WO2019041788A1 - Matériau cœur-écorce - Google Patents

Matériau cœur-écorce Download PDF

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WO2019041788A1
WO2019041788A1 PCT/CN2018/079942 CN2018079942W WO2019041788A1 WO 2019041788 A1 WO2019041788 A1 WO 2019041788A1 CN 2018079942 W CN2018079942 W CN 2018079942W WO 2019041788 A1 WO2019041788 A1 WO 2019041788A1
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core
shell
shell material
precursor
material according
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PCT/CN2018/079942
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Chinese (zh)
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毕玉敬
刘孟
姜阳
秦银平
王德宇
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中国科学院宁波材料技术与工程研究所
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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 a core-shell material and belongs to the field of electrode materials.
  • lithium-ion battery As a new green energy source, lithium-ion battery has outstanding advantages such as high energy density, long cycle life, low self-discharge efficiency, no memory effect, and good safety. It has been widely used in electronic products and power car batteries. At present, the challenge of on-board lithium-ion batteries is to improve the cruising range on the premise of ensuring safety, and on the other hand to reduce costs.
  • the positive electrode material is an important component in determining the energy density of a lithium ion battery in a lithium ion battery, and the energy density of the lithium ion battery can be effectively improved by increasing the capacity of the positive electrode material.
  • Nickel-cobalt-manganese-lithium and nickel-cobalt-aluminum silicate-based layered cathode materials are considered to be the most promising cathode materials for on-board lithium batteries due to their high capacity, good rate performance and low price.
  • high nickel ternary materials have problems such as high surface activity and instability in humid air.
  • the currently used improvement method is to coat the surface of the material with an inert substance such as MgO, TiO 2 , Al 2 O 3 (Ultrathin Al 2 O 3 Coatings for Improved Cycling Performance and Thermal Stability of LiNi 0.5 Co 0.2 Mn 0.3 O 2 Cathode.Material Electrochimica Acta 203 (2016) 154-161 and patent "a lithium ion battery and its positive electrode material", publication number: CN102332577A), SiO 2 (High-performance lithium ion batteries using SiO 2 -coated LiNi 0.5 Co 0.2 Mn 0.3 O 2 microspheres as cathodes. Journal of Alloys and Compounds 709 (2017) 708-716).
  • an inert substance such as MgO, TiO 2 , Al 2 O 3 (Ultrathin Al 2 O 3 Coatings for Improved Cycling Performance and Thermal Stability of LiNi 0.5 Co 0.2 Mn 0.3 O 2 Cathode.Material Electrochimica Acta 203 (2016)
  • the principle of coating is to reduce the direct contact between the ternary material and the air and electrolyte, and to inhibit the formation of side reactions on the surface of the ternary material.
  • most of the coating methods are for the processing of the sintered material. Since the coating process usually requires the sintered ternary material to be treated in water or an organic solvent, secondary calcination is required, and the calcination process is inevitable. The local spinel phase will be generated, causing the material capacity to decrease, the cycle to deteriorate, the gas production, and the battery safety hazard.
  • the current coating method has a small coating amount, cannot form a uniform coating layer, and the coating layer material is not electrochemically active, and cannot have lithium ion deintercalation ability, thereby affecting the electrochemical performance of the cathode material.
  • a core-shell material for use in a positive electrode material of a lithium ion battery to provide excellent long-cycle stability of the positive electrode while improving safety and storage stability of the material.
  • the positive electrode material with thick composite coating layer proposed in the invention has simple material preparation process, and has the advantages of easy processing in the process of manufacturing the battery using the material; has good application potential and huge market space.
  • the core material of the core-shell material is at least one selected from the group consisting of compounds having the formula of formula (I) and formula (II);
  • M is at least one selected from the group consisting of metals.
  • M is at least one selected from the group consisting of Cr, Mg, Ga, Ti, Fe, Cu, Sb, Sr, Ca, K, Na, Sn, and Zn.
  • x, y, z, r are independently selected from the range of -0.1 ⁇ x ⁇ 0.2, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 0.5, 0. ⁇ r ⁇ 0.5.
  • x, y, z, r are independently selected from the following ranges: 0 ⁇ x ⁇ 0.1, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 0.5, 0 ⁇ r ⁇ 0.5.
  • the shell layer has electrochemical activity and lithium ion transport capability.
  • the shell layer of the core-shell material is selected from at least one of a crystalline phase material and an amorphous phase material;
  • the crystalline phase material is selected from at least one of the compounds having the chemical formulas of formula (III), formula (IV), formula (V), and formula (VI):
  • the amorphous phase material is selected from at least one of the compounds having the chemical formulas of formula (VII), (VIII):
  • the Q is at least selected from the group consisting of Nb, Zr, Ta, Y, Sb, Mo, La, Pb, Bi, In, W, Sn, Ga, Cd, Sc, Ba, V, Cr, Ti, and Zn.
