WO2022105696A1 - Précurseur de matériau actif d'électrode positive et procédé de préparation associé, matériau actif d'électrode positive et procédé de préparation associé, électrode positive de batterie secondaire lithium-ion et batterie secondaire lithium-ion - Google Patents

Précurseur de matériau actif d'électrode positive et procédé de préparation associé, matériau actif d'électrode positive et procédé de préparation associé, électrode positive de batterie secondaire lithium-ion et batterie secondaire lithium-ion Download PDF

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WO2022105696A1
WO2022105696A1 PCT/CN2021/130504 CN2021130504W WO2022105696A1 WO 2022105696 A1 WO2022105696 A1 WO 2022105696A1 CN 2021130504 W CN2021130504 W CN 2021130504W WO 2022105696 A1 WO2022105696 A1 WO 2022105696A1
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active material
positive electrode
electrode active
material precursor
water
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PCT/CN2021/130504
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English (en)
Chinese (zh)
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武怿达
黄学杰
詹元杰
马晓威
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松山湖材料实验室
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Priority claimed from CN202011286686.7A external-priority patent/CN114512660B/zh
Priority claimed from CN202111308255.0A external-priority patent/CN116081588A/zh
Application filed by 松山湖材料实验室 filed Critical 松山湖材料实验室
Publication of WO2022105696A1 publication Critical patent/WO2022105696A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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

  • the present application relates to the field of lithium ion batteries, in particular to a positive electrode active material precursor and a preparation method thereof, a positive electrode active material and a preparation method thereof, a positive electrode of a lithium ion secondary battery and a lithium ion secondary battery.
  • lithium-ion secondary batteries Compared with other rechargeable battery systems, lithium-ion secondary batteries have the advantages of high operating voltage, light weight, small size, no memory effect, low self-discharge rate, long cycle life, and high energy density.
  • Mobile terminal products such as mobile phones, notebook computers, and tablet computers.
  • lithium-ion secondary batteries have become an ideal power source for a new generation of electric vehicles due to their excellent performance.
  • the positive active materials of lithium ion secondary batteries that people pay attention to can be roughly divided into three categories: layered materials represented by lithium cobalt oxide (LiCoO 2 ), and olivine represented by lithium iron phosphate (LiFePO 4 ). type materials and spinel structure materials represented by lithium manganate (LiMn 2 O 4 ).
  • spinel-structured materials have been widely studied due to their advantages of environmentally friendly raw materials, low cost, simple process, high safety and good rate capability.
  • High-voltage materials with spinel structure are considered to be the most likely cathode active materials for next-generation high-performance lithium batteries.
  • the theoretical specific capacity of lithium nickel manganese oxide with spinel structure is 146.7mAh/g
  • the working voltage is 4.7V vs. Li/Li +
  • the theoretical capacity density can reach 695Wh/kg, which is the lithium for future electric vehicles. Ideal material for ion secondary batteries.
  • the surface of the positive active material loses oxygen, thereby dissolving the surface structure of the material, and the surface defects will gradually extend. to the bulk phase, resulting in particle breakage, which eventually leads to a rapid decline in battery performance.
  • element doping can form new chemical bonds inside and on the surface of the material to stabilize the bulk phase and surface lattice oxygen, and solve the problem of the interface and the surface of the positive electrode active material. Phase stability issues.
  • the positive electrode active material is modified by doping with phosphorus element.
  • the traditional modification method of phosphorus element is to mix the nickel-manganese precursor synthesized by co-precipitation method with phosphorus source and lithium source for high temperature sintering. It is difficult for phosphorus element to modify the lithium nickel manganate cathode material very uniformly. At the same time, traditional methods cannot achieve precise control of doping in specific regions of phosphorus element, which has great limitations.
  • the present application provides a positive electrode active material precursor, the general chemical formula of which is Ni 0.5-x Mn 1.5-ys As (PO 4 ) z (B) u , wherein A is a non-lithium metal element, a metalloid element or Combination of non-lithium metal elements and metalloid elements, B is OH - or CO 3 2- , -0.2 ⁇ x ⁇ 0.2, -0.2 ⁇ y ⁇ 0.2, 0 ⁇ s ⁇ 0.1, 0.003 ⁇ z ⁇ 0.07 and 0.8 ⁇ u ⁇ 4.4.
  • the present application also provides a positive electrode active material precursor, the general chemical formula of which is Ni 0.5-x Mn 1.5-ys As (PO 4 ) z (B) u , wherein A is a non-lithium metal element or a metalloid element Or a combination of a non-lithium metal element and a metalloid element, B is OH ⁇ , -0.2 ⁇ x ⁇ 0.2, -0.2 ⁇ y ⁇ 0.2, 0 ⁇ s ⁇ 0.1, 0.003 ⁇ z ⁇ 0.07, and 3.6 ⁇ u ⁇ 4.4.
  • A is a non-lithium metal element or a metalloid element Or a combination of a non-lithium metal element and a metalloid element
  • B is OH ⁇ , -0.2 ⁇ x ⁇ 0.2, -0.2 ⁇ y ⁇ 0.2, 0 ⁇ s ⁇ 0.1, 0.003 ⁇ z ⁇ 0.07, and 3.6 ⁇ u ⁇ 4.4.
  • the present application also provides a positive electrode active material precursor, the general chemical formula of which is Ni 0.5-x Mn 1.5-ys As (PO 4 ) z (B) u , wherein A is a non-lithium metal element or a metalloid element Or a combination of non-lithium metal elements and metalloid elements, B is CO 3 2- , -0.2 ⁇ x ⁇ 0.2, -0.2 ⁇ y ⁇ 0.2, 0 ⁇ s ⁇ 0.1, 0.003 ⁇ z ⁇ 0.07 and 1.8 ⁇ u ⁇ 2.2 .
  • the present application also provides a positive electrode active material precursor, the general chemical formula of which is Ni 0.5-x Mn 1.5-ys As (PO 4 ) z (B) u , wherein A is a non-lithium metal element or a metalloid element Or a combination of non-lithium metal elements and metalloid elements, B is OH - , -0.2 ⁇ x ⁇ 0.2, -0.2 ⁇ y ⁇ 0.2, 0 ⁇ s ⁇ 0.1, 0.003 ⁇ z ⁇ 0.07 and 3.6 ⁇ u ⁇ 4.4, so
  • the P element in the positive electrode active material precursor is unevenly distributed along the radial direction of the precursor particles.
