WO2024250135A1 - 一种改性高镍三元正极材料及其制备方法与电池 - Google Patents

一种改性高镍三元正极材料及其制备方法与电池 Download PDF

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WO2024250135A1
WO2024250135A1 PCT/CN2023/098257 CN2023098257W WO2024250135A1 WO 2024250135 A1 WO2024250135 A1 WO 2024250135A1 CN 2023098257 W CN2023098257 W CN 2023098257W WO 2024250135 A1 WO2024250135 A1 WO 2024250135A1
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lithium
positive electrode
preparation
electrode material
nickel ternary
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English (en)
French (fr)
Inventor
李爱霞
谢英豪
余海军
李长东
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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 PCT/CN2023/098257 priority Critical patent/WO2024250135A1/zh
Priority to CN202380009313.0A priority patent/CN116941066A/zh
Publication of WO2024250135A1 publication Critical patent/WO2024250135A1/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

Definitions

  • Ternary positive electrode materials can be divided into types 111, 523, 622 and 811 according to the different proportions of their constituent elements nickel, cobalt and manganese. As the nickel content increases, the material capacity also increases. However, the residual alkali on the surface of high-nickel ternary positive electrode materials makes them exhibit strong alkalinity and strong moisture absorption during the preparation process, which not only makes the slurry preparation process difficult, but also accelerates the decomposition of the electrolyte.
  • Surface coating is an effective means to improve the performance of high-nickel positive electrode materials. Although the existing surface coating methods can reduce the residual alkali content on the surface of the material, it will also cause a decrease in the gram capacity of the material.
  • One of the purposes of the present disclosure includes providing a modified high-nickel ternary positive electrode material, which has a low surface residual alkali content and can maintain a high gram capacity.
  • the second object of the present disclosure includes providing a method for preparing the above-mentioned modified high-nickel ternary positive electrode material.
  • the third object of the present disclosure includes providing a battery containing the above-mentioned modified high-nickel ternary positive electrode material.
  • the present disclosure provides a modified high-nickel ternary positive electrode material, which is obtained by coating a high-nickel ternary positive electrode material with a lithium-free or lithium-deficient Prussian blue material and then supplementing the coating layer with lithium in an electrolyte.
  • the molecular formula of the lithium-free or lithium-deficient Prussian blue material is Li x M y [Fe(CN) 6 ] z , where x ⁇ 1, 1 ⁇ y ⁇ 3, 1 ⁇ z ⁇ 2, and M is a transition metal.
  • M comprises Ni, Co or Mn.
  • the lithium-free or lithium-poor Prussian blue material includes at least one of LiFe[Fe(CN) 6 ], Ni 3 [Fe(CN) 6 ] 2 , Co 3 [Fe(CN) 6 ] 2 , and Mn 3 [Fe(CN) 6 ] 2 .
  • the mass of the lithium-free or lithium-deficient Prussian blue material is 5%-10% of the high-nickel ternary positive electrode material.
  • the present disclosure provides a method for preparing a modified high-nickel ternary positive electrode material as described in any of the aforementioned embodiments, comprising the following steps: coating the surface of a high-nickel ternary positive electrode material with a lithium-free or lithium-poor Prussian blue material to obtain a lithium-free or lithium-poor Prussian blue material coating layer; performing lithium supplementation treatment on the lithium-free or lithium-poor Prussian blue material coating layer to obtain a lithium-rich Prussian blue material coating layer.
  • the preparation of the lithium-free or lithium-deficient Prussian blue material coating layer includes: coating a dispersion of the lithium-free or lithium-deficient Prussian blue material on the surface of the high-nickel ternary positive electrode material by spray coating, and drying.
  • the dispersion of the lithium-free or lithium-deficient Prussian blue material contains a dispersion solvent and the lithium-free or lithium-deficient Prussian blue material;
  • the boiling point of the dispersion solvent is 50°C to 150°C.
  • the spray coating time is 0.5h-1.5h.
  • the drying temperature is 100° C.-200° C., and/or the drying time is 3 h-5 h.
  • the lithium replenishment treatment is performed by electrochemical lithium replenishment.
  • the lithium replenishment treatment includes: making a high-nickel ternary positive electrode material with a lithium-free or lithium-deficient Prussian blue material coating layer into a pole piece, and then subjecting the pole piece and the lithium-containing metal material to an electrochemical reaction in an electrolyte under the condition that the pole piece is separated by a diaphragm.
  • the preparation of the pole piece includes: preparing a high-nickel ternary positive electrode material having a lithium-free or lithium-deficient Prussian blue material coating layer with a conductive agent, a binder and a solvent into a slurry, coating the slurry on a current collector, and drying.
  • the preparation conditions of the pole piece include at least one of the following characteristics:
  • Feature 1 The mass ratio of the high nickel ternary positive electrode material with a lithium-free or lithium-deficient Prussian blue material coating layer to the conductive agent, the binder and the solvent is 90-95:2-8:2-8:40-50;
  • the conductive agent includes at least one of acetylene black, carbon black, carbon nanotubes, Ketjen black and carbon fiber;
  • the binder includes at least one of polyvinylidene fluoride and polytetrafluoroethylene;
  • the solvent includes at least one of N-methylpyrrolidone, dimethylformamide, diethylformamide, dimethyl sulfoxide and tetrahydrofuran;
  • the current collector includes at least one of aluminum foil, copper foil, titanium mesh, titanium sheet, carbon cloth and carbon paper;
  • Drying temperature is 60°C-80°C
  • Drying time is 3h-12h.
  • the electrolyte includes a lithium salt electrolyte and a non-aqueous solvent.
  • the lithium salt electrolyte includes at least one of lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium chloride, lithium bromide, and lithium chloroaluminate.
  • the non-aqueous solvent includes at least one of a chain acid ester, a cyclic acid ester, a chain ether, and a cyclic ether.
  • the non-aqueous solvent includes at least one of dimethyl carbonate, diethyl carbonate, ethylene carbonate, dimethylformamide and tetrahydrofuran.
  • the concentration of the lithium salt electrolyte is 1 mol/L-5 mol/L.
  • the membrane comprises a polyethylene membrane or a polypropylene membrane.
  • the voltage during the lithium replenishment process is 0.3V-1V.
  • the preparation of the high-nickel ternary positive electrode material includes: sintering a mixture of a high-nickel ternary positive electrode material precursor and a lithium source.
  • the preparation conditions of the high-nickel ternary positive electrode material include at least one of the following characteristics:
  • the lithium source is lithium hydroxide
  • Feature 3 The molar ratio of lithium in the lithium source to the metal element in the high nickel ternary cathode material precursor is 1.01:1-1.05:1;
  • Feature 4 Sintering is carried out in an oxygen atmosphere
  • Sintering temperature is 650°C-1200°C
  • the preparation of the high-nickel ternary positive electrode material precursor includes: subjecting a mixed metal soluble salt solution containing nickel, cobalt and manganese to a co-precipitation reaction with a complexing agent and a precipitant.
  • the preparation conditions of the high-nickel ternary cathode material precursor include at least one of the following characteristics:
  • the mixed metal soluble salt solution includes a mixed metal chloride solution, a mixed metal sulfate solution, a mixed metal nitrate solution, a mixed metal acetate solution or a mixed metal oxalate solution;
  • the total concentration of metal ions in the mixed metal soluble salt solution is 1mol/L-3mol/L;
  • the complexing agent includes ammonia water
  • the precipitant includes a strong alkaline solution
  • the temperature of the coprecipitation reaction is 40°C-60°C;
  • Feature 8 The co-precipitation reaction is carried out under protective atmosphere conditions.
  • the strong alkaline solution includes at least one of a sodium hydroxide solution and a potassium hydroxide solution.
  • the concentration of the strong base in the strong base solution is 3 mol/L-8 mol/L.
  • the present disclosure provides a battery comprising the modified high-nickel ternary positive electrode material of any one of the aforementioned embodiments.
  • the modified high-nickel ternary positive electrode material disclosed in the present invention is obtained by coating the high-nickel ternary positive electrode material with a lithium-free or lithium-deficient Prussian blue material, and then subjecting the coating layer to a lithium supplementation treatment in an electrolyte.
  • a coating layer of Prussian blue material is coated without lithium or with poor lithium.
  • the coating layer is hydrophobic and can isolate moisture in the air, thereby preventing Li2O on the surface of the high-nickel ternary positive electrode material from being converted into LiOH or Li2CO3 after contacting water, thereby helping to reduce the surface residual alkali content of the material; subsequently, the hydrophobic coating layer is treated with lithium supplementation in an electrolyte, at which time the coating layer will not contact moisture in the air. After lithium supplementation, the coating layer can be lithium-rich and have good hydrophilicity, thereby enabling the material to have a higher gram capacity.
  • FIG1 is a flow chart of the preparation of a modified high-nickel ternary positive electrode material in Example 1 of the present disclosure
  • FIG2 is a flow chart of the preparation of a modified high-nickel ternary positive electrode material in Example 2 of the present disclosure
  • FIG3 is a flow chart of the preparation of a modified high-nickel ternary positive electrode material in Example 3 of the present disclosure
  • Figure 4 is a flow chart for preparing the modified high-nickel ternary positive electrode material in Example 4 of the present disclosure.