  • the crystalline phase material is uniformly dispersed in the amorphous phase material.
  • the concentration of Ni in the shell layer C Ni shell is smaller than the concentration of Ni in the core C Ni core ;
  • the C Ni core at a certain position in the core (the number of moles of Ni in the core / the sum of the positions of Ni and the number of moles of other metal elements) ⁇ 100%;
  • C Ni housing shell in a position (the number of moles of Ni in the shell of the number of moles of the location / position of the Ni and other metal elements) ⁇ 100%.
  • the core shell material has a shell thickness of from 1 to 500 nm.
  • the core shell material has a shell thickness of 50 to 100 nm.
  • the core shell material has a shell thickness of 100 to 300 nm.
  • the number of layers of the shell layer is from 1 to 50 layers.
  • the number of layers of the shell layer is from 1 to 30 layers.
  • the core shell material comprises at least one surface protective layer outside the shell layer.
  • the surface protective layer is selected from at least one of oxides.
  • the oxide is selected from the group consisting of Al 2 O 3 , MgO, ZrO 2 , ZnO, Y 2 O 3 , Ta 2 O 5 , Cr 2 O 3 , Nb 2 O 5 , Mo 2 O 3 , V 2 O 5 At least one of TiO 2 , Ga 2 O 3 , SrO, BaO, WO 2 , Sb 2 O 5 , SnO, CdO, Bi 2 O 3 , and PbO.
  • a method of preparing the core-shell material comprising at least a multilayer precursor method
  • the structure of the multilayer precursor is: at least one of Ni y Co z Mn 1-yz M 1-yzr (OH) 2 and Ni y Co z Al 1-yz M 1-yzr (OH) 2 inside.
  • the outer layer is in turn an oxide, hydroxide or oxyhydroxide corresponding to Q, and/or an oxide, hydroxide or oxyhydroxide corresponding to N;
  • Q is at least one selected from the group consisting of Nb, Zr, Ta, Y, Sb, Mo, La, Pb, Bi, In, W, Sn, Ga, Cd, Sc, Ba, V, Cr, Ti, and Zn;
  • N is at least one selected from the group consisting of Co, Fe, Ni, and Mn.
  • the precursor P1 in the step (1) is mixed with the solution containing the Q element, the pH of the system is adjusted to 2 to 14, after stirring, washing, separating, and drying, the precursor P2 is obtained;
  • step (3) repeating step (2) a total of n times, n is a positive integer greater than or equal to 1, to obtain a precursor Pn;
  • the precursor Pn obtained in the step (3) is mixed with the solution containing the N element, the pH of the system is adjusted to 7 to 14, after stirring, washing, separating, and drying, the precursor P3 is obtained;
  • the precursor P3 obtained in the step (4) is uniformly mixed with a lithium source, and after sintering, the core-shell material is obtained.
  • the method further comprises the steps of:
  • the core-shell material is in contact with the raw material for preparing the surface protective layer, and is coated;
  • the layer-by-layer coating is performed in a direction away from the core.
  • the pH of the system is adjusted to 7 to 14 as described in the step (1), the step (2), and the step (4), using a solution of an alkali metal hydroxide and/or an aqueous ammonia solution.
  • the alkali metal hydroxide is at least one selected from the group consisting of LiOH, NaOH, and KOH.
  • the stirring in the step (1), the step (2), and the step (4) is stirred for 5 to 24 hours;
  • the dried drying temperature is 50 to 200 °C.
  • the drying has a drying temperature of 80 to 200 °C.
  • the pH of the system is adjusted to a value within a range of 10 to 12.
  • the lithium source in the step (5) is at least one selected from the group consisting of lithium carbonate, lithium hydroxide, lithium chloride, lithium nitrate, and lithium acetate.
  • the sintering in the step (5) is carried out in an oxygen-containing atmosphere.
  • the oxygen-containing atmosphere is selected from the group consisting of air, oxygen, a mixture of oxygen and nitrogen and/or argon, and a mixture of air and nitrogen and/or argon.
  • the sintering in the step (5) is first performed at 400 to 700 ° C for 2 to 16 hours, and then at 700 to 1000 ° C for 10 to 24 hours.
  • the sintering in the step (5) is first performed at 450 to 600 ° C for 4 to 7 hours, and then at 800 to 1000 ° C for 10 to 15 hours.
