实施例提供一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，与实施例1的区别仅在于，步骤3中，对烧杯进行密封，放在陶瓷加热台上以100℃反应6h。
实施例13：
本实施例提供一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，与实施例1的区别仅在于，步骤3中，将硝酸铜，硝酸锌，硝酸铁，硝酸铈，氯化锆，氯化镍，按照元素摩尔比1:1:1:1:1:1加入到锥形平底烧杯中(金属元素摩尔总量与实施例1相等)。
实施例14：
本实施例提供一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，与实施例1的区别仅在于，步骤3中，将硝酸铜，硝酸锌，硝酸铁，硝酸铈，氯化锆，氯化镍，按照元素摩尔比1:1:1:1:1:0.015加入到锥形平底烧杯中(金属元素摩尔总量与实施例1相等)。
实施例15：
本实施例提供一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，与实施例1的区别仅在于，步骤3中，对烧杯进行密封，放在陶瓷加热台上以100℃反应1h。
实施例16：
本实施例提供一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，与实施例1的区别仅在于，步骤4中，烧结温度为1100℃。
实施例17：
本实施例提供一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，与实施例1的区别仅在于，步骤4中，烧结温度为800℃。
实施例18：
本实施例提供一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，与实施例1的区别仅在于，步骤3中，将硝酸铜，硝酸锌，硝酸铁，硝酸铈，氯化锆按照元素摩尔比0.25: 0.25:0.25:0.15:0.15加入到锥形平底烧杯中(金属元素摩尔总量与实施例1相等)。
实施例19：
本实施例提供一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，与实施例1的区别仅在于，步骤3中，将硝酸铜，硝酸锌，硝酸铁，硝酸铈，氯化锆按照元素摩尔比0.15:0.15:0.25:0.25:0.25加入到锥形平底烧杯中(金属元素摩尔总量与实施例1相等)。
实施例20：
本实施例提供一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，与实施例1的区别仅在于，步骤1中，调整混合料A的组成，使得步骤2分别得到Na0.9Ni0.2Mn0.6Fe0.2O2、Na0.73Ni0.6Co0.05Mn0.35O2；或，步骤3分别得到Cu0.125Zn0.125Fe0.125Ce0.125Zr0.125Ni0.125Co0.125Cr0.125O2、Mg0.2Al0.2Ni0.2Zn0.2Ti0.2O2，包覆高熵氧化物后1C/0.1C相较于基材均有一定提升，1C循环100圈容量保持率增加超过5％。
对比例1：
本对比例提供一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，包括以下步骤：
步骤1：将氧化镍，三氧化二锰，氧化锌和碳酸钠按照Ni、Mn、Zn、Na元素的摩尔比例为0.20:0.7:0.1:0.95的比例混合，记为混料A；
步骤2：在空气气氛下880℃烧结保温12h，得到基材B。
步骤3：将2.02g六水硝酸锌，1.58g氯化锆加入到锥形平底烧杯中，加入30g基材B，使得正极材料中高熵氧化物理论上的最大质量分数为5％，再加入体积比为1:1:3的乙醇、油胺和己烷100ml，放入磁子，对烧杯进行密封，放在陶瓷加热台上以100℃反应120min，搅拌速度150rpm，搅拌时间1min，间隔10min搅拌一次，反应完后过滤烘干，得到材料C。
步骤4：将材料C在空气气氛下900℃烧结保温10h，得到具有高熵包覆的正极材料。
对比例2：
本对比例一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，包括以下步骤：