  • the modified high-nickel ternary positive electrode material, preparation method and battery provided by the present invention are described in detail below.
  • the present disclosure provides a modified high-nickel ternary positive electrode material, wherein the modified high-nickel ternary positive electrode material is obtained by coating a high-nickel ternary positive electrode material with a lithium-free or lithium-deficient Prussian blue material and then supplementing the coating layer with lithium in an electrolyte.
  • the preparation method of the modified high-nickel ternary positive electrode material comprises: The surface of the high-nickel ternary positive electrode material is coated with a blue material to obtain a lithium-free or lithium-poor Prussian blue material coating layer; the lithium-free or lithium-poor Prussian blue material coating layer is supplemented with lithium in an electrolyte to obtain a lithium-rich Prussian blue material coating layer.
  • lithium-free or lithium-poor Prussian blue material By using lithium-free or lithium-poor Prussian blue material to coat the high-nickel ternary positive electrode, since the hygroscopicity of the lithium-free or lithium-poor Prussian blue material is much lower than that of the high-nickel positive electrode material, small particles of high-nickel positive electrode material can be prevented from absorbing water and agglomerating when in contact with air, thereby avoiding screening difficulties and blockages in the actual production process.
  • lithium-free or lithium-poor Prussian blue materials as hydrophobic substances to coat high-nickel ternary positive electrode materials can isolate moisture in the air, so that Li 2 O on the surface of the high-nickel ternary positive electrode material cannot be converted into LiOH or Li 2 CO 3 , effectively reducing the surface residual alkali content of the high-nickel ternary positive electrode material. Further, by supplementing the lithium-free or lithium-poor Prussian blue material coating layer in the electrolyte, the coating layer will not come into contact with moisture in the air.
  • the coating layer can be transformed from a lithium-poor or lithium-free state to a lithium-rich state and become hydrophilic, while effectively maintaining the gram capacity of the material and not preventing lithium ions from escaping during the cycle. Moreover, after the lithium-rich Prussian blue material coating layer is de-lithiated during the cycle, the lithium vacancies generated can accommodate crystal water to prevent it from reacting with the electrolyte.
  • the high-nickel ternary positive electrode material can be purchased directly or prepared by oneself.
  • the mixture of high-nickel ternary positive electrode material precursor and lithium source can be sintered to obtain the desired high-nickel ternary positive electrode material.
  • the high nickel ternary cathode material precursor may be Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 , Ni 0.83 Co 0.1 Mn 0.07 (OH) 2 , Ni 0.85 Co 0.1 Mn 0.05 (OH) 2 , Ni 0.88 Co 0.09 Mn 0.03 (OH) 2 , Ni 0.9 Co 0.05 Mn 0.05 (OH) 2 , Ni 0.9 Co 0.06 Mn 0.04 (OH) 2 , Ni 0.92 Co 0.06 Mn 0.02 (OH) 2 , or Ni 0.94 Co 0.04 Mn 0.02 (OH) 2.
  • the high nickel ternary cathode material may also be any other high nickel ternary cathode material satisfying the above molecular formula.
  • the high-nickel ternary positive electrode material precursor can be purchased directly or prepared by itself.
  • the preparation method of the high-nickel ternary positive electrode material precursor can refer to: co-precipitating a mixed metal soluble salt solution containing nickel, cobalt, and manganese with a complexing agent and a precipitant.
  • the mixed metal soluble salt solution may include, for example, a mixed metal chloride solution, a mixed metal sulfate solution, a mixed metal nitrate solution, a mixed metal acetate solution or a mixed metal oxalate solution, etc.
  • soluble salt solutions of mixed metals may also be used.
  • the total concentration of metal ions in the mixed metal soluble salt solution can be 1mol/L-3mol/L, such as 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L or 3mol/L, or any other value within the range of 1mol/L-3mol/L.
  • the complexing agent can be, for example, aqueous ammonia, whose mass concentration can be 20%-30%, such as 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29% or 30%, or any other value within the range of 20%-30%.
  • the precipitant may be, for example, a strong alkali solution.
  • the concentration of the strong alkali in the strong alkali solution may be 3mol/L-8mol/L, such as 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L, 5mol/L, 5.5mol/L, 6mol/L, 6.5mol/L, 7mol/L, 7.5mol/L or 8mol/L, etc., or any other value within the range of 3mol/L-8mol/L.
  • the coprecipitation reaction can be carried out at a pH value of 11 to 13.
  • the pH value corresponding to the coprecipitation reaction can be 11, 11.2, 11.5, 11.8, 12, 12.2, 12.5, 12.8 or 13, or any other value within the range of 11-13.
  • the temperature of the coprecipitation reaction can be 40°C-60°C, such as 40°C, 45°C, 50°C, 51°C, 52°C, 53°C, 54°C, 55°C, 56°C, 57°C, 58°C, 59°C or 60°C, etc., or it can be any other value within the range of 40°C-60°C.
  • the coprecipitation reaction time can be 2 h-5 h, such as 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h or 5 h, etc., or any other value within the range of 2 h-5 h.
  • the coprecipitation reaction is carried out under a protective atmosphere (such as a nitrogen atmosphere or an inert gas atmosphere) to avoid Prevent metal elements from being oxidized.
  • a protective atmosphere such as a nitrogen atmosphere or an inert gas atmosphere
  • the lithium source used to prepare the high-nickel ternary positive electrode material is lithium hydroxide.
  • the molar ratio of lithium element in the lithium source to metal element in the high nickel ternary positive electrode material precursor can be 1.01:1-1.05:1, such as 1.01:1, 1.02:1, 1.03:1, 1.04:1 or 1.05:1, or any other value within the range of 1.01:1-1.05:1.
  • Sintering is carried out in an oxygen atmosphere.
  • the sintering temperature may be 650°C-1200°C, such as 650°C, 700°C, 750°C, 800°C, 850°C, 900°C, 950°C, 1000°C, 1050°C or 1200°C, or any other value within the range of 650°C-1200°C.
  • the sintering time can be 5h-12h, such as 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h, 10h, 10.5h, 11h, 11.5h or 12h, etc., or it can be any other value within the range of 5h-12h.
  • the preparation of the lithium-free or lithium-deficient Prussian blue material coating layer can refer to: coating the dispersion of the lithium-free or lithium-deficient Prussian blue material on the surface of the high-nickel ternary positive electrode material by spray coating, and drying.
  • the dispersion liquid of the lithium-free or lithium-deficient Prussian blue material contains a dispersion solvent and the lithium-free or lithium-deficient Prussian blue material.
  • the molecular formula of the lithium-free or lithium-poor Prussian blue material is Li x M y [Fe(CN) 6 ] z , where x ⁇ 1, 1 ⁇ y ⁇ 3, 1 ⁇ z ⁇ 2, and M is a transition metal.
  • M may include Ni, Co, or Mn.
  • the lithium-free or lithium-poor Prussian blue material may include at least one of LiFe[Fe(CN) 6 ], Ni 3 [Fe(CN) 6 ] 2 , Co 3 [Fe(CN) 6 ] 2 , and Mn 3 [Fe(CN) 6 ] 2 .
  • the mass of lithium-free or lithium-deficient Prussian blue material can be 5%-10% of the high-nickel ternary positive electrode material, such as 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5% or 10%, etc., or it can be any other value within the range of 5%-10%.
  • the boiling point of the dispersion solvent is 50°C-150°C.
  • the dispersion solvent may be ethanol, isopropanol, Or cyclohexane, etc.
  • the mass ratio of the lithium-free or lithium-deficient Prussian blue material and the dispersion solvent may be 5:100-25:100, such as 5:100, 10:100, 15:100, 20:100 or 25:100, or any other value within the range of 5:100-25:100.
  • the spray coating time can be 0.5h-1.5h, such as 0.5h, 0.8h, 1h, 1.2h or 1.5h, etc., or any other value within the range of 0.5h-1.5h.
  • the drying temperature during the preparation of the lithium-free or lithium-poor Prussian blue material coating layer can be 100° C.-200° C., such as 100° C., 120° C., 150° C., 180° C. or 200° C., or any other value within the range of 100° C.-200° C.
  • the drying time can be 3 h-5 h, such as 3 h, 3.5 h, 4 h, 4.5 h or 5 h, or any other value within the range of 3 h-5 h.
  • the corresponding material when the Prussian blue material does not contain Li, the corresponding material is in a lithium-free state and has poor hydrophilicity. By lithium supplementation, it can be transformed into a lithium-rich state to improve its hydrophilicity. When the Prussian blue material contains Li before the lithium supplementation, the corresponding material is in a lithium-poor state. By lithium supplementation, the lithium content can also be increased to improve its hydrophilicity.
  • lithium-rich in the present disclosure is based on the lithium content of the Prussian blue material before the lithium supplementation treatment.
  • the lithium content in the corresponding Prussian blue material is increased, thereby defining the corresponding material obtained after the lithium supplementation treatment as being lithium-rich, and the corresponding material before the lithium supplementation treatment is lithium-free or lithium-poor. Relatively speaking, the more lithium content, the stronger the hydrophilicity of the material.