  • the present application also provides a positive electrode active material precursor, the general chemical formula of which is Ni 0.5-x Mn 1.5-ys As (PO 4 ) z (B) u , wherein A is a non-lithium metal element or a metalloid element Or a combination of non-lithium metal elements and metalloid elements, B is CO 3 2- , -0.2 ⁇ x ⁇ 0.2, -0.2 ⁇ y ⁇ 0.2, 0 ⁇ s ⁇ 0.1, 0.003 ⁇ z ⁇ 0.07 and 1.8 ⁇ u ⁇ 2.2 , the P element in the cathode active material precursor is unevenly distributed along the radial direction of the precursor particles.
  • the present application also provides a positive electrode active material precursor, the general chemical formula of which is Ni 0.5-x Mn 1.5-ys As (PO 4 ) z (B) u , wherein A is a non-lithium metal element or a metalloid element Or a combination of non-lithium metal elements and metalloid elements, B is OH - or CO 3 2- , -0.2 ⁇ x ⁇ 0.2, -0.2 ⁇ y ⁇ 0.2, 0 ⁇ s ⁇ 0.1, 0.003 ⁇ z ⁇ 0.07 and 0.8 ⁇ u ⁇ 2.2, the P element in the positive electrode active material precursor is uniformly distributed.
  • the particle size of the particles of the cathode active material precursor is 0.1-30 microns.
  • the content of the P element in a partial region in the radial direction of the particles of the cathode active material precursor, has a gradient decrease or gradient from the center to the outer surface of the particles of the cathode active material precursor at least one of the increments.
  • the distribution length of each region in the radial direction of the particles of the positive electrode active material precursor accounts for the positive electrode active material.
  • the ratio of the total radial length of the precursor particles is 0.001-1.
  • s is 0, and the molar ratio of elements Ni, Mn and P is 1:(2.5-3.5):(0.006-0.2).
  • the non-lithium metal element is selected from at least one of alkaline earth metal elements, metalloid elements, transition metal elements, and Al.
  • A is selected from Al, Mg, Zn, Fe, Co, Ti, Y, Sc, Ru, Cu, Mo, Ge, W, Zr, Ca, Nb, Ta, Ni, Mn, Sr at least one.
  • the A is selected from at least one of Y, W, Ti, Mg, Cu, Ca, and Al.
  • the molar ratio of the elements Ni, Mn, A, and P in the positive electrode active material precursor is 1:(2.5-3.5):(0.2-0.001):(0.006-0.2).
  • the present application further provides a method for preparing a positive electrode active material precursor, comprising the following steps:
  • An aqueous solution of a complexing agent and an aqueous solution of an alkaline precipitating agent are provided, and part of the aqueous solution of the complexing agent and part of the aqueous solution of the alkaline precipitating agent is configured as the bottom liquid of the reactor;
  • the mixed solution optionally also contains at least one water-soluble non-lithium metal salt, at least one water-soluble metalloid element salt or at least one water-soluble metalloid element salt.
  • the mixed solution and the water-soluble phosphate solution are respectively added to the reaction kettle containing the reaction kettle bottom liquid, and the coprecipitation reaction is carried out under stirring, and the aqueous solution of the remaining amount of the complexing agent is also added at the same time.
  • the pH of the reaction system and the concentration of the complexing agent are controlled by controlling the feed amount of the aqueous solution of the complexing agent and the aqueous solution of the alkaline precipitating agent, and the reaction finishes to obtain mixed slurry; and
  • the mixed slurry is aged, centrifuged, washed and dried to obtain a uniformly phosphorus-doped positive electrode active material precursor.
  • the mixed solution and the water-soluble phosphate solution are controlled Separate and simultaneous feeds were made at the same feed rate.
  • the mixed solution and the water-soluble phosphate solution are controlled At least one of the feeding speed and concentration of the water-soluble phosphate solution changes with time, so that the particle size of the phosphorus element in the process of the growth of the precursor particles Uneven distribution upwards.
  • the non-lithium metal salt is any one of Al, Mg, Zn, Fe, Co, Ti, Y, Sc, Ru, Cu, Mo, W, Zr, Ca, Nb, Ta and Sr Any one or more of sulfates, chlorides and nitrates of metal elements.
  • the metalloid element salt is any one or more of Ge sulfate, chloride and nitrate.
  • the phosphate ion concentration in the water-soluble phosphate solution is 0.0025mol/L ⁇ 0.3mol/L
  • the water-soluble phosphate is sodium phosphate, potassium phosphate, ammonium phosphate, sodium dihydrogen phosphate, At least one of lithium dihydrogen phosphate, ammonium monohydrogen phosphate and ammonium dihydrogen phosphate.
  • the complexing agent is at least one of hydrazine hydrate, crown ether, ammonia water, oxalic acid, ammonium bicarbonate, ethylenediamine, and ethylenediaminetetraacetic acid, and the molar concentration of the complexing agent is 2mol/L ⁇ 8mol/L.
  • the precipitating agent is at least one of NaOH, KOH, Ba(OH) 2 , Na 2 CO 3 , Li 2 CO 3 , K 2 CO 3 or LiOH, and the molar concentration of the precipitating agent is It is 2mol/L ⁇ 6mol/L.
  • the pH of the reaction kettle bottom liquid is 10 to 12.5, and the concentration of the complexing agent in the reaction kettle bottom liquid is 15 g/L to 20 g/L.
  • the pH of the reaction kettle bottom liquid is 12-12.5.
  • the reaction temperature of the co-precipitation reaction is 40 °C ⁇ 70 °C
  • the pH of the reaction system is 10 ⁇ 12.5
  • the concentration of the complexing agent is 15g/L ⁇ 25g/L
  • the stirring speed is 200rpm ⁇ 250rpm
  • the reaction time is 5h ⁇ 120h.
  • the pH of the reaction system is 11.5-12.
  • the total molar concentration of metal ions in the mixed solution is 1 mol/L to 3 mol/L
  • the water-soluble nickel salt is at least one of nickel sulfate, nickel chloride, and nickel nitrate
  • the The water-soluble manganese salt is at least one of manganese sulfate, manganese chloride, and manganese nitrate.