步骤1：将氧化镍，三氧化二锰，氧化锌和碳酸钠按照Ni、Mn、Zn、Na元素的摩尔比例为0.20:0.7:0.1:0.95的比例混合，记为混料A；
步骤2：在空气气氛下880℃烧结保温12h，得到基材B。
步骤3：将B使用混料机混合均匀，在空气气氛下900℃烧结保温10h，得到Na0.95Ni0.2Zn0.1Mn0.7O2正极材料。
对比例3：
本对比例一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，包括以下步骤：
步骤1：将氧化镍，三氧化二锰，氧化锌和碳酸钠按照Ni、Mn、Zn、Na元素的摩尔比例为0.20:0.7:0.1:0.95的比例混合，记为混料A；
步骤2：在空气气氛下880℃烧结保温12h，得到基材B。
步骤3：将30g基材B加入到锥形平底烧杯中，加入基材B，再加入体积比为1:1:3的乙醇、油胺和己烷100ml，对烧杯进行密封，放在加热台上以100℃反应120min，反应完后过滤烘干，得到材料C。
步骤4：将材料C在空气气氛下900℃烧结保温10h，得到无包覆正极材料。
对比例4：
本对比例提供一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，与实施例1的区别仅在于，步骤3中，将硝酸铈，氯化锆，氯化镍，按照元素摩尔比1:1:1加入到锥形平底烧杯中(金属元素摩尔总量与实施例1相等)。
对比例5：
本对比例提供一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，与实施例1的区别仅在于，步骤3中，将硝酸铜，硝酸锌，硝酸铁，硝酸铈按照元素摩尔比1:1:1:1加入到锥形平底烧杯中(金属元素摩尔总量与实施例1相等)。
对比例6：
本对比例提供一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，与实施例1的区别仅在于，步骤3中，加入体积比为1:0.5:4的乙醇、油胺和己烷。
对比例:7：
本对比例提供一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，与实施例1的区别仅在于，步骤3中，加入体积比为1:1.5:2的乙醇、油胺和己烷。
对比例8：
本对比例提供一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，与对比例1的区别仅在于，步骤3中，搅拌时搅拌速度为1000rpm。
对比例9：
本对比例提供一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，与对比例1的区别仅在于，步骤3中，对烧杯进行密封，放在陶瓷加热台上以100℃反应10h。
对比例10：
本对比例提供一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，与对比例1的区别仅在于，步骤3中，对烧杯进行密封，放在陶瓷加热台上以30℃反应120min。
对比例11：
本对比例提供一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，与对比例1的区别仅在于，步骤3中，对烧杯进行密封，放在陶瓷加热台上以180℃反应120min。
对比例12：
本对比例提供一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，与实施例1的区别仅在于，步骤3中，搅拌时间30s，间隔15min搅拌一次。
对比例13：
本对比例提供一种高熵氧化物掺杂包覆共修饰钠离子正极材料的方法，与实施例1的区别仅在于，步骤3中，搅拌时间90s，间隔5min搅拌一次。
将上述实施例和对比例得到的正极材料制备成扣式电池，具体包括：①制备浆料，称取材料与导电剂，粘结剂混合，其中材料：导电剂：粘结剂的质量比为8:1:1，所用粘结剂为PVDF，导电剂为导电炭；②涂布，使用刮刀在铝箔上进行涂布；③干燥，将涂布好的极片在真空干燥箱中进行干燥，干燥温度为120℃，干燥时间为4h；④压片，将干燥后极片使用对辊机进行压片；⑤将正极极片，负极极片，隔膜，电解液等电池零件组装成扣式电池。然后对电池的电性能进行测试，测试电压为1.5-4.2V，测试温度为25℃，得到表1。