  • the present disclosure makes full use of the different properties of Prussian materials at different lithium contents, so that the prepared positive electrode material maintains a hydrophobic surface during storage, avoiding contact between Li2O and moisture in the air, and can be converted into a hydrophilic material after being prepared into an electrode sheet, ensuring that the positive electrode material is a hydrophobic material when hydrophobic properties are required, and a hydrophilic material when hydrophilic properties are required, thereby achieving a controllable conversion between hydrophobic and hydrophilic.
  • the lithium replenishment treatment of the present application is carried out by electrochemical lithium replenishment.
  • the lithium supplementation process may include: forming a high nickel ternary positive electrode material having a lithium-free or lithium-deficient Prussian blue material coating layer into a pole piece, and then separating the pole piece from the lithium-containing metal material through a separator. Under the conditions, the electrochemical reaction is carried out in the electrolyte.
  • the preparation of the pole piece may include: preparing a slurry of a high-nickel ternary positive electrode material having a lithium-free or lithium-poor Prussian blue material coating layer, a conductive agent, a binder and a solvent, coating the slurry on a current collector, and drying.
  • the mass ratio of the high nickel ternary positive electrode material having a lithium-free or lithium-deficient Prussian blue material coating layer to the conductive agent, binder and solvent can be 90-95:2-8:2-8:40-50, such as 92:4:4:45 or 90:5:5:45.
  • the conductive agent may include at least one of acetylene black, carbon black, carbon nanotubes, Ketjen black and carbon fiber.
  • the binder may include at least one of polyvinylidene fluoride and polytetrafluoroethylene.
  • the solvent may include at least one of N-methylpyrrolidone, dimethylformamide, diethylformamide, dimethyl sulfoxide and tetrahydrofuran.
  • the current collector may include, for example, at least one of aluminum foil, copper foil, titanium mesh, titanium sheet, carbon cloth, and carbon paper.
  • the drying temperature during the preparation of the pole piece may be 60°C-80°C, such as 60°C, 65°C, 70°C, 75°C or 80°C, or any other value within the range of 60°C-80°C.
  • the drying time may be 3h-12h, such as 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12h, or any other value within the range of 3h-12h.
  • the lithium-containing metal material may be a lithium-containing metal sheet, for example, a lithium metal sheet.
  • the membrane may include, for example, a polyethylene membrane or a polypropylene membrane.
  • the electrolyte includes a lithium salt electrolyte and a non-aqueous solvent.
  • the lithium salt electrolyte may include, for example, at least one of lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium chloride, lithium bromide, and lithium chloroaluminate.
  • the non-aqueous solvent may include at least one of a chain acid ester, a cyclic acid ester, a chain ether, and a cyclic ether, such as at least one of dimethyl carbonate, diethyl carbonate, ethylene carbonate, dimethylmethane, and tetrahydrofuran.
  • the concentration of the lithium salt electrolyte can be 1mol/L-5mol/L, such as 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L or 5mol/L, etc., or it can be any other value within the range of 1mol/L-5mol/L.
  • the voltage during lithium replenishment can be 0.3V-1V, such as 0.3V, 0.4V, 0.5V, 0.6V, 0.7V, 0.8V, 0.9V or 1V, etc., or any other value in the range of 0.3V-1V.
  • the lithium replenishment time can be set as needed.
  • the lithium replenishment is stopped when the current drops to 0.2 mA during the lithium replenishment process.
  • the present disclosure also provides a battery, which contains the above-mentioned modified high-nickel ternary positive electrode material.
  • the battery also contains a negative electrode plate and a separator.
  • Nickel chloride, cobalt chloride and manganese chloride are mixed with water according to the ratio in Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 (the molar ratio of nickel, cobalt and manganese is 0.8:0.1:0.1) to obtain a mixed metal soluble salt solution.
  • the total concentration of metal ions in the mixed metal soluble salt solution is 2 mol/L.
  • the mixed metal soluble salt solution is mixed with ammonia water (ammonia water mass concentration is 25%) and a NaOH aqueous solution (the concentration of NaOH in the NaOH aqueous solution is 5 mol/L), and a coprecipitation reaction is carried out for 3 hours under a nitrogen atmosphere at a pH value of 12.5 and a temperature of 55°C to obtain a Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 high nickel ternary material precursor.
  • the obtained high-nickel ternary material precursor was mixed with lithium hydroxide at a molar ratio of lithium element in lithium hydroxide to metal element in the precursor of 1.02:1, and sintered at 700° C. for 8 hours in a nitrogen atmosphere to obtain a high-nickel ternary positive electrode material.
  • LiFe[Fe(CN) 6 ] and ethanol were mixed at a mass ratio of 20:100 to obtain a dispersion of a lithium-poor Prussian blue material.
  • the dispersion of the lithium-poor Prussian blue material was coated on the surface of the high-nickel ternary positive electrode material obtained in S1 by spray coating (spraying time was 1h), and then dried at 180°C for 3h to obtain the lithium-poor Prussian blue-coated high-nickel ternary positive electrode material.
  • the electrode obtained in S3 and the lithium metal sheet are placed in an electrolyte (a dimethyl carbonate solution of lithium hexafluorophosphate, with a lithium hexafluorophosphate concentration of 3 mol/L in the electrolyte), the electrode and the lithium metal sheet are separated by a polypropylene diaphragm, the electrode is connected to the positive electrode of the power supply, the lithium metal sheet is connected to the negative electrode of the power supply, the power supply is turned on, and lithium is replenished at 0.5V until the current drops to 0.2mA and lithium replenishment is stopped. The electrode after lithium replenishment is washed, dried and stored.
  • electrolyte a dimethyl carbonate solution of lithium hexafluorophosphate, with a lithium hexafluorophosphate concentration of 3 mol/L in the electrolyte
  • the material of the coating layer changes from a lithium-poor state to a lithium-rich state.
  • the corresponding chemical equation can be referred to as: LiFe[Fe(CN) 6 ]+Li + +e - ⁇ Li 2 Fe[Fe(CN) 6 ].
  • the preparation flow chart of the modified high-nickel ternary positive electrode material in this embodiment is shown in Figure 2.
  • the material of the coating layer changes from a lithium-free state to a lithium-rich state.
  • the corresponding chemical equation can be referred to: Ni 3 [Fe(CN) 6 ] 2 +2Li + +2e - ⁇ Li 2 NiFe(CN) 6 +Ni 2 Fe(CN) 6 .
  • the preparation flow chart of the modified high-nickel ternary positive electrode material in this embodiment is shown in Figure 3.
  • the material of the coating layer changes from a lithium-free state to a lithium-rich state.
  • the corresponding chemical equation can be referred to: Co 3 [Fe(CN) 6 ] 2 +2Li + +2e - ⁇ Li 2 CoFe(CN) 6 +Co 2 Fe(CN) 6 .
  • LiFe[Fe(CN) 6 ] is replaced by Mn 3 [Fe(CN) 6 ] 2 .
  • the preparation flow chart of the modified high-nickel ternary positive electrode material in this embodiment is shown in FIG4 .
  • the material of the coating layer changes from a lithium-free state to a lithium-rich state.
  • the corresponding chemical equation can be referred to as: Mn 3 [Fe(CN) 6 ] 2 +2Li + +2e - ⁇ Li 2 MnFe(CN) 6 +Mn 2 Fe(CN) 6 .
  • Nickel chloride, cobalt chloride and manganese chloride are mixed with water according to the ratio in Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 (the molar ratio of nickel, cobalt and manganese is 0.8:0.1:0.1) to obtain a mixed metal soluble salt solution.
  • the total concentration of metal ions in the mixed metal soluble salt solution is 1 mol/L.
  • LiFe[Fe(CN) 6 ] and ethanol were mixed at a mass ratio of 5:100 to obtain a dispersion of a lithium-poor Prussian blue material.
  • the dispersion of the lithium-poor Prussian blue material is coated on the surface of the high-nickel ternary positive electrode material obtained in S1 by spray coating (spraying time is 1.5h), and then dried at 100°C for 5h to obtain the lithium-poor Prussian blue-coated high-nickel ternary positive electrode material.
  • the lithium-poor Prussian blue-coated high-nickel positive electrode material obtained in S2 is mixed with carbon black, polytetrafluoroethylene and dimethylformamide in a mass ratio of 90:2:8:40 to obtain a slurry.
  • the slurry is coated on a carbon cloth.
  • the electrode was dried at 70°C for 12 hours to obtain an electrode.
  • the electrode obtained in S3 and the lithium metal sheet are placed in an electrolyte (a diethyl carbonate solution of lithium perchlorate, the concentration of lithium perchlorate in the electrolyte is 1 mol/L), the electrode and the lithium metal sheet are separated by a polyethylene diaphragm, the electrode is connected to the positive electrode of the power supply, the lithium metal sheet is connected to the negative electrode of the power supply, the power supply is turned on, and lithium is replenished at 0.3V until the current drops to 0.2mA and lithium replenishment is stopped. The electrode after lithium replenishment is washed, dried and stored.