  • the molar ratio of the precursor P1, P2, Pn or P3 to the lithium source is 1:0.98-1.2;
  • the number of moles of the precursor P1, P2, Pn or P3 is calculated by the sum of the molar amounts of the Ni element, the Co element, the M element, the Al element/Mn element and the metal element in the shell precursor in the core; The number is in terms of the number of moles of lithium contained therein.
  • the preparation method of the precursor in the steps (1) to (4) includes at least one of dry mixing, wet ball milling, and coprecipitation.
  • the method for preparing a core-shell material comprises at least the following steps:
  • Q salt is: Q is Nb, Zr, Ta, Y, Sb, Mo, La, Pb, Bi, In, Any one or a combination of two or more of soluble salts (such as sulfates, nitrates, chlorides, acetates) of W, Sn, Ga, Cd, Sc, Ba, V, Cr, Ti, and Zn.
  • soluble salts such as sulfates, nitrates, chlorides, acetates
  • N salt is a soluble salt such as a sulfate, a nitrate, a chloride or an acetate of Co, Fe, Ni or Mn. Any one or a combination of two or more.
  • the precursor P2 is uniformly mixed with the lithium salt, and the uniformly mixed material is sintered in an oxygen atmosphere to obtain a positive electrode material.
  • the molar ratio of the lithium salt to the precursor is 0.98-1.20
  • the lithium salt is one or more of lithium carbonate, lithium hydroxide, lithium chloride, lithium nitrate and lithium acetate.
  • a protective layer oxide may be added to the surface of the positive electrode material. Specifically, the following steps are taken:
  • step (v) Put the material obtained by the step (iv) sintering into water, stir to form a dispersion, add a solution of the C salt, and simultaneously add the alkali solution to adjust the pH to 5-14, and coat the surface of the sintered material.
  • the hydroxide of layer C was obtained as a positive electrode material having a surface coated with a hydroxide of C. After filtration, calcination was carried out to obtain a positive electrode material having an oxide coated with C on its surface.
  • the C salt is a soluble salt of Al, Mg, Zr, Zn, Y, Ta, Cr, Nb, Mo, V, Ti, Ga, Sr, Ba, W, Sb, Sn, Ga, Cd, Bi, Pb.
  • the alkali solution is one or more of NaOH, LiOH, and KOH.
  • the final pH is controlled at different values depending on the type of salt selected.
  • the calcination temperature is 300-700 ° C, and the calcination atmosphere is air or oxygen.
  • the internal body can be obtained as a nickel-cobalt-manganese/lithium aluminate material, and the composite coating layer can be stabilized in air except for the active material, and the protective layer on the surface is an oxide, which protects the electrode material. .
  • the use of the core-shell material and/or the core-shell material prepared by the method is provided, namely:
  • a positive electrode material for a lithium ion battery comprising the core-shell material and/or a core-shell material prepared according to the method.
  • a lithium ion battery comprising the lithium ion battery cathode material.
  • the positive electrode of the lithium ion battery can be used for a positive electrode material in a lithium ion battery using an organic solvent or an aqueous solution as an electrolyte, and can also be used for a positive electrode material in a lithium ion battery using a solid electrolyte.
  • the preparation method of the lithium ion battery mixing the positive electrode material with the conductive agent acetylene black and the binder polyvinylidene fluoride in a solvent of nitrogen methylpyrrolidone (NMP), and mass ratio of the positive electrode material, the conductive agent and the binder At 85:10:5, the uniformly mixed slurry was coated on an aluminum foil and dried to prepare a positive electrode of a lithium ion battery.
  • NMP nitrogen methylpyrrolidone
  • a new positive electrode material and a preparation method for a thicker composite cladding layer are proposed, and the positive electrode material prepared by the method still has a high discharge capacity, since the first phase has a crystalline phase and an amorphous phase.
  • the thicker composite coating provides excellent long-cycle stability of the positive electrode while improving the safety and storage stability of the material.
  • the positive electrode material with thick composite coating layer proposed in the invention has simple material preparation process, and has the advantages of easy processing during the process of manufacturing the battery using the material. Therefore, the material and its preparation process have good application potential and huge market space.
  • the core-shell material provided by the present application has a high discharge capacity, and a thick composite coating layer having a crystalline phase and an amorphous phase is used for the battery positive electrode material, so that the positive electrode has excellent long cycle stability. At the same time, the safety and storage stability of the material are improved.
  • the core-shell material provided by the present application wherein the shell layer has a composite coating layer composed of an amorphous phase and/or a crystal phase, which effectively suppresses outward diffusion of a portion of the nickel of the inner host material, and has a low nickel surface. Applied to the electrode material, it can overcome the defects in the prior art that are easily reduced to affect performance.