  • the feed rate of the mixed solution and the water-soluble phosphate is 0.1L/h ⁇ 100L/h
  • the feed rate of the aqueous solution of the complexing agent is 0.1L/h ⁇ 100L/h h
  • the feed rate of the aqueous solution of the alkaline precipitant is 0.1L/h ⁇ 100L/h.
  • the feed rate of the water-soluble phosphate salt increases or decreases with time for a certain period of time throughout the dropping cycle.
  • the concentration of the water-soluble phosphate increases or decreases with time for a certain period of time throughout the dripping cycle.
  • the present application further provides a positive electrode active material prepared from the positive electrode active material precursor obtained by the positive electrode active material precursor or the positive electrode active material precursor obtained by the method for preparing the positive electrode active material precursor.
  • the present application further provides a method for preparing a positive electrode active material, comprising the following steps:
  • the present application further provides a positive electrode of a lithium ion secondary battery, comprising a positive electrode current collector and a positive electrode active material layer on the positive electrode current collector, the positive electrode active material layer comprising the above-mentioned positive electrode active material.
  • the present application further provides a lithium ion secondary battery, including a positive electrode, a negative electrode, a separator and an electrolyte.
  • the negative electrode includes a negative electrode current collector and a negative electrode active material layer on the negative electrode current collector.
  • the precursor of this composition structure the problem that the later traditional method uses high-temperature solid-phase method for lithium doping and phosphorus doping at the same time is difficult to dope uniform and controllable region doping problem. .
  • the cathode active material and the lithium ion battery with better performance are prepared.
  • FIG. 1 is a SEM cross-sectional view of the positive electrode active material precursor prepared in Example 1.
  • FIG. 1 is a SEM cross-sectional view of the positive electrode active material precursor prepared in Example 1.
  • Fig. 2 is the SEM mapping distribution diagram of the cross section of the positive electrode active material precursor prepared in Example 1.
  • Fig. 3 is the SEM mapping distribution diagram of the cross-section of the positive electrode active material precursor prepared in Example 2.
  • FIG. 4 shows a picture of laser ion beam cutting of the gradient phosphorus-doped cathode active material precursor prepared in Example 8.
  • FIG. 5 shows a schematic diagram of a line scan performed on the radial region of the gradient phosphorus-doped cathode active material precursor prepared in Example 8.
  • the embodiments of the present application provide a positive electrode active material precursor, the general chemical formula of which is Ni 0.5-x Mn 1.5-ys As (PO 4 ) z (B) u , wherein A is a non-lithium metal element and/or Metalloid element, B is OH - or CO 3 2- , -0.2 ⁇ x ⁇ 0.2, -0.2 ⁇ y ⁇ 0.2, 0 ⁇ s ⁇ 0.1, 0.003 ⁇ z ⁇ 0.07 and 0.8 ⁇ u ⁇ 4.4.
  • the P element in the positive electrode active material precursor is uniformly distributed or non-uniformly distributed in a specific area.
  • phosphorus element is uniformly distributed at the atomic level inside the precursor, and at the same time, the precursor maintains the properties and element ratio of the traditional nickel-manganese precursor.
  • the precursor of the composition structure solves the problem that the later traditional method uses the high-temperature solid-phase method to dope lithium and it is difficult to dope uniformly with phosphorus.
  • phosphorus doping will face three major problems in the later stage. First, the lithium salt will react with the phosphorus source to generate lithium phosphate and other substances, which will affect the activity of the lithium salt during the whole sintering process; secondly, the phosphorus element is in the lithium nickel manganate material.
  • the P element is uniformly distributed in the cathode active material precursor.
  • the P element is not uniformly distributed in the cathode active material precursor.
  • the content of the P element in a partial region in the radial direction of the particles of the cathode active material precursor, has a gradient decrease or gradient from the center to the outer surface of the particles of the cathode active material precursor at least one of the increments.
  • the distribution length of each region in the radial direction of the positive electrode active material accounts for the total radial length of the positive electrode active material The ratio is 0.001-1.
  • s is 0, and the general chemical formula of the positive active material precursor is Ni 0.5-x Mn 1.5-y (PO 4 ) z (B) u , wherein A is a non-lithium metal element and /or metalloid element, B is OH - or CO 3 2- , wherein -0.2 ⁇ x ⁇ 0.2, -0.2 ⁇ y ⁇ 0.2, 0.005 ⁇ z ⁇ 0.05 and 0.8 ⁇ u ⁇ 4.4.
  • the molar ratio of elements Ni, Mn and P may be any ratio between 1:(2.5-3.5):(0.006-0.2).
  • s is not 0, and the non-lithium metal element A is selected from at least one of alkaline earth metal elements, transition metal elements and Al.
  • the A is selected from Al, Mg, Zn, Fe, Co, Ti, Y, Sc, Ru, Cu, Mo, Ge, W, Zr, Ca, Nb, Ta, Sr, B, Si at least one. In some embodiments, the A is selected from at least one of Y, W, Ti, Mg, Cu, Ca, and Al.
  • the molar ratio of elements Ni, Mn, A and P can be any ratio between 1:(2.5-3.5):(0.2-0.001):(0.006-0.2).
  • B is OH - or CO 3 2- , 0.8 ⁇ u ⁇ 2.2, and the P element is uniformly distributed in the cathode active material precursor.
  • B is OH ⁇ , 3.6 ⁇ u ⁇ 4.4, and the P element in the cathode active material precursor is unevenly distributed along the radial direction of the particles of the cathode active material precursor.
  • B is CO 3 2 ⁇ , 1.8 ⁇ u ⁇ 2.2, and the P element in the cathode active material precursor is unevenly distributed along the radial direction of the particles of the cathode active material precursor.
  • the particle size of the particles of the cathode active material precursor is 0.1-30 microns.
  • the present application also provides a method for preparing a positive electrode active material precursor, comprising the following steps:
  • Step a provide the aqueous solution X of the complexing agent and the aqueous solution Y of the alkaline precipitating agent, and configure the aqueous solution X of part of the complexing agent and the aqueous solution Y of part of the alkaline precipitating agent into the bottom liquid of the reactor;
  • Step b mixing water-soluble nickel salt, water-soluble manganese salt and water to form a mixed solution; optionally also containing at least one water-soluble non-lithium metal salt and/or metalloid element salt in the mixed solution;
  • Step c under the protection of inert gas, the mixed solution and the water-soluble phosphate solution are respectively added to the reactor containing the bottom liquid of the reactor, and the feeding speed of the mixed solution and the water-soluble phosphate solution is controlled.