  • an electrolyte a diethyl carbonate solution of lithium perchlorate, the concentration of lithium perchlorate in the electrolyte is 1 mol/L
  • This embodiment provides a modified high-nickel ternary positive electrode material, which is prepared by the following method:
  • Nickel chloride, cobalt chloride and manganese chloride are mixed with water according to the ratio in Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 (the molar ratio of nickel, cobalt and manganese is 0.8:0.1:0.1) to obtain a mixed metal soluble salt solution.
  • the total concentration of metal ions in the mixed metal soluble salt solution is 3 mol/L.
  • the mixed metal soluble salt solution is mixed with ammonia water (ammonia water mass concentration is 30%) and a KOH aqueous solution (the concentration of KOH in the KOH aqueous solution is 8 mol/L), and a coprecipitation reaction is carried out for 2 hours under a nitrogen atmosphere at a pH value of 13 and a temperature of 60°C to obtain a Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 high nickel ternary material precursor.
  • the obtained high-nickel ternary material precursor was mixed with lithium hydroxide at a molar ratio of lithium element in lithium hydroxide to metal element in the precursor of 1.05:1, and sintered at 800° C. for 5 hours in a nitrogen atmosphere to obtain a high-nickel ternary positive electrode material.
  • LiFe[Fe(CN) 6 ] and ethanol were mixed at a mass ratio of 25:100 to obtain a dispersion of a lithium-poor Prussian blue material.
  • the dispersion of the lithium-poor Prussian blue material is coated on the surface of the high-nickel ternary positive electrode material obtained in S1 by spray coating (spraying time is 0.5h), and then dried at 200°C for 3h to obtain the lithium-poor Prussian blue-coated high-nickel ternary positive electrode material.
  • the lithium-poor Prussian blue-coated high-nickel cathode material obtained in S2 was mixed with carbon fiber, polyvinylidene fluoride and diethylformamide in a mass ratio of 95:3:2:50 to obtain a slurry.
  • the slurry was coated on a titanium mesh and dried at 80° C. for 3 h to obtain a pole piece.
  • the electrode obtained in S3 and the lithium metal sheet are placed in an electrolyte (lithium chloride ethylene carbonate solution, the concentration of lithium chloride in the electrolyte is 5 mol/L), the electrode and the lithium metal sheet are separated by a polypropylene diaphragm, the electrode is connected to the positive electrode of the power supply, the lithium metal sheet is connected to the negative electrode of the power supply, the power supply is turned on, and lithium replenishment is performed under the condition of 1V until the current drops to 0.2mA and lithium replenishment is stopped. The electrode after lithium replenishment is washed, dried and stored.
  • an electrolyte lithium chloride ethylene carbonate solution, the concentration of lithium chloride in the electrolyte is 5 mol/L
  • the high-nickel ternary positive electrode material precursor is Ni 0.9 Co 0.05 Mn 0.05 (OH) 2 .
  • the high-nickel ternary positive electrode material precursor is Ni 0.92 Co 0.06 Mn 0.02 (OH) 2 .
  • Example 1 The difference between this comparative example and Example 1 is that Li 2 Fe[Fe(CN) 6 ] is directly coated on the surface of the high-nickel ternary positive electrode material, and no lithium supplementation treatment is performed.
  • the comparative example is the Prussian blue-coated high-nickel ternary positive electrode material obtained in S2 in Example 1.
  • Example 1 The only difference between this comparative example and Example 1 is that hydrophobic carbon nanotubes are used instead of LiFe[Fe(CN) 6 ].
  • Example 1 The only difference between this comparative example and Example 1 is that hydrophilic lithium manganate is used instead of LiFe[Fe(CN) 6 ].
  • the modified high-nickel ternary positive electrode material provided in the embodiment of the present disclosure can enable the battery to have a higher discharge gram capacity and cycle capacity retention rate after being prepared into a battery.
  • Example 1 Comparative Example 3