  • the core-shell material provided by the present application has an electrochemical activity and a lithium ion transport capability, and the electrode material can block the direct contact between the electrode material and the electrolyte, reduce side reactions inside the battery, and improve safety performance; At the same time, since the shell layer has lithium ion transport capability, it is possible to finitely reduce the impedance increase during battery cycling.
  • the thickness of the shell material of the core-shell material provided by the present application is thicker than the conventional method, between 1-500 nm; the material can work stably under high voltage, and the number of cycles is more than that of ordinary materials, and the lithium ion battery using the cathode material is used. It has a long practical life; it has high stability in wet air and the material is easy to process.
  • Example 1 is a topographical view of a precursor P1 prepared in Example 11.
  • Example 2 is a topographical view of the precursor P2 prepared in Example 12.
  • Example 4 is a topographical view of the precursor P4 prepared in Example 1.
  • Figure 5 is a topographical view of the preparation of the precursor P5 in Example 2.
  • Figure 6 is a topographical view of the preparation of precursor P6 in Example 3.
  • Fig. 7 is a topographical view showing the preparation of the precursor P7 in Example 4.
  • Figure 8 is a topographical view of the preparation of precursor P8 in Example 5.
  • Figure 9 is a topographical view of the preparation of precursor P9 in Example 6.
  • Figure 10 is a topographical view of the preparation of the precursor P10 in Example 7.
  • Figure 11 is a topographical view of the preparation of core shell material 2 # in Example 2.
  • Figure 12 is a topographical view of the preparation of the core-shell material 4 # in Example 4.
  • Figure 13 is a topographical view of the preparation of the core-shell material 7 # in Example 7.
  • Figure 14 is a cross-sectional elemental distribution diagram of the precursor P6 particles prepared in Example 3.
  • FIG 15 is a core-shell material prepared in Example # 33 particle cross-sectional view of an element distribution.
  • Figure 16 is a transmission electron micrograph of the core shell material 11 # prepared in Example 11.
  • Figure 17 is a transmission electron micrograph of the core shell material 2 # prepared in Example 2.
  • Figure 18 is a transmission electron micrograph of the core shell material 3 # prepared in Example 3.
  • Figure 19 is a comparison of X-ray diffraction of core shell materials 11 # , 1 # and 3 # in Example 11, Example 1, and Example 3.
  • Example 20 is an X-ray diffraction comparison diagram of the core shell materials 12 # , 4 # , 5 # in Example 12, Example 4, and Example 5.
  • Figure 21 is a comparison of X-ray diffraction of core shell materials 13 # , 6 # and 7 # in Example 13, Example 6, and Example 7.
  • Example 22 is a comparison diagram of discharge curves of lithium ion batteries DC11, DC1, DC2, and DC3 prepared by preparing the core-shell materials in Example 11, Example 1, Example 2, and Example 3.
  • Example 23 is a comparison diagram of the ratio performance of lithium ion batteries DC11, DC1, DC2, and DC3 prepared by using the core-shell materials in Example 11, Example 1, Example 2, and Example 3.
  • Example 24 is a comparison diagram of cycle performance of lithium ion batteries DC11, DC1, and DC3 prepared by preparing core-shell materials in Example 11, Example 1, and Example 3.
  • Example 25 is a comparison diagram of discharge curves of lithium ion batteries DC12, DC4, and DC5 prepared by preparing core-shell materials in Example 12, Example 4, and Example 5.
  • Example 26 is a comparison diagram of the rate performance of lithium ion batteries DC12, DC4, and DC5 prepared by preparing the core-shell materials in Example 12, Example 4, and Example 5.
  • Example 27 is a comparison diagram of cycle performance of lithium ion batteries DC12, DC4, and DC5 prepared by preparing core-shell materials in Example 12, Example 4, and Example 5.
  • Example 28 is a comparison diagram of discharge curves of lithium ion batteries DC13, DC6, and DC7 prepared by preparing core-shell materials in Example 13, Example 6, and Example 7.
  • Example 29 is a comparison diagram of the rate performance of lithium ion batteries DC13, DC6, and DC7 prepared by preparing the core-shell materials in Example 13, Example 6, and Example 7.
  • Example 30 is a comparison diagram of cycle performance of lithium ion batteries DC13, DC6, and DC7 prepared by preparing core-shell materials in Example 13, Example 6, and Example 7.
  • Morphological test analysis was performed using a scanning electron microscope S4800H manufactured by Hitachi, Japan, and a transmission electron microscope Tecnai F20 manufactured by FEI, the Netherlands.