  • concentration carry out co-precipitation reaction under stirring, also add the remaining amount of the aqueous solution X of the complexing agent and the remaining amount of the aqueous solution Y of the alkaline precipitant, and control the pH and the pH of the reaction system by controlling the feeding amounts of X and Y.
  • step d the mixed slurry is aged, centrifuged, washed and dried to obtain a positive electrode active material precursor uniformly doped with phosphorus.
  • “simultaneously” means that the time periods in which the two or more solutions to be added to the reactor are added to the reactor at least partially overlap. In some embodiments, “simultaneously” means that the two or more solutions are added to the reaction kettle at the same starting time.
  • the mixed solution and the water-soluble phosphate solution are added to the reaction kettle at the same time, and the mixed solution and the water-soluble phosphate solution are fed at the same feed rate.
  • the mixed solution and the water-soluble phosphate solution are not added to the reaction kettle at the same time, that is, The time at which the mixed solution and the water-soluble phosphate solution are added to the reactor only partially overlaps; and/or the feed rate of the water-soluble phosphate solution varies with time, and the feed rate of the mixed solution or The concentration is always constant, or also varies with time.
  • the feed rate of the water-soluble phosphate salt increases or decreases with time for a certain period of time throughout the dropping cycle.
  • the concentration of the water-soluble phosphate increases or decreases with time for a certain period of time throughout the dropping period.
  • the three elements of nickel, manganese and phosphorus are uniformly precipitated simultaneously in the form of nickel hydroxide, manganese hydroxide and phosphate by co-precipitation method or in different distributions of specific elements.
  • the uniform precipitation constitutes the cathode active material precursor.
  • the phosphorus element is uniformly distributed inside the positive electrode active material precursor or non-uniformly distributed in the positive electrode active material precursor in a specific manner.
  • the preparation principle of the positive electrode active material precursor of the present application is as follows: water-soluble phosphate, water-soluble nickel salt and water-soluble manganese salt are added to the reaction kettle, and the reaction conditions are controlled to realize co-precipitation of phosphorus, nickel and manganese metal ions. Water-soluble phosphates provide precipitation of phosphate and nickel-manganese ions. In the preparation process, the reaction conditions need to be strictly controlled, and the positive electrode active material precursor is obtained through reaction, aging, centrifugation, washing and drying.
  • the non-lithium metal salt may be a water-soluble sulfate, chloride or nitrate salt of any one of alkaline earth metal elements, transition metal elements and Al.
  • the non-lithium metal salt is Al, Mg, Zn, Fe, Co, Ti, Y, Sc, Ru, Cu, Mo, Ge, W, Zr, Ca, Nb, Ta, Sr, B, Si Any one or more of water-soluble sulfates, chlorides and nitrates of at least one metal element in .
  • the non-lithium metal salt is any one of water-soluble sulfate, chloride and nitrate of any metal element in Y, W, Ti, Mg, Cu, Ca and Al or variety.
  • the metalloid element salt is any one or more of Ge sulfate, chloride and nitrate.
  • the complexing agent can be at least one of hydrazine hydrate, crown ether, ammonia water, oxalic acid, ammonium bicarbonate, ethylenediamine, ethylenediaminetetraacetic acid, and in some embodiments, ammonia water.
  • the molar concentration of the complexing agent in the aqueous solution X of the complexing agent can be any value between 2mol/L ⁇ 8mol/L, such as 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 7.5mol/L.
  • the precipitant may be at least one of NaOH, KOH, Ba(OH) 2 , Na 2 CO 3 , Li 2 CO 3 , K 2 CO 3 or LiOH.
  • NaOH NaOH, KOH, Ba(OH) 2 , Na 2 CO 3 , Li 2 CO 3 , K 2 CO 3 or LiOH.
  • NaOH NaOH, KOH, Ba(OH) 2 , Na 2 CO 3 , Li 2 CO 3 , K 2 CO 3 or LiOH.
  • NaOH NaOH
  • the molar concentration of the precipitant in the aqueous solution Y of the alkaline precipitant can be any value between 2 mol/L and 6 mol/L, for example, it can also be 2.5 mol/L, 3 mol/L, 3.2 mol/L, 3.5 mol /L, 3.8mol/L, 4mol/L, 4.2mol/L, 4.5mol/L, 4.8mol/L, 5mol/L, 5.5mol/L.
  • the pH of the reaction kettle bottom liquid can be any value between 10 and 12.5, and in some embodiments, it is 12 to 12.5.
  • the concentration of the complexing agent in the bottom liquid of the reaction kettle can be any value between 15g/L and 20g/L, for example, it can also be 16g/L, 17g/L, 18g/L and 19g/L.
  • the water-soluble nickel salt can be at least one of nickel sulfate, nickel chloride, and nickel nitrate.
  • the water-soluble manganese salt can be at least one of manganese sulfate, manganese chloride, and manganese nitrate.
  • the water-soluble phosphate can be sodium phosphate, sodium monohydrogen phosphate, potassium dihydrogen phosphate, diammonium hydrogen phosphate, potassium phosphate, ammonium phosphate, sodium dihydrogen phosphate, lithium dihydrogen phosphate, ammonium monohydrogen phosphate, phosphoric acid, phosphoric acid at least one of ammonium dihydrogen.
  • the total molar concentration of metal ions in the mixed solution is 1 mol/L to 3 mol/L.
  • the phosphate ion concentration in the water-soluble phosphate solution is 0.0025 mol/L to 0.3 mol/L.
  • step c the feed rate of the mixed solution and the water-soluble phosphate is 0.1mL/h ⁇ 100mL/h, and the feed rate of the aqueous solution X of the complexing agent is 0.1mL/h ⁇ -100mL/h,
  • the feed rate of the aqueous solution Y of the alkaline precipitant is 0.1 mL/h to 100 mL/h.
  • the reaction temperature can be 40 °C ⁇ 70 °C
  • the pH of the reaction system is controlled at 10 ⁇ 12.5, in some embodiments, it is 11.5 ⁇ 12
  • the concentration of the complexing agent is controlled at 15g/L ⁇ 25g/L
  • the stirring speed can be 200rpm ⁇ 250rpm
  • the reaction time can be 80h ⁇ 120h.
