CN112382734A - Lithium ion battery positive plate using cobalt-free high-nickel positive electrode material - Google Patents

Lithium ion battery positive plate using cobalt-free high-nickel positive electrode material Download PDF

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CN112382734A
CN112382734A CN202010863990.7A CN202010863990A CN112382734A CN 112382734 A CN112382734 A CN 112382734A CN 202010863990 A CN202010863990 A CN 202010863990A CN 112382734 A CN112382734 A CN 112382734A
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positive electrode
cobalt
free high
nickel
electrode material
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CN112382734B (en
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肖彪彪
陈瑶
许梦清
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Wanxiang A123 Systems Asia Co Ltd
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Wanxiang Group Corp
Wanxiang A123 Systems Asia Co Ltd
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a lithium ion battery positive plate using a cobalt-free high-nickel positive electrode material, which comprises a positive electrode current collector and a positive electrode active material layer loaded on the positive electrode current collector, wherein the components of the positive electrode active material layer comprise the cobalt-free high-nickel positive electrode material, a conductive agent and a binder, and the molecular formula of the cobalt-free high-nickel positive electrode material is Li (Ni)1‑ xMnx)ZryO2Wherein x is more than or equal to 0.1 and less than or equal to 0.5, and y is more than or equal to 0.002 and less than or equal to 0.003. When the cobalt-free high-nickel cathode material is prepared, the cobalt-free high-nickel cathode material is prepared by a coprecipitation method (Ni)1‑xMnx)Zry(OH)2A precursor; then the precursor is reacted with LiOH2And O mixing and calcining. According to the invention, the zirconium-doped cobalt-free high-nickel layered positive electrode material is used, so that the cycle performance and the rate performance of the positive electrode plate can be effectively improved; the precursor prepared by the coprecipitation method has complete appearance and uniform size, the tested Zr content is basically consistent with the doping amount, and the structural stability and the high-temperature stability are good.