  • Elemental zone analysis test analysis was performed using a scanning electron microscope S4800 EDS manufactured by Hitachi, Japan.
  • Electrochemical performance test analysis was carried out using LAND electrochemical test system CT2001A produced by Wuhan Xinnuo Electronics Co., Ltd.
  • Example 1 The shell layer is an amorphous phase core-shell material
  • the mixed solution was prepared according to a molar ratio of Ni, Co, and Mn of 1:1:1, and nickel sulfate hexahydrate, cobalt sulfate heptahydrate, and manganese sulfate monohydrate 87.61 g, 93.72 g, 56.34 g were weighed and dissolved in 500 mL of water. 1000 mL of a 4 mol/L NaOH solution and 1000 mL of a 2 mol/L aqueous ammonia solution were prepared.
  • a nitrogen-protected reaction vessel 200 mL of water was added, and the mixed solution was simultaneously added to the reaction vessel with a 4 mol/L NaOH solution and a 2 mol/L aqueous ammonia solution, and the final pH of the solution was controlled at 11. After the completion of the sedimentation, the precipitate was washed by filtration, and dried at 80 ° C to obtain a precursor P1.
  • the Zr(SO 4 ) 2 solution was added to the dispersion of the precursor P1. After the end of the addition, the pH was adjusted to 8.0 with aqueous ammonia, filtered, washed three times with water, and dried at 100 ° C to obtain a precursor coated with ZrO(OH) 2 . P4.
  • Example 2 Core-shell material in which the shell layer is a crystalline phase
  • the mixed solution was prepared according to a molar ratio of Ni, Co, and Mn of 1:1:1, and nickel sulfate hexahydrate, cobalt sulfate heptahydrate, and manganese sulfate monohydrate 87.61 g, 93.72 g, 56.34 g were weighed and dissolved in 500 mL of water. 1000 mL of a 4 mol/L NaOH solution and 1000 mL of a 2 mol/L aqueous ammonia solution were prepared.
  • a nitrogen-protected reaction vessel 200 mL of water was added, and the mixed solution was simultaneously added to the reaction vessel with a 4 mol/L NaOH solution and a 2 mol/L aqueous ammonia solution, and the final pH of the solution was controlled at 11. After the completion of the sedimentation, the precipitate was washed by filtration, and dried at 80 ° C to obtain a precursor P1.
  • the Co(CH 3 COO) 2 solution was added to the dispersion of the precursor P1. After the end of the addition, the pH was adjusted to 12 with ammonia water, filtered, washed three times with water, and dried at 100 ° C to obtain a precursor of surface coated Co(OH) 2 . Body P5.
  • Example 3 The shell layer is a core-shell material of a crystalline phase and an amorphous phase
  • Example 2 50 g of the precursor P4 in Example 1 was weighed, 200 mL of water was added thereto, and stirred to form a dispersion; 13.03 g of Co(CH 3 COO) 2 ⁇ 4H 2 O was weighed and dissolved in 30 mL of water. A 4 mol/L LiOH solution and a 1 mol/L aqueous ammonia solution were prepared.
  • the Co(CH 3 COO) 2 solution was simultaneously added to the dispersion of the precursor P4 at 4 mol/L of LiOH and an aqueous ammonia solution, and Co(OH) 2 was deposited on the surface of the precursor P4, and the sedimentation pH was controlled at 12.
  • the mixture was filtered and washed with water, and dried at 100 ° C to obtain a composite precursor P6.
  • Example 4 The shell layer is an amorphous phase core-shell material
  • the mixed solution was prepared according to a molar ratio of Ni, Co and Mn of 5:2:3, and respectively, nickel sulfate hexahydrate, cobalt sulfate heptahydrate, manganese sulfate monohydrate 131.42 g, 56.22 g, 50.70 g were weighed and dissolved in 500 mL of water. 1000 mL of a 4 mol/L NaOH solution and 1000 mL of a 2 mol/L aqueous ammonia solution were prepared.
  • a nitrogen-protected reaction vessel 200 mL of water was added, and the mixed solution was simultaneously added to the reaction vessel with a 4 mol/L NaOH solution and a 2 mol/L aqueous ammonia solution, and the final pH of the solution was controlled at 11.5. After the completion of the sedimentation, the precipitate was washed by filtration, and dried at 80 ° C to obtain a precursor P2, as shown in Fig. 2, which was spherical.
  • the Zr(SO 4 ) 2 solution was added to the dispersion of the precursor P2. After the end of the addition, the pH was adjusted to 8.0 with aqueous ammonia, filtered, washed three times with water, and dried at 100 ° C to obtain a precursor coated with ZrO(OH) 2 . P7.