  • the feed rate or concentration of the water-soluble phosphate increases or decreases with time.
  • the pH of the reaction system can be controlled to be 12.
  • the inert gas may be nitrogen.
  • the aging time of the mixed slurry may be 20 hours to 24 hours, and the aging temperature may be 15°C to 80°C.
  • the present application further provides a positive electrode active material prepared from the above-mentioned positive electrode active material precursor or the positive electrode active material precursor obtained by the above-mentioned preparation method of the positive electrode active material precursor.
  • the phosphorus element can be distributed in a specific form, uniformly or unevenly distributed in the positive electrode active material precursor. in the body.
  • This specific distribution form will help to further regulate the distribution of phosphorus elements in the bulk phase and surface of the final synthesized lithium nickel manganate material under the premise of realizing the comprehensive modification of the lithium nickel manganate material by phosphorus elements, and at the same time It can also adjust the morphology of the synthesized lithium nickel manganate materials.
  • the phosphorus content of the lithium nickel manganate precursor gradually increases from the inside to the surface, the high content of phosphorus on the surface of the precursor will inhibit the lithium nickel manganate sintering process using the precursor.
  • the final synthesized lithium nickel manganate material has a smaller particle size and a more uniform particle size distribution.
  • the polarization of the battery is smaller and the rate performance is better.
  • the content of phosphorus in the lithium nickel manganate precursor gradually decreases from the surface of the lithium nickel manganate precursor to the inside, in the process of synthesizing the lithium nickel manganate material, the content of phosphorus on the surface of the precursor is less, which is more conducive to Fusion, absorption and growth between NiMnO precursors.
  • the final synthesized lithium nickel manganate material can obtain a larger material particle size and better particle size distribution on the basis of doping with phosphorus element, and then obtain a lithium nickel manganate material with a higher tap density. Then, the volume energy density of the finally obtained lithium nickel manganate battery product is improved.
  • the doping of phosphorus element to the lithium nickel manganate precursor is a more flexible doping method.
  • the precursor is doped with phosphorus during the co-precipitation synthesis of the lithium nickel manganate precursor.
  • the concentration of phosphorus in nickel can be precisely regulated.
  • the distribution in the lithium manganate precursor is not only the synthesis of uniform phosphorus element doped nickel lithium manganate precursor to obtain excellent battery performance in all aspects. Due to the complexity of the battery, it is usually difficult to take into account the comprehensive indicators of the battery's high and low temperature cycling, mass energy density, volume energy density, and rate performance.
  • the inventor first found that doping the precursor with phosphorus element can ultimately greatly improve the comprehensive performance of the synthesized lithium nickel manganate material. Further, by adjusting the distribution of phosphorus element content in the lithium nickel manganate material, some physical properties of the lithium nickel manganate material itself can be adjusted, such as particle size, particle size distribution, and the overall composition of the final synthesized lithium nickel manganate material. Phosphorus distribution. All of these utilize the different characteristics brought about by the distribution of phosphorus in the lithium nickel manganate precursor and the final distribution in the final lithium nickel manganate material to stabilize the surface of the lithium nickel manganate material, enabling it to achieve commercial application. status.
  • lithium nickel manganate cathode material under a certain range of phosphorus element content and sintering conditions, the higher the distribution of phosphorus element on the surface, the less conducive to the final synthesis of large particle size lithium nickel manganate material; nickel manganese The narrower the particle size distribution of lithium oxide, the more stable the surface of the final synthesized lithium nickel manganate material. Therefore, when a lithium nickel manganate material precursor with a small particle size but a more stable surface and a narrower particle size distribution is required, it is most suitable to synthesize a lithium nickel manganate cathode precursor with a higher surface phosphorus distribution. .
  • this type of precursor can save cost very well, and the same content of phosphorus source is used to finally synthesize a more satisfactory lithium nickel manganate cathode material.
  • the lower the distribution of phosphorus elements on the surface the more favorable the final synthesis of large particle size lithium nickel manganate material, the more small particle size lithium nickel manganese oxide, and the greater the tap density of the final synthesized lithium nickel manganate material.
  • the uniform and non-uniform distribution of phosphorus element in the lithium nickel manganate precursor brings rich and diverse adjustments to the properties of the final synthesized lithium nickel manganate material. People have not noticed this in the past.
  • the phosphorus element enters the positive electrode active material precursor in a uniform form or forms the positive electrode active material precursor unevenly in a specific distribution.
  • the positive electrode active material precursor of the present application the general chemical formula of which is Ni 0.5-x Mn 1.5-ys As (PO 4 ) z (B) u , and the positive electrode active material precursor in the molecule is
  • the distribution of manganese and nickel in the body is also not limited.
  • the nickel or manganese in the formula can be uniformly distributed or non-uniformly distributed, for example, the gradient increases or decreases gradually from the center of the precursor particle to the outer surface.
  • the increasing or decreasing gradient mentioned in this application means that the phosphorus content has a tendency to increase or decrease in a certain part of the radial direction of the precursor, and this increasing or decreasing trend does not need to have a fixed slope.
  • the characteristics of the synthetic materials of the present application can be detected by the most common methods in the industry, such as cutting the synthesized materials by means of a focused laser ion beam, etc., and determining the increasing or decreasing distribution of phosphorus elements or different regions through various electron microscope line scans. The ratio of the internal phosphorus content. In addition, other methods reported in the industry and literature can also be used for discrimination.
  • water-soluble phosphate, water-soluble nickel salt and manganese salt into the reaction kettle, and controlling the reaction conditions, co-precipitation of phosphorus, nickel and manganese metal ions is achieved.
  • Water-soluble phosphates provide precipitation of phosphate and nickel-manganese ions.
  • the present application further provides a method for preparing the positive electrode active material, comprising the following steps:
  • the lithium source is lithium carbonate or lithium hydroxide, in some embodiments lithium carbonate.
  • the sintering can be carried out in an oxygen atmosphere such as oxygen and air.
  • the specific operation of the sintering process is: raising the temperature to 600°C-1200°C at a heating rate of 0.5-10°C/min, then sintering for 0.5-10 h, and then cooling at a rate of 0.5-10°C/min to room temperature.