  • the use of a hydrophobic material lacking lithium to coat the high-nickel ternary positive electrode material will lead to a significant decrease in gram capacity.
  • the modified high-nickel ternary positive electrode material provided in the present disclosure has a low surface residual alkali content and a high gram capacity.
  • the preparation method of the modified high-nickel ternary positive electrode material is simple, easy to operate, and can be promoted industrially. Batteries containing the above-mentioned modified high-nickel ternary positive electrode material can have higher electrochemical properties.
  • the modified high-nickel ternary positive electrode material provided by the present disclosure has a low surface residual alkali content and a high gram capacity.
  • the preparation method thereof is simple, easy to operate, and can be industrially promoted.
  • the battery containing the modified high-nickel ternary positive electrode material can have high electrochemical performance and can be used in the fields of automobiles and the like.

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Abstract

本文公开了一种改性高镍三元正极材料及其制备方法与电池，属于电池技术领域。该改性高镍三元正极材料由无锂或贫锂的普鲁士蓝材料对高镍三元正极材料进行包覆后，于电解液中再对包覆层进行补锂处理而得。该改性高镍三元正极材料的表面残碱含量低，克容量较高。该改性高镍三元正极材料的制备方法简单，易操作，可工业化推广。含有上述改性高镍三元正极材料的电池能够具有较高的电化学性能。

Description

一种改性高镍三元正极材料及其制备方法与电池 技术领域
本公开涉及电池技术领域，具体而言，涉及一种改性高镍三元正极材料及其制备方法与电池。
背景技术
三元正极材料按照其组成元素镍、钴、锰的不同比例，可分为111型、523型、622型以及811型等，随着镍含量的增高，材料容量也随之提升，但高镍三元正极材料表面存在的残碱，使其在制备过程中表现出强碱性和强吸潮性，不仅导致浆料制备过程困难，而且还会加速电解液的分解。
表面包覆是改善高镍正极材料性能的一种有效手段，现有的表面包覆方法虽能降低材料表面的残碱含量，但同时又会引起材料克容量的降低。
鉴于此，特提出本公开。
发明内容
本公开的目的之一包括提供一种改性高镍三元正极材料，该改性高镍三元正极材料的表面残碱含量较低，且能够保持较高的克容量。
本公开的目的之二包括提供一种上述改性高镍三元正极材料的制备方法。
本公开的目的之三包括提供一种含有上述改性高镍三元正极材料的电池。
本公开可这样实现：
第一方面，本公开提供一种改性高镍三元正极材料，改性高镍三元正极材料由无锂或贫锂的普鲁士蓝材料对高镍三元正极材料进行包覆后，于电解液中再对包覆层进行补锂处理而得。
在可选的实施方式中，无锂或贫锂的普鲁士蓝材料的分子式为LixMy[Fe(CN)6]z，x≤1，1≤y≤3，1≤z≤2，M为过渡金属。
在可选的实施方式中，M包括Ni、Co或Mn。
在可选的实施方式中，无锂或贫锂的普鲁士蓝材料包括LiFe[Fe(CN)6]、Ni3[Fe(CN)6]2、Co3[Fe(CN)6]2和Mn3[Fe(CN)6]2中的至少一种。
在可选的实施方式中，无锂或贫锂的普鲁士蓝材料的质量为高镍三元正极材料的5％-10％。
第二方面，本公开提供如前述实施方式任一项的改性高镍三元正极材料的制备方法，包括以下步骤：将无锂或贫锂的普鲁士蓝材料对高镍三元正极材料的表面进行包覆，得到无锂或贫锂的普鲁士蓝材料包覆层；对无锂或贫锂的普鲁士蓝材料包覆层进行补锂处理，得到富锂普鲁士蓝材料包覆层。
在可选的实施方式中，无锂或贫锂的普鲁士蓝材料包覆层的制备包括：将无锂或贫锂的普鲁士蓝材料的分散液通过喷雾包覆方式包覆于高镍三元正极材料的表面，干燥。
在可选的实施方式中，无锂或贫锂的普鲁士蓝材料的分散液中含有分散溶剂以及无锂或贫锂的普鲁士蓝材料；
分散溶剂的沸点为50℃-150℃。
在可选的实施方式中，喷雾包覆的时间为0.5h-1.5h。
在可选的实施方式中，干燥温度为100℃-200℃，和/或，干燥时间为3h-5h。
在可选的实施方式中，补锂处理采用电化学补锂方式进行。
在可选的实施方式中，补锂处理包括：将具有无锂或贫锂的普鲁士蓝材料包覆层的高镍三元正极材料制成极片，再将极片与含锂金属材料在隔膜隔开的条件下，于电解液中进行电化学反应。
在可选的实施方式中，极片的制备包括：将具有无锂或贫锂的普鲁士蓝材料包覆层的高镍三元正极材料与导电剂、粘结剂以及溶剂制成浆料，将浆料涂覆于集流体上，干燥。
在可选的实施方式中，极片的制备条件包括以下特征中的至少一种：
特征一：具有无锂或贫锂的普鲁士蓝材料包覆层的高镍三元正极材料与导电剂、粘结剂以及溶剂的质量比为90-95:2-8:2-8:40-50；
特征二：导电剂包括乙炔黑、炭黑、碳纳米管、科琴黑和碳纤维中的至少一种；
特征三：粘结剂包括聚偏氟乙烯和聚四氟乙烯中的至少一种；
特征四：溶剂包括N-甲基吡咯烷酮、二甲基甲酰胺、二乙基甲酰胺、二甲基亚砜和四氢呋喃中的至少一种；
特征五：集流体包括铝箔、铜箔、钛网、钛片、碳布和碳纸中的至少一种；
特征六：干燥温度为60℃-80℃；
特征七：干燥时间为3h-12h。
在可选的实施方式中，电解液包括锂盐电解质和非水溶剂。
在可选的实施方式中，锂盐电解质包括六氟磷酸锂、高氯酸锂、四氟硼酸锂、氯化锂、溴化锂和氯铝酸锂中的至少一种。
在可选的实施方式中，非水溶剂包括链状酸酯、环状酸酯、链状醚和环状醚中的至少一种。
在可选的实施方式中，非水溶剂包括碳酸二甲酯、碳酸二乙酯、碳酸乙烯酯、二氧甲基甲烷和四氢呋喃中的至少一种。
在可选的实施方式中，电解液中，锂盐电解质的浓度为1mol/L-5mol/L。
在可选的实施方式中，隔膜包括聚乙烯隔膜或聚丙烯隔膜。
在可选的实施方式中，补锂处理过程中的电压为0.3V-1V。
在可选的实施方式中，高镍三元正极材料的制备包括：将高镍三元正极材料前驱体与锂源的混合物进行烧结。
在可选的实施方式中，高镍三元正极材料的制备条件包括以下特征中的至少一种：
特征一：高镍三元正极材料前驱体的分子式为NiaCobMnc(OH)2，a+b+c＝1，0.8≤a＜1，0＜b≤0.1，0＜c≤0.1；
特征二：锂源为氢氧化锂；
特征三：锂源中锂元素与高镍三元正极材料前驱体中金属元素的摩尔比为 1.01:1-1.05:1；
特征四：烧结于氧气气氛下进行；
特征五：烧结温度为650℃-1200℃；
特征六：烧结时间为5h-12h。
在可选的实施方式中，高镍三元正极材料前驱体的制备包括：将含镍、钴、锰的混合金属可溶性盐溶液与络合剂以及沉淀剂进行共沉淀反应。
在可选的实施方式中，高镍三元正极材料前驱体的制备条件包括以下特征中的至少一种：
特征一：混合金属可溶性盐溶液包括混合金属的氯化盐溶液、混合金属的硫酸盐溶液、混合金属的硝酸盐溶液、混合金属的醋酸盐溶液或混合金属的草酸盐溶液；
特征二：混合金属可溶性盐溶液中金属离子的总浓度为1mol/L-3mol/L；
特征三：络合剂包括氨水；
特征四：沉淀剂包括强碱溶液；
特征五：共沉淀反应在pH值为11-13的条件下进行；
特征六：共沉淀反应的温度为40℃-60℃；
特征七：共沉淀反应的时间为2h-5h；
特征八：共沉淀反应于保护气氛条件下进行。
在可选的实施方式中，强碱溶液包括氢氧化钠溶液和氢氧化钾溶液中的至少一种。
在可选的实施方式中，强碱溶液中强碱的浓度为3mol/L-8mol/L。
第三方面，本公开提供一种电池，其含有前述实施方式任一项的改性高镍三元正极材料。
本公开的有益效果包括：
本公开中的改性高镍三元正极材料由无锂或贫锂的普鲁士蓝材料对高镍三元正极材料进行包覆后，于电解液中再对包覆层进行补锂处理而得。通过先 包覆无锂或贫锂的普鲁士蓝材料包覆层，该包覆层具有疏水性，能够隔绝空气中的水分，避免高镍三元正极材料表面的Li2O与水接触后转化成LiOH或Li2CO3，从而有利于降低材料的表面残碱含量；随后再在电解液中对该疏水性的包覆层进行补锂处理，此时包覆层不会与空气中的水分接触，补锂后能够使该包覆层呈富锂态并具有较好的亲水性，从而能够使材料具有较高的克容量。