  • Example 5 The shell layer is a core-shell material of a crystalline phase and an amorphous phase
  • Example 4 50 g of the precursor P7 in Example 4 was weighed, 200 mL of water was added, and stirred to form a dispersion; 11.93 g of Co(CH 3 COO) 2 ⁇ 4H 2 O was weighed and dissolved in 50 mL of water. A 4 mol/L LiOH solution and a 1 mol/L aqueous ammonia solution were prepared.
  • the Co(CH 3 COO) 2 solution was simultaneously added to the dispersion of the precursor P7 at 4 mol/L of LiOH and an aqueous ammonia solution, and Co(OH) 2 was deposited on the surface of the precursor P7, and the sedimentation pH was controlled at 12.
  • the mixture was filtered and washed with water, and dried at 100 ° C to obtain a composite precursor P8.
  • the shell-shell material of the embodiment 6 is an amorphous phase
  • the mixed solution was prepared according to a molar ratio of Ni, Co and Mn of 8:1:1, and respectively, nickel nitrate hexahydrate, cobalt nitrate hexahydrate and manganese nitrate 232.63 g, 29.10 g, 25.10 g were weighed and dissolved in 500 mL of water. 1000 Ml of a 5 mol/L NaOH solution and 1000 mL of a 2 mol/L aqueous ammonia solution were prepared.
  • the Zr(SO 4 ) 2 solution was added to the dispersion of the precursor P3. After the end of the addition, the pH was adjusted to 8.0 with ammonia water, filtered, washed three times with water, and dried at 100 ° C to obtain a precursor of surface-coated ZrO(OH) 2 . Body P9.
  • Example 7 The shell layer is a core-shell material of a crystalline phase and an amorphous phase
  • Example 6 50 g of the precursor P9 in Example 6 was weighed, 200 mL of water was added thereto, and stirred to form a dispersion; 14.32 g of Mn(CH 3 COO) 2 ⁇ 4H 2 O was weighed and dissolved in 60 mL of water. A 4 mol/L LiOH solution and a 1 mol/L aqueous ammonia solution were prepared.
  • the Mn(CH 3 COO) 2 solution was simultaneously added to the dispersion of the precursor P9 with 4 mol/L of LiOH and an aqueous ammonia solution, and Mn(OH) 2 was deposited on the surface of the precursor P9, and the sedimentation pH was controlled at 12, and filtered. The mixture was washed with water and dried at 100 ° C to obtain a composite precursor P10.
  • the shell layer of the embodiment 8 is a crystalline phase and an amorphous phase, and has a surface protective layer core-shell material.
  • the sintered core-shell material 2 # 50g in Example 2 was weighed, and 100 mL of water was added to form a suspension. 6.74 g of Mg(NO 3 ) 2 ⁇ 6H 2 O was weighed and dissolved in 50 mL of water to prepare a 1 mol/L NaOH solution.
  • the solution of Mg(NO 3 ) 2 was slowly added to the suspension of 2 # together with the solution of NaOH, and Mg(OH) 2 was allowed to settle on the surface of the positive electrode material, and the pH of the end point was 11.5.
  • the material was calcined at 500 ° C for 6 hours to obtain a surface coated with MgO, the core was LiNi 1/3 Co 1/3 Mn 1/3 O 2 , the shell layer was crystalline phase LiCoO 2 and amorphous phase Li 6 Zr 2 O 7 core-shell material, labeled 8 # .
  • the shell layer of the embodiment 9 is a crystalline phase and an amorphous phase, and has a surface protective layer core-shell material.
  • the sintered core-shell material 4 # 50g in Example 4 was weighed, and 100 mL of water was added to form a suspension. 6.45 g of MgSO 4 ⁇ 7H 2 O was weighed and dissolved in 50 mL of water to prepare a 1 mol/L NaOH solution.
  • the shell layer of the embodiment 10 is a crystalline phase and an amorphous phase, and has a surface protective layer core-shell material.
  • the sintered core-shell material 7 # 50g in Example 7 was weighed, and 100 mL of water was added to form a suspension.
  • the solution of Mg(CH 3 COO) 2 was slowly added to the suspension of the positive electrode material together with the solution of NaOH to precipitate Mg(OH) 2 on the surface of the positive electrode material, and the pH value was 11.5; after filtration and washing, The material was calcined at 500 ° C for 6 hours to obtain a core-shell material coated with MgO, a core of LiNi 0.8 Co 0.1 Mn 0.1 O 2 , a shell of crystalline phase LiMn 2 O 4 and an amorphous phase of Li 6 Zr 2 O 7 . , marked as 10 # .