  • the above-mentioned positive electrode active material precursor contains phosphorus element
  • the positive electrode active material precursor contained in this application can be cut out by a laser ion beam cutting method, and combined with XPS by SEM mapping, TEM-mapping, ion beam etching Photoelectron imaging or secondary ion mass spectrometry and other methods are used to characterize the content and distribution of phosphorus elements in the positive electrode active material, and further determine the characteristics of the positive electrode active material precursor contained in this patent.
  • the present application also provides a positive electrode of a lithium ion secondary battery, comprising a positive electrode current collector and a positive electrode active material layer on the positive electrode current collector, wherein the positive electrode active material layer includes the above-mentioned positive electrode active material.
  • the positive electrode current collector may be a conductive member formed of a highly conductive metal used in the positive electrode of a lithium ion secondary battery of the related art.
  • the positive electrode current collector may use aluminum or an alloy including aluminum as a main component.
  • the shape of the positive electrode current collector is not particularly limited and may vary depending on the shape and the like of the lithium ion secondary battery.
  • the positive electrode current collector may have various shapes such as a rod shape, a plate shape, a sheet shape, and a foil shape.
  • the positive electrode active material layer further includes a conductive additive and a binder.
  • the conductive additive may be a conventional conductive additive in the art, which is not particularly limited in the present application.
  • the conductive additive is carbon black (eg, acetylene black or Ketjen black).
  • the adhesive may be a conventional adhesive in the art, which is not particularly limited in the present application, and may be composed of polyvinylidene fluoride (PVDF), or may be composed of carboxymethyl cellulose (CMC) and butylbenzene Made of rubber (SBR).
  • the binder is polyvinylidene fluoride (PVDF).
  • the application also provides a lithium-ion secondary battery, comprising:
  • a negative electrode comprising a negative electrode current collector and a negative electrode active material layer on the negative electrode current collector;
  • the negative electrode, separator and electrolyte can use conventional negative electrode current collector, separator and electrolyte materials in the art, which are not particularly limited in the present application.
  • the negative electrode current collector may be copper, and the shape of the negative electrode current collector is also not particularly limited, and may be rod-shaped, plate-shaped, sheet-shaped, and foil-shaped, and may vary depending on the shape of the lithium ion secondary battery and the like.
  • the negative electrode active material layer includes a negative electrode active material, a conductive additive and a binder. Negative active materials, conductive additives and binders are also conventional materials in the art. In some embodiments, the negative active material is metallic lithium. The conductive additives and binders are described above and will not be repeated here.
  • the separator can be selected from those commonly used in lithium ion secondary batteries, including microporous films made of polyethylene and polypropylene; porous polyethylene films and polypropylene multi-layer films; Nonwoven fabrics formed of aramid fibers, glass fibers, etc.; and base films formed by adhering ceramic particles such as silica, alumina, and titania to their surfaces, and the like.
  • the separator is a triple-layer film of PP/PE/PP coated with alumina on both sides.
  • the electrolytic solution may include an electrolyte and a non-aqueous organic solvent.
  • the electrolyte can be selected from LiPF 6 , LiBF 4 , LiSbF 6 , and LiAsF 6 .
  • the non-aqueous organic solvent can be carbonate, ester and ether.
  • carbonates such as ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), and ethylmethyl carbonate (EMC) may be employed.
  • the electrolyte is an ethylene carbonate (EC)/dimethyl carbonate (DMC) non-aqueous electrolyte with a concentration of LiPF 6 of 1 mol/L, wherein the volume ratio of EC to DMC is 1: 1.
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • step (2) feed nitrogen into the reactor equipped with bottom liquid, under nitrogen protection, in step (2), mixing solution and water-soluble phosphate solution are at the feed rate of 0.5L/h, and sodium hydroxide solution is at 0.5 L/h
  • the feed rate of L/h and ammonia water are added to the reaction kettle at the feed rate of 0.5L/h.
  • the feed can be fed through a metering pump.
  • the pH of the control reaction system is 12, and the ammonia concentration is 15g/ L
  • the co-precipitation reaction was carried out at 40° C. and a stirring speed of 200 rpm, and the reaction time was 100 h to obtain a mixed slurry.
  • the mixed slurry is transferred to an aging tank for aging, centrifugation, washing and drying to obtain a uniform phosphorus-doped cathode active material precursor, wherein the aging temperature is 70°C and the aging time is 80h.
  • FIG. 1 shows a picture of laser ion beam cutting of the uniformly phosphorus-doped cathode active material precursor prepared in this example.
  • Figure 2 is a SEM element mapping distribution diagram of a uniform phosphorus-doped cathode active material precursor obtained after laser ion beam cutting. As can be seen from Figure 2, phosphorus is uniformly distributed inside the precursor.
  • feed nitrogen into the reactor equipped with bottom liquid, under nitrogen protection, mixing solution and water-soluble phosphate solution are at the feed rate of 0.5L/h, and sodium hydroxide solution is at the feed rate of 0.5L/h
  • the feed rate and ammonia water are added to the reaction kettle at a feed rate of 0.5L/h.
  • the feed can be fed through a metering pump.
  • the pH of the reaction system is controlled to be 10.8, and the ammonia concentration is 15g/L.
  • the co-precipitation reaction was carried out at a stirring speed of 200 rpm, and the reaction time was 100 h to obtain a mixed slurry.
  • the mixed slurry is transferred to an aging tank for aging, centrifugation, washing, and drying to obtain a uniform phosphorus-doped cathode active material precursor, wherein the aging temperature is 60° C. and the aging time is 20 hours.
  • FIG. 3 is a scanning electron microscope element mapping distribution diagram of the uniform phosphorus-doped cathode active material precursor obtained after laser ion beam cutting. It can be seen from Figure 3 that phosphorus is uniformly distributed inside the precursor.
  • Example 2 Take 10 g of the precursor synthesized in Example 1 and 2.169 g of lithium carbonate for grinding and mixing, and place it in a furnace at 950 ° C for high-temperature calcination for 20 h, with a heating rate of 3 ° C/min and a cooling rate of 5 ° C/min to obtain sintered phosphorus.
  • Element-doped lithium nickel manganate cathode material Take 10 g of the precursor synthesized in Example 1 and 2.169 g of lithium carbonate for grinding and mixing, and place it in a furnace at 950 ° C for high-temperature calcination for 20 h, with a heating rate of 3 ° C/min and a cooling rate of 5 ° C/min to obtain sintered phosphorus.