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为本公开实施例1中改性高镍三元正极材料的制备流程图；
图2为本公开实施例2中改性高镍三元正极材料的制备流程图；
图3为本公开实施例3中改性高镍三元正极材料的制备流程图；
图4为本公开实施例4中改性高镍三元正极材料的制备流程图。
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。
下面对本公开提供的改性高镍三元正极材料及其制备方法与电池进行具体说明。
本公开提出一种改性高镍三元正极材料，该改性高镍三元正极材料由无锂或贫锂的普鲁士蓝材料对高镍三元正极材料进行包覆后，于电解液中再对包覆层进行补锂处理而得。
也即，该改性高镍三元正极材料的制备方法包括：将无锂或贫锂的普鲁士 蓝材料对高镍三元正极材料的表面进行包覆，得到无锂或贫锂的普鲁士蓝材料包覆层；于电解液中对无锂或贫锂的普鲁士蓝材料包覆层进行补锂处理，得到富锂普鲁士蓝材料包覆层。
通过采用无锂或贫锂的普鲁士蓝材料包覆高镍三元正极，由于无锂或贫锂的普鲁士蓝材料的吸湿性远低于高镍正极材料，能够避免小颗粒的高镍正极材料与空气接触吸水团聚，避免实际生产工艺中出现过筛困难及堵料等现象。
此外，采用无锂或贫锂的普鲁士蓝材料作为疏水物质包覆高镍三元正极材料，可隔绝空气中的水分，使得高镍三元正极材料表面的Li2O不能转化为LiOH或Li2CO3，有效降低了高镍三元正极材料的表面残碱含量。进一步地，通过在电解液中对无锂或贫锂的普鲁士蓝材料包覆层进行补锂处理，此时包覆层不会与空气中的水分接触，补锂后能够使包覆层由贫锂或无锂状态转变为富锂状态并具有亲水性，在有效维持材料的克容量的同时也不会阻止锂离子在循环过程中脱出。并且，富锂普鲁士蓝材料包覆层在循环过程中脱锂后，产生的锂空位能够容纳结晶水，防止其与电解液反应。
本公开中，高镍三元正极材料可直接购买得到，也可自行制备。
当自行制备高镍三元正极材料时，可将高镍三元正极材料前驱体与锂源的混合物进行烧结，从而得到所需的高镍三元正极材料。
作为参考地，高镍三元正极材料前驱体的分子式为NiaCobMnc(OH)2，a+b+c＝1，0.8≤a＜1，0＜b≤0.1，0＜c≤0.1。
在一些实施方式中，高镍三元正极材料前驱体可以为Ni0.8Co0.1Mn0.1(OH)2、Ni0.83Co0.1Mn0.07(OH)2、Ni0.85Co0.1Mn0.05(OH)2、Ni0.88Co0.09Mn0.03(OH)2、Ni0.9Co0.05Mn0.05(OH)2、Ni0.9Co0.06Mn0.04(OH)2、Ni0.92Co0.06Mn0.02(OH)2或Ni0.94Co0.04Mn0.02(OH)2。在其它实施方式中，高镍三元正极材料也可以为满足上述分子式的其它任意高镍三元正极材料。
在本公开中，高镍三元正极材料前驱体可直接购买得到，也可自行制备得到。
在一些实施方式中，高镍三元正极材料前驱体的制备方法可参照：将含镍、钴、锰的混合金属可溶性盐溶液与络合剂以及沉淀剂进行共沉淀反应。
其中，混合金属可溶性盐溶液例如可包括混合金属的氯化盐溶液、混合金属的硫酸盐溶液、混合金属的硝酸盐溶液、混合金属的醋酸盐溶液或混合金属的草酸盐溶液等，此外，也可采用混合金属的其它可溶性盐溶液的形式。
混合金属可溶性盐溶液中金属离子的总浓度可以为1mol/L-3mol/L，如1mol/L、1.5mol/L、2mol/L、2.5mol/L或3mol/L等，也可以为1mol/L-3mol/L范围内的其它任意值。
络合剂例如可为氨水。氨水的质量浓度可以为20％-30％，如20％、21％、22％、23％、24％、25％、26％、27％、28％、29％或30％等，也可以为20％-30％范围内的其它任意值。
沉淀剂例如可以为强碱溶液。强碱溶液中强碱的浓度可以为3mol/L-8mol/L，如3mol/L、3.5mol/L、4mol/L、4.5mol/L、5mol/L、5.5mol/L、6mol/L、6.5mol/L、7mol/L、7.5mol/L或8mol/L等，也可以为3mol/L-8mol/L范围内的其它任意值。示例性地，强碱溶液例如可包括氢氧化钠溶液和氢氧化钾溶液中的至少一种。通过调节强碱溶液的用量以使反应体系的pH值在预设范围(pH＝11-13)。
共沉淀反应可在pH值为11-13的条件下进行。示例性地，共沉淀反应对应的pH值可以为11、11.2、11.5、11.8、12、12.2、12.5、12.8或13等，也可以为11-13范围内的其它任意值。
共沉淀反应的温度可以为40℃-60℃，如40℃、45℃、50℃、51℃、52℃、53℃、54℃、55℃、56℃、57℃、58℃、59℃或60℃等，也可以为40℃-60℃范围内的其它任意值。
共沉淀反应的时间可以为2h-5h，如2h、2.5h、3h、3.5h、4h、4.5h或5h等，也可以为2h-5h范围内的其它任意值。
共沉淀反应于保护气氛(如氮气气氛或惰性气体气氛)条件下进行，以避 免金属元素被氧化。
本公开中，用于制备高镍三元正极材料的锂源为氢氧化锂。
锂源中锂元素与高镍三元正极材料前驱体中金属元素的摩尔比可以为1.01:1-1.05:1，如1.01:1、1.02:1、1.03:1、1.04:1或1.05:1等，也可以为1.01:1-1.05:1范围内的其它任意值。
烧结于氧气气氛下进行。
烧结温度可以为650℃-1200℃，如650℃、700℃、750℃、800℃、850℃、900℃、950℃、1000℃、1050℃或1200℃等，也可以为650℃-1200℃范围内的其它任意值。
烧结时间可以为5h-12h，如5h、5.5h、6h、6.5h、7h、7.5h、8h、8.5h、9h、9.5h、10h、10.5h、11h、11.5h或12h等，也可以为5h-12h范围内的其它任意值。
本公开中，无锂或贫锂的普鲁士蓝材料包覆层的制备可参照：将无锂或贫锂的普鲁士蓝材料的分散液通过喷雾包覆方式包覆于高镍三元正极材料的表面，干燥。
无锂或贫锂的普鲁士蓝材料的分散液中含有分散溶剂以及无锂或贫锂的普鲁士蓝材料。
其中，无锂或贫锂的普鲁士蓝材料的分子式为LixMy[Fe(CN)6]z，x≤1，1≤y≤3，1≤z≤2，M为过渡金属。
在一些实施方式中，M可以包括Ni、Co或Mn。示例性地，无锂或贫锂的普鲁士蓝材料例如可包括LiFe[Fe(CN)6]、Ni3[Fe(CN)6]2、Co3[Fe(CN)6]2和Mn3[Fe(CN)6]2中的至少一种。
作为参考地，无锂或贫锂的普鲁士蓝材料的质量可以为高镍三元正极材料的5％-10％，如5％、5.5％、6％、6.5％、7％、7.5％、8％、8.5％、9％、9.5％或10％等，也可以为5％-10％范围内的其它任意值。
分散溶剂的沸点为50℃-150℃，示例性地，分散溶剂可以为乙醇、异丙醇 或环己烷等。
无锂或贫锂的普鲁士蓝材料以及分散溶剂的质量比可以为5:100-25:100，如5:100、10:100、15:100、20:100或25:100等，也可以为5:100-25:100范围内的其它任意值。
喷雾包覆的时间可以为0.5h-1.5h，如0.5h、0.8h、1h、1.2h或1.5h等，也可以为0.5h-1.5h范围内的其它任意值。
无锂或贫锂的普鲁士蓝材料包覆层制备过程中的干燥温度可以为100℃-200℃，如100℃、120℃、150℃、180℃或200℃等，也可以为100℃-200℃范围内的其它任意值。干燥时间可以为3h-5h，如3h、3.5h、4h、4.5h或5h等，也可以为3h-5h范围内的其它任意值。
本公开中，当普鲁士蓝材料中不含Li时，相应的材料为无锂状态，亲水性较差，通过补锂处理，能够使其转变为富锂状态，提高其亲水性能。当未进行补锂处理前的普鲁士蓝材料中含Li时，相应的材料为贫锂状态，通过补锂处理，同样能提高其含锂量，提高其亲水性能。
需强调的是，本公开中“富锂”是以补锂处理前普鲁士蓝材料的锂含量为比较基础，通过补锂处理，相应的普鲁士蓝材料中锂含量得以提高，从而定义经补锂处理后所得的相应材料呈富锂状态，补锂处理前对应的材料为无锂或贫锂状态。相对而言，锂含量越多，材料的亲水性更强。
承上，本公开充分利用了普鲁士类材料在不同锂含量时表现的不同性质，使制备的正极材料在储存过程中保持表面疏水，避免了Li2O与空气中的水分接触，并能够在制备成极片后，转化为亲水材料，保证正极材料在需要疏水性质的时候为疏水材料，需要亲水性质的时候为亲水材料，实现了疏水和亲水之间可控的转化。
本申请的补锂处理采用电化学补锂方式进行。
在一些实施方式中，补锂处理可包括：将具有无锂或贫锂的普鲁士蓝材料包覆层的高镍三元正极材料制成极片，再将极片与含锂金属材料在隔膜隔开的 条件下，于电解液中进行电化学反应。
极片的制备可包括：将具有无锂或贫锂的普鲁士蓝材料包覆层的高镍三元正极材料与导电剂、粘结剂以及溶剂制成浆料，将浆料涂覆于集流体上，干燥。
其中，具有无锂或贫锂的普鲁士蓝材料包覆层的高镍三元正极材料与导电剂、粘结剂以及溶剂的质量比可以为90-95:2-8:2-8:40-50，如92:4:4:45或90:5:5:45等。
导电剂例如可包括乙炔黑、炭黑、碳纳米管、科琴黑和碳纤维中的至少一种。粘结剂例如可包括聚偏氟乙烯和聚四氟乙烯中的至少一种。溶剂例如可包括N-甲基吡咯烷酮、二甲基甲酰胺、二乙基甲酰胺、二甲基亚砜和四氢呋喃中的至少一种。
集流体例如可包括铝箔、铜箔、钛网、钛片、碳布和碳纸中的至少一种。
在一些实施方式中，极片制备过程中的干燥温度可以为60℃-80℃，如60℃、65℃、70℃、75℃或80℃等，也可以为60℃-80℃范围内的其它任意值。干燥时间可以为3h-12h，如3h、4h、5h、6h、7h、8h、9h、10h、11h或12h等，也可以为3h-12h范围内的其它任意值。