  • the mixed solution was prepared according to a molar ratio of Ni, Co, and Mn of 1:1:1, and nickel sulfate hexahydrate, cobalt sulfate heptahydrate, and manganese sulfate monohydrate 87.61 g, 93.72 g, 56.34 g were weighed and dissolved in 500 mL of water. 1000 mL of a 4 mol/L NaOH solution and 1000 mL of a 2 mol/L aqueous ammonia solution were prepared.
  • a nitrogen-protected reaction vessel 200 mL of water was added, and the mixed solution was simultaneously added to the reaction vessel with a 4 mol/L NaOH solution and a 2 mol/L aqueous ammonia solution, and the final pH of the solution was controlled at 11. After the completion of the sedimentation, the precipitate was washed by filtration, and dried at 80 ° C to obtain a precursor P1.
  • the mixed solution was prepared according to a molar ratio of Ni, Co and Mn of 5:2:3, and respectively, nickel sulfate hexahydrate, cobalt sulfate heptahydrate, manganese sulfate monohydrate 131.42 g, 56.22 g, 50.70 g were weighed and dissolved in 500 mL of water. 1000 mL of a 4 mol/L NaOH solution and 1000 mL of a 2 mol/L aqueous ammonia solution were prepared.
  • LiOH ⁇ H 2 O 23.94 g was weighed and mixed uniformly with the precursor, sintered at 400 ° C for 6 hours, and then sintered at 850 ° C for 12 hours.
  • a LiNi 0.5 Co 0.2 Mn 0.3 O 2 material was obtained, labeled 12 # .
  • the mixed solution was prepared according to a molar ratio of Ni, Co and Mn of 8:1:1, and respectively, nickel nitrate hexahydrate, cobalt nitrate hexahydrate and manganese nitrate 232.63 g, 29.10 g, 25.10 g were weighed and dissolved in 500 mL of water. 1000 mL of a 5 mol/L NaOH solution and 1000 mL of a 2 mol/L aqueous ammonia solution were prepared.
  • LiNi 0.8 Co 0.1 Mn 0.1 . O 2 material labeled 13 # .
  • the materials 1 # to 13 # obtained in Examples 1 to 13 were used as a positive electrode material, and the conductive agent acetylene black and the binder polyvinylidene fluoride (PVDF) were uniformly mixed in a solvent of nitrogen methylpyrrolidone (NMP), and the positive electrode material,
  • NMP nitrogen methylpyrrolidone
  • the mass ratio of the conductive agent to the binder was 85:10:5, and the uniformly mixed slurry was coated on an aluminum foil, and vacuum-dried at 120 ° C for 12 hours to obtain positive electrodes C1 to C13 of the lithium ion battery.
  • the above-mentioned pole piece is used as a positive electrode, metal lithium is used as a negative electrode, the electrolyte is a solution of 1 mol/L lithium hexafluorophosphate ethylene carbonate and dimethyl carbonate, and the separator is assembled into a CR2032 type by using a 20 ⁇ m thick polyethylene and polypropylene composite material.
  • the precursors P1 to P10 were subjected to morphology test, and the obtained structure is shown in Figs. 1 to 10.
  • the precursor material is spherical and has a diameter of 10 to 40 ⁇ m; the shape of 1 # to 7 #
  • the appearance test, such as the material 2 # , 4 # , 7 # corresponds to Figure 11 ⁇ Figure 13, respectively, from the figure, it can be seen that the material is spherical, and the morphology of other materials is similar.
  • the prepared precursor and the positive electrode material are spherical secondary particles having a particle diameter of about 10 ⁇ m, and the particles are composed of primary particles of 200 to 500 nm.
  • Figures 16, 17 and 18 are projection electron micrographs of the core shell materials prepared in 11 # , 2 # and 3 # respectively. It can be seen from the figure that the surface of the 3 # surface having the composite coating layer prepared in Example 3 is relatively Many tiny crystalline regions and amorphous regions.
  • FIG. 19 is a sample of 13# in Example 13
  • the X-ray diffraction comparison chart of the 6# sample in Example 6 and the 7# sample in Example 7 shows that the synthesized uncoated material is an ⁇ -NaFeO 2 type crystal having a space group of R-3m.
  • the positive electrode material having the composite coating layer (shell layer) is a layered structure in which the space group is R-3m and a structure in which the olivine structure of Pmnb is symbiotic.
  • the element selection analysis is performed on the precursors P1 to P10 and the materials 1 # to 10 # , and the precursors and core-shell materials as in the example 3 are typically as follows.