  • Element-doped lithium nickel manganate cathode material Take 10 g of the precursor synthesized in Example 1 and 2.169 g of lithium carbonate for grinding and mixing, and place it in a furnace at 950 ° C for high-temperatur
  • step (2) feed nitrogen into the reactor equipped with bottom liquid, under nitrogen protection, in step (2), mixing solution and water-soluble phosphate solution are at the feed rate of 0.2L/h, and sodium hydroxide solution is at 0.5
  • the feed rate of L/h and ammonia water are jointly added to the reaction kettle with the feed rate of 0.5L/h, and the feed can be fed by a metering pump, and the pH of the control reaction system in the feeding process is 12, and the ammonia concentration is 15g/ L, the co-precipitation reaction was carried out at 40 °C and a stirring speed of 200 rpm.
  • the total reaction time was 100 h, and the dropping rate of the water-soluble phosphate solution was increased by 0.1 L/h every 20 h.
  • the acceleration is fine-tuned to meet the pH stability of the entire reaction system and the stability of the ammonia concentration. After the reaction is completed, a mixed slurry is finally obtained.
  • the mixed slurry is transferred to an aging tank for aging, centrifugation, washing, and drying, to obtain a positive active material precursor with a gradually increasing content of phosphorus from the inside to the outside.
  • the aging temperature is 70°C, and the aging time is 80h. .
  • step (2) feed nitrogen into the reactor equipped with bottom liquid, under nitrogen protection, in step (2), mixing solution and water-soluble phosphate solution are at the feed rate of 0.8L/h, and sodium hydroxide solution is at 0.5
  • the feed rate of L/h and ammonia water are added to the reaction kettle at the feed rate of 0.5L/h.
  • the feed can be fed through a metering pump.
  • the pH of the control reaction system is 12, and the ammonia concentration is 15g/ L
  • the co-precipitation reaction was carried out at 40 °C and a stirring speed of 200 rpm.
  • the total reaction time was 100 h, and the dropping rate of the water-soluble phosphate solution was reduced by 0.1 L/h every 20 h.
  • the acceleration is fine-tuned to meet the pH stability of the entire reaction system, and the mixed slurry is finally obtained after the reaction is completed.
  • the mixed slurry is transferred to an aging tank for aging, centrifugation, washing, and drying to obtain a cathode active material precursor with a gradually decreasing content of phosphorus from the inside to the outside.
  • the aging temperature is 70°C and the aging time is 80h. .
  • Example 4 Take 10 g of the precursor synthesized in Example 4 and 2.169 g of lithium carbonate for grinding and mixing, and place it in a furnace at 950 ° C for high-temperature calcination for 20 h, with a heating rate of 3 ° C/min and a cooling rate of 5 ° C/min, to obtain the phosphorus after sintering.
  • Element-doped lithium nickel manganate cathode material Take 10 g of the precursor synthesized in Example 4 and 2.169 g of lithium carbonate for grinding and mixing, and place it in a furnace at 950 ° C for high-temperature calcination for 20 h, with a heating rate of 3 ° C/min and a cooling rate of 5 ° C/min, to obtain the phosphorus after sintering.
  • Element-doped lithium nickel manganate cathode material Take 10 g of the precursor synthesized in Example 4 and 2.169 g of lithium carbonate for grinding and mixing, and place it in a furnace
  • Example 5 Take 10 g of the precursor synthesized in Example 5 and 2.169 g of lithium carbonate for grinding and mixing, and place it in a furnace at 950 ° C for high-temperature calcination for 20 h, with a heating rate of 3 ° C/min and a cooling rate of 5 ° C/min to obtain sintered phosphorus.
  • Element-doped lithium nickel manganate cathode material Take 10 g of the precursor synthesized in Example 5 and 2.169 g of lithium carbonate for grinding and mixing, and place it in a furnace at 950 ° C for high-temperature calcination for 20 h, with a heating rate of 3 ° C/min and a cooling rate of 5 ° C/min to obtain sintered phosphorus.
  • Element-doped lithium nickel manganate cathode material Take 10 g of the precursor synthesized in Example 5 and 2.169 g of lithium carbonate for grinding and mixing, and place it in a furnace at 950 ° C for high-temperatur
  • step (2) feed nitrogen into the reactor equipped with bottom liquid, under nitrogen protection, in step (2), mixing solution and water-soluble phosphate solution are about with the feed rate of 0.2L/h, sodium carbonate solution with 0.5
  • the feed rate of L/h and ammonia water are added to the reaction kettle at a feed rate of 0.4L/h.
  • the feed can be fed by a metering pump.
  • the pH of the reaction system is controlled to be 11, at 40°C and 200rpm.
  • the co-precipitation reaction was carried out under the stirring speed of 100 h, the total reaction time was 100 h, and the dripping rate of the water-soluble phosphate solution was increased by 0.1 L/h every 20 h.
  • the dripping rate of sodium carbonate and ammonia water was fine-tuned to meet the whole reaction
  • the pH of the system is stable and the concentration of ammonia water is stable, and the mixed slurry is finally obtained after the reaction is completed.
  • the mixed slurry is transferred to an aging tank for aging, centrifugation, washing, and drying, to obtain a positive active material precursor with a gradually increasing content of phosphorus from the inside to the outside.
  • the aging temperature is 70°C, and the aging time is 80h. .
  • FIG. 4 shows a picture of laser ion beam cutting of the gradient phosphorus-doped cathode active material precursor prepared in Example 8.
  • FIG. 5 shows a schematic diagram of a line scan performed on the radial region of the gradient phosphorus-doped positive active material precursor prepared in Example 8.
  • the black line represents the line scan region.
  • I (solid line box) / I (dotted line box) 1.84, where I (solid line box) is the signal intensity of phosphorus element obtained from the line scan collection point in the solid line box, I (dotted line) Box) is the signal intensity of phosphorus element obtained by scanning the collection points in the dotted box.
  • Example 8 Take 10 g of the precursor synthesized in Example 8 and 1.594 g of lithium carbonate for grinding and mixing, and place it in a furnace at 950 ° C for high-temperature calcination for 20 h, with a heating rate of 3 ° C/min and a cooling rate of 5 ° C/min to obtain the phosphorus after sintering.