本公开中，含锂金属材料可以为含锂的金属片，例如可以为锂金属片。
隔膜例如可以包括聚乙烯隔膜或聚丙烯隔膜。
电解液包括锂盐电解质和非水溶剂。其中，锂盐电解质例如可包括六氟磷酸锂、高氯酸锂、四氟硼酸锂、氯化锂、溴化锂和氯铝酸锂中的至少一种。非水溶剂可包括链状酸酯、环状酸酯、链状醚和环状醚中的至少一种，如可包括碳酸二甲酯、碳酸二乙酯、碳酸乙烯酯、二氧甲基甲烷和四氢呋喃中的至少一种。
示例性地，电解液中，锂盐电解质的浓度可以为1mol/L-5mol/L，如1mol/L、1.5mol/L、2mol/L、2.5mol/L、3mol/L、3.5mol/L、4mol/L、4.5mol/L或5mol/L等，也可以为1mol/L-5mol/L范围内的其它任意值。
补锂处理过程中的电压可以为0.3V-1V，如0.3V、0.4V、0.5V、0.6V、 0.7V、0.8V、0.9V或1V等，也可以为0.3V-1V范围内的其它任意值。
补锂时间可根据需要进行设置，在一些实施方式中，补锂过程中电流降低至0.2mA时停止补锂。
进一步地，本公开还提供了一种电池，其含有上述改性高镍三元正极材料。除此以外，电池还含有负极极片和隔膜等。
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
本实施例提供一种改性高镍三元正极材料，请参照图1，其经以下方法制备得到：
S1：高镍正极材料的制备。
将氯化镍、氯化钴和氯化锰按照Ni0.8Co0.1Mn0.1(OH)2中的配比(镍、钴和锰的摩尔比为0.8:0.1:0.1)与水混合，得到混合金属可溶性盐溶液。该混合金属可溶性盐溶液中金属离子的总浓度为2mol/L。将混合金属可溶性盐溶液与氨水(氨水质量浓度为25％)、NaOH水溶液(NaOH水溶液中NaOH的浓度为5mol/L)混合，在氮气氛围下，于pH值为12.5、温度为55℃的条件下共沉淀反应3h，得到Ni0.8Co0.1Mn0.1(OH)2高镍三元材料前驱体。
将所得的高镍三元材料前驱体与氢氧化锂，按氢氧化锂中锂元素与前驱体中金属元素的摩尔比为1.02:1进行混合，在氮气气氛下700℃烧结8h，得到高镍三元正极材料。
S2：于高镍三元正极材料的表面包覆贫锂的普鲁士蓝材料。
将LiFe[Fe(CN)6]与乙醇按质量比为20:100进行混合，得到贫锂的普鲁士蓝材料的分散液。
按贫锂的普鲁士蓝材料的用量为高镍三元正极材料的7wt％，将贫锂的普鲁士蓝材料的分散液采用喷雾包覆(喷雾时间为1h)的方式包覆于S1所得的高镍三元正极材料的表面，然后再在180℃的条件下干燥3h，得到贫锂的普鲁士蓝包覆的高镍三元正极材料。
S3：制备极片。
将S2所得的贫锂的普鲁士蓝包覆的高镍正极材料与乙炔黑、聚偏氟乙烯和N-甲基吡咯烷酮按质量比为92:4:4:45混合，得到浆料。将该浆料涂覆于铝箔上，于60℃的条件下干燥8h，得到极片。
S4：电化学补锂。
将S3所得的极片与锂金属片置于电解液(六氟磷酸锂的碳酸二甲酯溶液，电解液中六氟磷酸锂的浓度为3mol/L)中，极片与锂金属片以聚丙烯隔膜隔开，将极片与电源的正极相连，锂金属片与电源的负极相连，接通电源，于0.5V的条件下进行补锂，直至电流降低至0.2mA时停止补锂。将补锂后的极片洗涤干燥后保存。
上述补锂过程中，包覆层的材料由贫锂转变为富锂状态，相应的化学方程式可参照：LiFe[Fe(CN)6]+Li++e-→Li2Fe[Fe(CN)6]。
实施例2
本实施例与实施例1的区别仅在于：将LiFe[Fe(CN)6]等量替换为Ni3[Fe(CN)6]2。
该实施例中改性高镍三元正极材料的制备流程图如图2所示，在补锂过程中，包覆层的材料由无锂转变为富锂状态，相应的化学方程式可参照：Ni3[Fe(CN)6]2+2Li++2e-→Li2NiFe(CN)6+Ni2Fe(CN)6。
实施例3
本实施例与实施例1的区别仅在于：将LiFe[Fe(CN)6]等量替换为Co3[Fe(CN)6]2。
该实施例中改性高镍三元正极材料的制备流程图如图3所示，在补锂过程中，包覆层的材料由无锂转变为富锂状态，相应的化学方程式可参照：Co3[Fe(CN)6]2+2Li++2e-→Li2CoFe(CN)6+Co2Fe(CN)6。
实施例4
本实施例与实施例1的区别仅在于：将LiFe[Fe(CN)6]等量替换为 Mn3[Fe(CN)6]2。
该实施例中改性高镍三元正极材料的制备流程图如图4所示，在补锂过程中，包覆层的材料由无锂转变为富锂状态，相应的化学方程式可参照：Mn3[Fe(CN)6]2+2Li++2e-→Li2MnFe(CN)6+Mn2Fe(CN)6。
实施例5
本实施例提供一种改性高镍三元正极材料，其经以下方法制备得到：
S1：高镍正极材料的制备。
将氯化镍、氯化钴和氯化锰按照Ni0.8Co0.1Mn0.1(OH)2中的配比(镍、钴和锰的摩尔比为0.8:0.1:0.1)与水混合，得到混合金属可溶性盐溶液。该混合金属可溶性盐溶液中金属离子的总浓度为1mol/L。将混合金属可溶性盐溶液与氨水(氨水质量浓度为20％)、NaOH水溶液(NaOH水溶液中NaOH的浓度为3mol/L)混合，在氮气氛围下，于pH值为11、温度为40℃的条件下共沉淀反应5h，得到Ni0.8Co0.1Mn0.1(OH)2高镍三元材料前驱体。
将所得的高镍三元材料前驱体与氢氧化锂，按氢氧化锂中锂元素与前驱体中金属元素的摩尔比为1.01:1进行混合，在氮气气氛下650℃烧结10h，得到高镍三元正极材料。
S2：于高镍三元正极材料的表面包覆贫锂的普鲁士蓝材料。
将LiFe[Fe(CN)6]与乙醇按质量比为5:100进行混合，得到贫锂的普鲁士蓝材料的分散液。
按贫锂的普鲁士蓝材料的用量为高镍三元正极材料的5wt％，将贫锂的普鲁士蓝材料的分散液采用喷雾包覆(喷雾时间为1.5h)的方式包覆于S1所得的高镍三元正极材料的表面，然后再在100℃的条件下干燥5h，得到贫锂的普鲁士蓝包覆的高镍三元正极材料。
S3：制备极片。
将S2所得的贫锂的普鲁士蓝包覆的高镍正极材料与炭黑、聚四氟乙烯和二甲基甲酰胺按质量比为90:2:8:40混合，得到浆料。将该浆料涂覆于碳布上， 于70℃的条件下干燥12h，得到极片。
S4：电化学补锂。
将S3所得的极片与锂金属片置于电解液(高氯酸锂的碳酸二乙酯溶液，电解液中高氯酸锂的浓度为1mol/L)中，极片与锂金属片以聚乙烯隔膜隔开，将极片与电源的正极相连，锂金属片与电源的负极相连，接通电源，于0.3V的条件下进行补锂，直至电流降低至0.2mA时停止补锂。将补锂后的极片洗涤干燥后保存。
实施例6
本实施例提供一种改性高镍三元正极材料，其经以下方法制备得到：
S1：高镍正极材料的制备。
将氯化镍、氯化钴和氯化锰按照Ni0.8Co0.1Mn0.1(OH)2中的配比(镍、钴和锰的摩尔比为0.8:0.1:0.1)与水混合，得到混合金属可溶性盐溶液。该混合金属可溶性盐溶液中金属离子的总浓度为3mol/L。将混合金属可溶性盐溶液与氨水(氨水质量浓度为30％)、KOH水溶液(KOH水溶液中KOH的浓度为8mol/L)混合，在氮气氛围下，于pH值为13、温度为60℃的条件下共沉淀反应2h，得到Ni0.8Co0.1Mn0.1(OH)2高镍三元材料前驱体。
将所得的高镍三元材料前驱体与氢氧化锂，按氢氧化锂中锂元素与前驱体中金属元素的摩尔比为1.05:1进行混合，在氮气气氛下800℃烧结5h，得到高镍三元正极材料。
S2：于高镍三元正极材料的表面包覆贫锂的普鲁士蓝材料。
将LiFe[Fe(CN)6]与乙醇按质量比为25:100进行混合，得到贫锂的普鲁士蓝材料的分散液。
按贫锂的普鲁士蓝材料的用量为高镍三元正极材料的10wt％，将贫锂的普鲁士蓝材料的分散液采用喷雾包覆(喷雾时间为0.5h)的方式包覆于S1所得的高镍三元正极材料的表面，然后再在200℃的条件下干燥3h，得到贫锂的普鲁士蓝包覆的高镍三元正极材料。
S3：制备极片。
将S2所得的贫锂的普鲁士蓝包覆的高镍正极材料与碳纤维、聚偏氟乙烯和二乙基甲酰胺按质量比为95:3:2:50混合，得到浆料。将该浆料涂覆于钛网上，于80℃的条件下干燥3h，得到极片。
S4：电化学补锂。
将S3所得的极片与锂金属片置于电解液(氯化锂的碳酸乙烯酯溶液，电解液中氯化锂的浓度为5mol/L)中，极片与锂金属片以聚丙烯隔膜隔开，将极片与电源的正极相连，锂金属片与电源的负极相连，接通电源，于1V的条件下进行补锂，直至电流降低至0.2mA时停止补锂。将补锂后的极片洗涤干燥后保存。
实施例7
本实施例与实施例1的区别仅在于：高镍三元正极材料前驱体为Ni0.9Co0.05Mn0.05(OH)2。
实施例8
本实施例与实施例1的区别仅在于：高镍三元正极材料前驱体为Ni0.92Co0.06Mn0.02(OH)2。
对比例1
本对比例与实施例1的区别仅在于：于高镍三元正极材料的表面直接包覆Li2Fe[Fe(CN)6]，并不再进行补锂处理。
对比例2
本对比例与实施例1的区别仅在于：无S3和S4步骤。
也即，该对比例为实施例1中S2得到的普鲁士蓝包覆的高镍三元正极材料。
对比例3
本对比例与实施例1的区别仅在于：以疏水的碳纳米管代替LiFe[Fe(CN)6]。
对比例4
本对比例与实施例1的区别仅在于：以亲水的锰酸锂代替LiFe[Fe(CN)6]。
对比例5
本对比例与实施例2的区别仅在于：无S3和S4步骤。
试验例
以金属锂片为对电极，Celgard 2400为隔膜，1mol/L的LiPF6的碳酸乙烯酯-碳酸二甲酯-碳酸甲乙酯混合溶液(碳酸乙烯酯-碳酸二甲酯-碳酸甲乙酯的体积比为1:1:1)为电解液，将实施例1-8以及对比例1-5的改性高镍三元正极材料分别组装成电池，将所得的电池在2.8-4.3V下进行电化学性能测试，其结果如表1所示。
表1电化学性能测试结果