  • Figure 14 is a diagram showing the element distribution of the cross section of the precursor P6 particles prepared in Example 3. It can be seen from the figure that the concentration of Ni in the precursor from the core to the shell gradually decreases, and the content of Co in the outermost layer appears most. The peak indicates that the content of Co in the shell is higher than that in the core. On the right side of the highest peak of Co concentration, the highest concentration of Zr is present. This result indicates that the synthesized precursor is a core-shell structure in which the core is Ni 0.33 Co 0.33 Mn 0.33 (OH) 2 , the intermediate layer is ZrO(OH) 2 , and the outermost layer is Co(OH) 2 . Fig.
  • Example 15 is a view showing the element distribution of the cross section of the core-shell material 3 # prepared in Example 3, and it can be seen from the figure that the Co element and the Zr element distribution do not show a peak having a higher concentration. Since the oxide precursor decomposes during high-temperature sintering, and reacts to form a uniform mixed region of the crystalline phase LiCoO 2 and the amorphous phase Li 6 Zr 2 O 7 .
  • the coin batteries DC1 to DC13 assembled in the fourteenth embodiment were subjected to a charge and discharge test with a voltage range of 2.8 to 4.3 volts, and the results were as follows.
  • 22 is a discharge curve of DC11, DC1, DC2, and DC3 corresponding to Example 11, Example 1, Example 2, and Example 3, and the discharge voltage was 4.3 V to 2.8 V, and the discharge ratio was 0.1 C. It can be seen from the comparison that the discharge capacity of the modified positive electrode material is similar to that of the unmodified positive electrode material.
  • 23 is a performance test of DC11, DC1, DC2, and DC3 corresponding to Example 11, Example 1, Example 2, and Example 3. The comparison shows that the prepared positive electrode material has improved rate performance and has The positive electrode material rate performance of the composite coating layer (including both the crystal phase and the amorphous phase in the shell layer) is significantly improved.
  • 24 is a cycle performance test curve of DC11, DC1, and DC3 corresponding to Example 11, Example 1, and Example 3. Obviously, the core-shell material coated by the crystalline phase and the amorphous phase improves the circulation of the positive electrode material. performance.
  • 25 is a discharge curve of DC12, DC3, and DC4 corresponding to Example 12, Example 3, and Example 4, and the discharge voltage was 4.3 V to 2.8 V, and the discharge magnification was 0.1 C. It can be seen from the comparison that the discharge capacity of the coated modified positive electrode material is similar to that of the uncoated positive electrode material.
  • 26 is a graph showing the rate performance test of DC12, DC3, and DC4 corresponding to Example 12, Example 3, and Example 4. By comparison, it can be seen that the rate performance of the cathode material having the composite coating layer and the performance of the uncoated sample. Relatively close, it indicates that the composite coating layer (shell layer) in the present application has good lithium ion transport ability.
  • 27 is a cycle performance curve of DC12, DC3, and DC4 corresponding to Example 12, Example 3, and Example 4. The positive electrode material having a composite coating layer (shell layer) has a marked improvement in cycle performance.
  • 28 is a discharge curve of DC13, DC5, and DC6 corresponding to Example 13, Example 5, and Example 6, and the discharge voltage was 4.3 V to 2.8 V, and the discharge magnification was 0.1 C. It can be seen from the comparison that the discharge capacity of the modified positive electrode material is similar to that of the uncoated positive electrode material.
  • 29 is a graph showing the rate performance test of DC13, DC5, and DC6 corresponding to Example 13, Example 5, and Example 6. As can be seen from the comparison, the ratio of the positive electrode material with the composite coating layer (shell layer) is not included. The rate performance of the coated positive electrode material is improved.
  • 30 is a cycle performance curve of DC13, DC5, and DC6 corresponding to Example 13, Example 5, and Example 6.
  • the positive electrode material having a composite coating layer (shell layer) has better cycle performance.

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Abstract

La présente invention concerne un matériau cœur-écorce. Une substance de cœur du matériau cœur-écorce est choisie parmi au moins l'un des composés ayant des formules moléculaires représentées par la formule (I) et la formule (II). Le matériau cœur-écorce est préparé à l'aide d'un procédé précurseur multicouche. Lorsqu'il est utilisé comme matériau d'électrode positive dans le domaine des batteries au lithium-ion, le matériau cœur-écorce n'a pas seulement une capacité élevée, mais également une bonne stabilité de l'air et une bonne performance de sécurité.
PCT/CN2018/079942 2017-08-28 2018-03-22 Matériau cœur-écorce WO2019041788A1 (fr)

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