  • Element-doped lithium nickel manganate cathode material Take 10 g of the precursor synthesized in Example 8 and 1.594 g of lithium carbonate for grinding and mixing, and place it in a furnace at 950 ° C for high-temperature calcination for 20 h, with a heating rate of 3 ° C/min and a cooling rate of 5 ° C/min to obtain the phosphorus after sintering.
  • Element-doped lithium nickel manganate cathode material Take 10 g of the precursor synthesized in Example 8 and 1.594 g of lithium carbonate for grinding and mixing, and place it in a furnace at
  • step (2) feed nitrogen into the reactor equipped with bottom liquid, under nitrogen protection, in step (2), mixing solution and water-soluble phosphate solution are about with the feed rate of 0.5L/h, and sodium carbonate solution is about 0.5L/h
  • the feed rate of L/h and ammonia water are added to the reaction kettle at a feed rate of 0.4L/h.
  • the feed can be fed by a metering pump.
  • the pH of the reaction system is controlled to be 11, at 40°C and 200rpm.
  • the co-precipitation reaction was carried out at the stirring speed of 100 h, and the total reaction time was 100 h.
  • the dropping speed of sodium carbonate and ammonia water was fine-tuned to meet the stability of pH and ammonia concentration of the whole reaction system. After the reaction was completed, a mixed slurry was finally obtained. material.
  • the mixed slurry is transferred to an aging tank for aging, centrifugation, washing and drying to obtain a positive electrode active material precursor, wherein the aging temperature is 70° C. and the aging time is 80 hours.
  • Example 10 Take 10 g of the precursor synthesized in Example 10 and 1.594 g of lithium carbonate, grind and mix, and place it in a furnace at 950 ° C for high temperature calcination for 20 h, with a heating rate of 3 ° C/min and a cooling rate of 5 ° C/min, to obtain the phosphorus after sintering.
  • Element-doped lithium nickel manganate cathode material Take 10 g of the precursor synthesized in Example 10 and 1.594 g of lithium carbonate, grind and mix, and place it in a furnace at 950 ° C for high temperature calcination for 20 h, with a heating rate of 3 ° C/min and a cooling rate of 5 ° C/min, to obtain the phosphorus after sintering.
  • Element-doped lithium nickel manganate cathode material Take 10 g of the precursor synthesized in Example 10 and 1.594 g of lithium carbonate, grind and mix, and place it in a furnace at 950
  • the positive electrode active materials prepared in Examples 3, 6, 7, 9, 11 and Comparative Examples 1 and 2 were assembled into coin cells according to the following steps.
  • the positive electrode active material and carbon black prepared in the examples were used as conductive additives and binders, and were uniformly mixed according to a weight ratio of 80:10:10 to prepare a uniform positive electrode slurry.
  • the uniform positive electrode slurry was evenly coated on the aluminum foil current collector with a thickness of 15 ⁇ m, and dried at 55 ° C to form a pole piece with a thickness of 100 ⁇ m, and the pole piece was placed under a roller press for rolling (pressure about 1MPa). ⁇ 1.5cm 2 ), cut into a circle with a diameter of ⁇ 14mm, and then placed in a vacuum oven at 120° C. for 6 hours. After natural cooling, it was taken out and placed in a glove box to be used as a positive pole piece.
  • metal lithium is used as the negative electrode of the battery, and a triple-layer film of PP/PE/PP coated with alumina on both sides is placed between the positive electrode and the negative electrode as a separator, and commonly used carbonates are added dropwise.
  • the electrolyte solution is assembled into a button battery with a model of CR2032, using the positive electrode plate prepared in step (1) as the positive electrode.
  • the button battery After standing the prepared button battery at room temperature (25°C) for 10 hours, the button battery was activated by charging and discharging, and then the button battery prepared above was charged and discharged using a blue battery charge and discharge tester. Loop test. First, cycle at room temperature (25°C) at a rate of 0.1C for 1 week, and then continue to cycle at a rate of 0.2C for 4 weeks, wherein the charge-discharge voltage range of the control battery is 3.5V-4.9V. Then, the button battery was transferred to a high temperature environment of 55°C, and the cycle was continued for 50 cycles at a rate of 0.2C, while the charge-discharge voltage range of the control battery was still 3.5V to 4.9V.
  • the positive electrode active material prepared in Example 6 has the best electrochemical performance
  • the positive electrode active material prepared in Example 7 has the second highest electrochemical performance
  • the positive electrode active material prepared in Comparative Example 1 has the best electrochemical performance.
  • the electrochemical performance is the worst.

Abstract

La présente invention concerne un précurseur de matériau actif d'électrode positive, dont la formule générale moléculaire chimique est Ni0,5-xMn1,5-y-sAs(PO4)z(B)u, A étant un élément métallique non-lithium et/ou un élément métalloïde, B représentant OH- ou CO3 2-, − 0,2 ≤ x ≤ 0,2, − 0,2 ≤ y ≤ 0,2, 0 ≤ s ≤ 0,1, 0,003 ≤ z ≤ 0,07, 1,8 ≤ u ≤ 4,4, et le phosphore dans le précurseur de matériau actif d'électrode positive étant réparti uniformément ou non uniformément. La présente invention concerne en outre un procédé de préparation d'un précurseur de matériau actif d'électrode positive, selon lequel un phosphate soluble dans l'eau conjointement avec un sel de nickel soluble dans l'eau et un sel de manganèse sont ajoutés dans une cuve de réaction, une condition de réaction est contrôlée et la coprécipitation du phosphore avec des ions métalliques de nickel et de manganèse est obtenue. En outre, la présente invention concerne également un matériau actif d'électrode positive et son procédé de préparation, une électrode positive et une batterie secondaire lithium-ion.
PCT/CN2021/130504 2020-11-17 2021-11-15 Précurseur de matériau actif d'électrode positive et procédé de préparation associé, matériau actif d'électrode positive et procédé de préparation associé, électrode positive de batterie secondaire lithium-ion et batterie secondaire lithium-ion WO2022105696A1 (fr)

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CN202011286686.7A CN114512660B (zh) 2020-11-17 2020-11-17 正极活性材料前驱体及其制备方法和正极活性材料
CN202111308255.0A CN116081588A (zh) 2021-11-05 2021-11-05 正极活性材料前驱体及其制备方法、正极活性材料及其制备方法、正极及锂离子二次电池
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