由表1可以看出，本公开实施例提供的改性高镍三元正极材料在制备成电池后，能够使电池具有较高的放电克容量以及循环容量保持率。此外，通过对比实施例1和对比例3可知，采用缺乏锂的疏水性材料对高镍三元正极材料进行包覆，会导致克容量的明显降低。综上所述，本公开提供的改性高镍三元正极材料的表面残碱含量低，克容量较高。该改性高镍三元正极材料的制备方法简单，易操作，可工业化推广。含有上述改性高镍三元正极材料的电池能够具有较高的电化学性能。
工业实用性
本公开所提供的改性高镍三元正极材料具有较低的表面残碱含量和较高的克容量。其制备方法简单，易操作，可工业化推广。含有上述改性高镍三元正极材料的电池能够具有较高的电化学性能，可用于汽车等领域。

Claims (28)

  1. 一种改性高镍三元正极材料，其特征在于，所述改性高镍三元正极材料由无锂或贫锂的普鲁士蓝材料对高镍三元正极材料进行包覆后，于电解液中再对包覆层进行补锂处理而得。
  2. 根据权利要求1所述的改性高镍三元正极材料，其特征在于，所述无锂或贫锂的普鲁士蓝材料的分子式为LixMy[Fe(CN)6]z，x≤1，1≤y≤3，1≤z≤2，M为过渡金属。
  3. 根据权利要求2所述的改性高镍三元正极材料，其特征在于，M包括Ni、Co或Mn。
  4. 根据权利要求2或3所述的改性高镍三元正极材料，其特征在于，所述无锂或贫锂的普鲁士蓝材料包括LiFe[Fe(CN)6]、Ni3[Fe(CN)6]2、Co3[Fe(CN)6]2和Mn3[Fe(CN)6]2中的至少一种。
  5. 根据权利要求1-4任一项所述的改性高镍三元正极材料，其特征在于，所述无锂或贫锂的普鲁士蓝材料的质量为所述高镍三元正极材料的5％-10％。
  6. 如权利要求1-5任一项所述的改性高镍三元正极材料的制备方法，其特征在于，包括以下步骤：将无锂或贫锂的普鲁士蓝材料对高镍三元正极材料的表面进行包覆，得到无锂或贫锂的普鲁士蓝材料包覆层；对所述无锂或贫锂的普鲁士蓝材料包覆层进行补锂处理，得到富锂普鲁士蓝材料包覆层。
  7. 根据权利要求6所述的制备方法，其特征在于，所述无锂或贫锂的普鲁士蓝材料包覆层的制备包括：将无锂或贫锂的普鲁士蓝材料的分散液通过喷雾包覆方式包覆于所述高镍三元正极材料的表面，干燥。
  8. 根据权利要求7所述的制备方法，其特征在于，所述无锂或贫锂的普鲁士蓝材料的分散液中含有分散溶剂以及无锂或贫锂的普鲁士蓝材料；
    所述分散溶剂的沸点为50℃-150℃。
  9. 根据权利要求7-8任一项所述的制备方法，其特征在于，喷雾包覆的时间为0.5h-1.5h。
  10. 根据权利要求7-9任一项所述的制备方法，其特征在于，干燥温度为100℃-200℃，和/或，干燥时间为3h-5h。
  11. 根据权利要求6-10任一项所述的制备方法，其特征在于，补锂处理采用电化学补锂方式进行。
  12. 根据权利要求11所述的制备方法，其特征在于，补锂处理包括：将具有无锂或贫锂的普鲁士蓝材料包覆层的高镍三元正极材料制成极片，再将所述极片与含锂金属材料在隔膜隔开的条件下，于电解液中进行电化学反应。
  13. 根据权利要求12所述的制备方法，其特征在于，极片的制备包括：将具有无锂或贫锂的普鲁士蓝材料包覆层的高镍三元正极材料与导电剂、粘结剂以及溶剂制成浆料，将所述浆料涂覆于集流体上，干燥。
  14. 根据权利要求13所述的制备方法，其特征在于，极片的制备条件包括以下特征中的至少一种：
    特征一：具有无锂或贫锂的普鲁士蓝材料包覆层的高镍三元正极材料与所述导电剂、所述粘结剂以及所述溶剂的质量比为90-95:2-8:2-8:40-50；
    特征二：所述导电剂包括乙炔黑、炭黑、碳纳米管、科琴黑和碳纤维中的至少一种；
    特征三：所述粘结剂包括聚偏氟乙烯和聚四氟乙烯中的至少一种；
    特征四：所述溶剂包括N-甲基吡咯烷酮、二甲基甲酰胺、二乙基甲酰胺、二甲基亚砜和四氢呋喃中的至少一种；
    特征五：所述集流体包括铝箔、钛网、钛片、碳布和碳纸中的至少一种；
    特征六：干燥温度为60℃-80℃；
    特征七：干燥时间为3h-12h。
  15. 根据权利要求12-14任一项所述的制备方法，其特征在于，所述电解液包括锂盐电解质和非水溶剂。
  16. 根据权利要求15所述的制备方法，其特征在于，所述锂盐电解质包括六氟磷酸锂、高氯酸锂、四氟硼酸锂、氯化锂、溴化锂和氯铝酸锂中的至少一 种。
  17. 根据权利要求15或16所述的制备方法，其特征在于，所述非水溶剂包括链状酸酯、环状酸酯、链状醚和环状醚中的至少一种。
  18. 根据权利要求17所述的制备方法，其特征在于，所述非水溶剂包括碳酸二甲酯、碳酸二乙酯、碳酸乙烯酯、二氧甲基甲烷和四氢呋喃中的至少一种。
  19. 根据权利要求15-18任一项所述的制备方法，其特征在于，所述电解液中，所述锂盐电解质的浓度为1mol/L-5mol/L。
  20. 根据权利要求12-19任一项所述的制备方法，其特征在于，所述隔膜包括聚乙烯隔膜或聚丙烯隔膜。
  21. 根据权利要求12-20任一项所述的制备方法，其特征在于，补锂处理过程中的电压为0.3V-1V。
  22. 根据权利要求6-21任一项所述的制备方法，其特征在于，所述高镍三元正极材料的制备包括：将高镍三元正极材料前驱体与锂源的混合物进行烧结。
  23. 根据权利要求22所述的制备方法，其特征在于，所述高镍三元正极材料的制备条件包括以下特征中的至少一种：
    特征一：所述高镍三元正极材料前驱体的分子式为NiaCobMnc(OH)2，a+b+c＝1，0.8≤a＜1，0＜b≤0.1，0＜c≤0.1；
    特征二：所述锂源为氢氧化锂；
    特征三：所述锂源中锂元素与所述高镍三元正极材料前驱体中金属元素的摩尔比为1.01:1-1.05:1；
    特征四：烧结于氧气气氛下进行；
    特征五：烧结温度为650℃-1200℃；
    特征六：烧结时间为5h-12h。
  24. 根据权利要求22所述的制备方法，其特征在于，所述高镍三元正极材料前驱体的制备包括：将含镍、钴、锰的混合金属可溶性盐溶液与络合剂以及 沉淀剂进行共沉淀反应。
  25. 根据权利要求24所述的制备方法，其特征在于，所述高镍三元正极材料前驱体的制备条件包括以下特征中的至少一种：
    特征一：所述混合金属可溶性盐溶液包括混合金属的氯化盐溶液、混合金属的硫酸盐溶液、混合金属的硝酸盐溶液、混合金属的醋酸盐溶液或混合金属的草酸盐溶液；
    特征二：所述混合金属可溶性盐溶液中金属离子的总浓度为1mol/L-3mol/L；
    特征三：所述络合剂包括氨水；
    特征四：所述沉淀剂包括强碱溶液；
    特征五：共沉淀反应在pH值为11-13的条件下进行；
    特征六：共沉淀反应的温度为40℃-60℃；
    特征七：共沉淀反应的时间为2h-5h；
    特征八：共沉淀反应于保护气氛条件下进行。
  26. 根据权利要求25所述的制备方法，其特征在于，所述强碱溶液包括氢氧化钠溶液和氢氧化钾溶液中的至少一种。
  27. 根据权利要求25或26所述的制备方法，其特征在于，所述强碱溶液中强碱的浓度为3mol/L-8mol/L。
  28. 一种电池，其特征在于，所述电池含有权利要求1-5任一项所述的改性高镍三元正极材料。
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107069006A (zh) * 2017-04-24 2017-08-18 北京理工大学 一种提高锂离子电池高镍三元正极材料电化学性能的方法
CN107452948A (zh) * 2017-08-02 2017-12-08 中国科学院成都有机化学有限公司 一种普鲁士蓝复合锂离子电池三元正极材料及其制备方法
CN112635756A (zh) * 2020-12-21 2021-04-09 国联汽车动力电池研究院有限责任公司 一种高镍正极材料及其制备方法和应用
CN112952185A (zh) * 2021-03-29 2021-06-11 湖北亿纬动力有限公司 一种锂离子电池及其制备方法
JP2021105140A (ja) * 2019-12-27 2021-07-26 財團法人工業技術研究院Ｉｎｄｕｓｔｒｉａｌ Ｔｅｃｈｎｏｌｏｇｙ Ｒｅｓｅａｒｃｈ Ｉｎｓｔｉｔｕｔｅ イオン伝導材料、それを含むコアシェル構造、ならびにそれにより形成される電極および金属イオン電池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107069006A (zh) * 2017-04-24 2017-08-18 北京理工大学 一种提高锂离子电池高镍三元正极材料电化学性能的方法
CN107452948A (zh) * 2017-08-02 2017-12-08 中国科学院成都有机化学有限公司 一种普鲁士蓝复合锂离子电池三元正极材料及其制备方法
JP2021105140A (ja) * 2019-12-27 2021-07-26 財團法人工業技術研究院Ｉｎｄｕｓｔｒｉａｌ Ｔｅｃｈｎｏｌｏｇｙ Ｒｅｓｅａｒｃｈ Ｉｎｓｔｉｔｕｔｅ イオン伝導材料、それを含むコアシェル構造、ならびにそれにより形成される電極および金属イオン電池
CN112635756A (zh) * 2020-12-21 2021-04-09 国联汽车动力电池研究院有限责任公司 一种高镍正极材料及其制备方法和应用
CN112952185A (zh) * 2021-03-29 2021-06-11 湖北亿纬动力有限公司 一种锂离子电池及其制备方法

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