表1应用实施例和对比例得到正极材料的电池的电性能

表1为实施案例和对比例电池制备的电性能，由实施例1-2和对比例2可以看出，从结果可以看出高熵氧化物修饰钠离子正极材料具有有益效果，尤其是对于倍率性能和循环性能提升较大；由实施例1和对比例1-2可知，高熵材料相较于直接包覆氧化物对性能提升的效果更加明显，这可能是由于高熵氧化物结构更稳定，离子传导性更好；由实施例1-2和对比例3可知，搅拌工艺对材料的性能也具有很大的影响，且通过其他实施例和对比例的对比可以看出，搅拌速率、搅拌频率和每次搅拌时间均会对产品有较大影响，这是由于搅拌工艺使得正极材料也分散在溶剂中，与分散的高熵材料协同作用，包覆更加均匀。
工业实用性
本公开利用高熵氧化物对基材进行包覆和掺杂，高熵氧化物的存在能够反应掉部分残碱，提升导电性，同时包覆物也具有一定的电化学活性，保证容量不损失；且高熵氧化物本身具有良好的结构稳定性和离子导电性，有利于提高正极材料的稳定性并减少副反应，同时提高钠离子的传输能力，进而提高正极材料的倍率和循环性能，且制备方法简单，对设备要求低，便于工业应用。

Claims (33)

  1. 一种高熵氧化物掺杂包覆共修饰的正极材料，其特征在于，包括基材和高熵氧化物，部分所述高熵氧化物包覆在基材表面形成包覆层，部分所述高熵氧化物进入所述基材的表层形成掺杂层；
    所述基材为O3型层状过渡金属氧化物，所述高熵氧化物结构式为AaBbCcDdEe(M)mO2，其中0.15<a<0.25，0.15<b<0.25，0.15<c<0.25，0.15<d<0.25，0.15<e<0.25，m<0.1，a+b+c+d+e+m＝1，所述A、B、C、D、E选自Li、Na、Mg、Ca、Al、Zn、Sc、Ti、V、Cr、Mn、Fe、Co、Y、Zr、Nb、Mo、Ga、Te、Sb、In、Ce和Sn中的五种，所述M选自Li、Na、Mg、Ca、Al、Zn、Sc、Ti、V、Cr、Mn、Fe、Co、Y、Zr、Nb、Mo、Ga、Te、Sb、In、Ce和Sn中的至少一种。
  2. 根据权利要求1所述的高熵氧化物掺杂包覆共修饰的正极材料，其特征在于，所述基材结构式为NaxNiyMnz(T)tO2，T为Cu、Cr、Fe、Zn、Ti和V中的至少一种，其中0.8<x<1，0≤y≤0.5，0≤z≤1.0，0≤t≤0.2，且y+z+t＝1。
  3. 根据权利要求1或2所述的高熵氧化物掺杂包覆共修饰的正极材料，其特征在于，所述T为Fe。
  4. 根据权利要求1-3任意一项所述的高熵氧化物掺杂包覆共修饰的正极材料，其特征在于，所述高熵氧化物为纳米级的高熵氧化物。
  5. 根据权利要求1-4任意一项所述的高熵氧化物掺杂包覆共修饰的正极材料，其特征在于，所述高熵氧化物的粒径小于200nm。
  6. 根据权利要求1-5任意一项所述的高熵氧化物掺杂包覆共修饰的正极材料，其特征在于，所述正极材料中高熵氧化物的质量分数小于5％。
  7. 根据权利要求1-6任意一项所述的高熵氧化物掺杂包覆共修饰的正极材料，其特征在于，所述正极材料D50为5um-10um。
  8. 一种权利要求1-7任意一项所述高熵氧化物掺杂包覆共修饰的正极材料的制备方法，其特征在于，包括：对表面附着有高熵氧化物的基材进行烧结，得到所述高熵氧化物掺杂包覆共修饰的正极材料。
  9. 根据权利要求8所述的高熵氧化物掺杂包覆共修饰的正极材料的制备方法，其特征在于，还包括表面附着有高熵氧化物的基材的制备：包括对基材、金属盐和溶剂的混合溶液进行加热，得到表面附着有高熵氧化物的基材。
  10. 根据权利要求9所述的高熵氧化物掺杂包覆共修饰的正极材料的制备方法，其特征在于，所述表面附着有高熵氧化物的基材的制备步骤中，所述混合溶液中基材的质量分数 为25％-35％，所述金属盐的质量分数为3.5％-4.5％。
  11. 根据权利要求9或10所述的高熵氧化物掺杂包覆共修饰的正极材料的制备方法，其特征在于，所述表面附着有高熵氧化物的基材的制备步骤中，加热温度为60℃-150℃，保温时间1h-6h。
  12. 根据权利要求9-11任意一项所述的高熵氧化物掺杂包覆共修饰的正极材料的制备方法，其特征在于，所述表面附着有高熵氧化物的基材的制备步骤在密闭反应器中进行。
  13. 根据权利要求9-12任意一项所述的高熵氧化物掺杂包覆共修饰的正极材料的制备方法，其特征在于，所述表面附着有高熵氧化物的基材的制备过程伴随搅拌。
  14. 根据权利要求13所述的高熵氧化物掺杂包覆共修饰的正极材料的制备方法，其特征在于，搅拌转速为100rpm-500rpm。
  15. 根据权利要求13或14所述的高熵氧化物掺杂包覆共修饰的正极材料的制备方法，其特征在于，搅拌采用间歇式搅拌。
  16. 根据权利要求15所述的高熵氧化物掺杂包覆共修饰的正极材料的制备方法，其特征在于，所述表面附着有高熵氧化物的基材的制备步骤中，每次搅拌50s-70s，间隔8min-12min搅拌一次。
  17. 根据权利要求9-16任意一项所述的高熵氧化物掺杂包覆共修饰的正极材料的制备方法，其特征在于，所述表面附着有高熵氧化物的基材的制备步骤中，金属盐为Li盐、Na盐、Mg盐、Ca盐、Al盐、Zn盐、Sc盐、Ti盐、V盐、Cr盐、Mn盐、Fe盐、Co盐、Y盐、Zr盐、Nb盐、Mo盐、Ga盐、Te盐、Sb盐、In盐、Sn盐中的5种或5种以上。
  18. 根据权利要求9-17任意一项所述的高熵氧化物掺杂包覆共修饰的正极材料的制备方法，其特征在于，所述金属盐为硝酸盐、氯盐中的至少一种。
  19. 根据权利要求9-18任意一项所述的高熵氧化物掺杂包覆共修饰的正极材料的制备方法，其特征在于，所述溶剂为乙醇、油胺和己烷，比例为1:(0.9-1.1):(2.5-3.5)。
  20. 根据权利要求9-19任意一项所述的高熵氧化物掺杂包覆共修饰的正极材料的制备方法，其特征在于，加热完成后还对反应液进行固液分离，并对分离出的固相进行烘干。
  21. 根据权利要求20所述的高熵氧化物掺杂包覆共修饰的正极材料的制备方法，其特征在于，所述烘干的温度为75℃-85℃，烘干时间为大于8h。
  22. 根据权利要求8-21任意一项所述的高熵氧化物掺杂包覆共修饰的正极材料的制备方法，其特征在于，所述烧结步骤的温度为烧结温度为800℃-1100℃，保温时间4h-15h。
  23. 根据权利要求22所述的高熵氧化物掺杂包覆共修饰的正极材料的制备方法，其特征在于，所述烧结步骤的温度为880℃-980℃，保温时间为8h-15h。
  24. 根据权利要求8-22任意一项所述的高熵氧化物掺杂包覆共修饰的正极材料的制备方法，其特征在于，烧结气氛为空气或氧气。
  25. 根据权利要求8-24任意一项所述的高熵氧化物掺杂包覆共修饰的正极材料的制备方法，其特征在于，还包括基材的制备步骤：包括对氧化物和钠源的混合物进行烧结，得到基材。
  26. 根据权利要求25所述的高熵氧化物掺杂包覆共修饰的正极材料的制备方法，其特征在于，所述氧化物包括氧化镍、氧化锰、氧化铬、氧化铁、氧化钒和氧化钛中的至少一种。
  27. 根据权利要求25或26所述的高熵氧化物掺杂包覆共修饰的正极材料的制备方法，其特征在于，所述钠源为碳酸钠、氢氧化钠、氧化钠、过氧化钠中的一种或多种。
  28. 根据权利要求25-27任意一项所述的高熵氧化物掺杂包覆共修饰的正极材料的制备方法，其特征在于，基材的制备步骤中，烧结温度为800℃-1000℃，烧结时间6h-24h。
  29. 根据权利要求25-28任意一项所述的高熵氧化物掺杂包覆共修饰的正极材料的制备方法，其特征在于，基材的制备步骤中，烧结的温度为850℃-950℃，保温时间为8h-15h。
  30. 一种权利要求1-7任意一项所述的正极材料或权利要求8-29任意一项所述方法得到的正极材料在钠离子电池中的应用。
  31. 一种电极，其特征在于，包括权利要求1-7任意一项所述的正极材料或权利要求8-29任意一项所述方法得到的正极材料。
  32. 一种钠离子电池，其特征在于，包括权利要求31所述的电极。
  33. 一种用电设备，其特征在于，包括权利要求32所述的钠离子电池。
PCT/CN2023/098757 2023-06-07 2023-06-07 高熵氧化物掺杂包覆共修饰的正极材料、制备方法及应用 Ceased WO2024250186A1 (zh)

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