Description

Lithium ion battery positive plate using cobalt-free high-nickel positive electrode material
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery positive plate using a cobalt-free high-nickel positive electrode material.
Background
Layered high-nickel ternary lithium ion battery anode material Li (Ni)1-x-yMnxCoy)O2(x+y<0.5) has a higher energy density and is currently one of the most promising positive electrode materials. The cobalt element is not only an active material, but also can effectively inhibit mixed arrangement of cations (Li/Ni) and stabilize the structure of the material, so that the cobalt-containing ternary material generally has good deep discharge characteristics and good rate performance. However, cobalt is expensive and scarce in storage, which is not suitable for large-scale use, and it is gradually becoming common knowledge in the industry to reduce the use of cobalt in the cathode material.
The cobalt-free ternary cathode material is usually LiNiO2The high nickel ternary material is formed by doping Mn, Al, Mg, Ti and other elements as a main body. For example, a "cobalt-free layered positive electrode material and a method for preparing the same, a positive electrode sheet and a lithium ion battery" disclosed in chinese patent literature has publication No. CN111435744A, and the cobalt-free layered positive electrode material includes: LiNixMnyO2The crystal, wherein x + y is 1, x is more than or equal to 0.55 and less than or equal to 0.95, and y is more than or equal to 0.05 and less than or equal to 0.45; and a lithium ion conductor attached to the LiNixMnyO2On at least part of the surface of the crystal. The cobalt-free layered positive electrode material has the advantages of low cost, low surface impedance, good conductivity, high diffusion speed of lithium ions in the cobalt-free layered positive electrode material and high electrochemical activity. However, the cobalt-free material is unsatisfactory in the aspects of rate cycle performance, element component regulation and the like, and a positive plate prepared by using the cobalt-free material is difficult to meet a long cycle test meeting a commercial standard.
Disclosure of Invention
The invention is toThe problem that the anode plate prepared by using the cobalt-free high-nickel anode material is difficult to meet the long cycle test meeting the commercial standard because the cobalt-free lithium ion battery anode material in the prior art is unsatisfactory in the aspects of rate cycle performance, element component regulation and the like is solved, and the cobalt-free high-nickel zirconium-doped precursor (Ni) prepared by a coprecipitation method is used for providing the lithium ion battery anode plate prepared by using the cobalt-free high-nickel anode material1-xMnx)Zry(OH)2With LiOH. H2The cobalt-free high-nickel zirconium-doped material prepared by O mixed sintering is used as a positive electrode material, and the obtained positive electrode plate has good cycle performance when used for a lithium ion battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
the lithium ion battery positive plate using the cobalt-free high-nickel positive electrode material comprises a positive electrode current collector and a positive electrode active material layer loaded on the positive electrode current collector, wherein the components of the positive electrode active material layer comprise the cobalt-free high-nickel positive electrode material, a conductive agent and a binder, and the molecular formula of the cobalt-free high-nickel positive electrode material is Li (Ni)1-xMnx)ZryO2Wherein x is more than or equal to 0.1 and less than or equal to 0.5, and y is more than or equal to 0.002 and less than or equal to 0.003.
The positive plate of the invention adopts the cobalt-free high-nickel positive material, and the cost can be effectively reduced without adding cobalt, but the increase of the nickel content enables the positive material to easily generate side reaction with electrolyte under the high-temperature environment to generate an SEI film, and the deterioration of the positive material is accelerated, so that the capacity of the positive material is seriously attenuated, and the performance of the battery is influenced. Therefore, in order to improve the structural stability of the cobalt-free high-nickel anode material, the zirconium is doped in the cobalt-free high-nickel anode material, the zirconium doping can increase the cell parameters a and c and the lithium ion diffusion coefficient, and the Li is reduced+/Ni+The ions are mixed and discharged, so that the zirconium doping can effectively improve the cycle performance and the rate capability of the cobalt-free high-nickel layered anode material, and the anode plate prepared by adopting the zirconium-doped cobalt-free high-nickel anode material has good electrical performance and structural stability.
Preferably, the preparation method of the cobalt-free high-nickel cathode material comprises the following steps:
(1) the volume ratio is (4.5-5.5): 1, mixing deionized water and 25-28% concentrated ammonia water, adding the mixture into a coprecipitation reaction kettle, and uniformly stirring at 40-80 ℃ to obtain a reaction base solution;
(2) mixing NiSO4·6H2O、MnSO4·5H2O and ZrCl4Dissolving Ni, Mn and Zr atoms in water according to the molar ratio to form a mixed salt solution;
(3) respectively adding the mixed salt solution, the NaOH solution and the concentrated ammonia water into a coprecipitation reaction kettle under the protection of nitrogen to be mixed with the reaction base solution, so that the pH of a reaction system is 11-12, and stirring and reacting for 18-24 hours at 40-80 ℃ under the protection of nitrogen;
(4) aging the reaction product in an aging reaction kettle for 4-6 h, vacuum filtering and drying to obtain (Ni)1-xMnx)Zry(OH)2A precursor;
(5) will (Ni)1-xMnx)Zry(OH)2Precursor and LiOH. H2And mixing the O according to the molar ratio, and calcining in an oxygen-rich atmosphere to obtain the cobalt-free high-nickel cathode material.
Preferably, the stirring speed in the step (1) is 500 to 900 r/min.
Preferably, the total concentration of all substances in the mixed salt solution in the step (2) is 1.5-2.5 mol/L.
Preferably, the concentration of the NaOH solution in the step (3) is 1.5-2.5 mol/L, and the feeding speed is 0.45-0.55 mL/min; the feeding speed of the mixed salt solution is 0.2-0.3 mL/min.
Preferably, the drying temperature in the step (4) is 90-110 ℃.
Preferably, the calcination method in step (5) is: heating from room temperature to 550-650 ℃ at a speed of 4-6 ℃/min, calcining for 5-7 h at constant temperature, and heating to 750-850 ℃ for 7-9 h at constant temperature.
The invention firstly adopts the steps (1) - (4) to prepare the zirconium-doped cobalt-free high nickel precursor (Ni) by a coprecipitation method1- xMnx)Zry(OH)2Then, the precursor is reacted with LiOH. H by the step (5)2And mixing and sintering O to obtain the cobalt-free high-nickel cathode material. The doping proportion of zirconium and the technological parameters of each step are adopted in the preparation processThe method has the advantages of accurate regulation and control, realization of synergistic effect of each process, complete shape and uniform size of the prepared precursor, basically consistent Zr content and doping amount in test, good structural stability and high-temperature stability, difficult phase change of surface particles and extension of the surface particles to the interior of the particles, and difficult reaction of Li with carbon dioxide and water in the air to generate Li in the sintering process2CO3Affecting high temperature cycle performance and storage stability. Therefore, the cobalt-free high-nickel cathode material prepared by the invention has good cycle performance and rate capability.
Preferably, the conductive agent is selected from one or two of acetylene black and single-walled carbon nanotubes.
Preferably, the preparation method of the adhesive comprises the following steps:
A) adding deionized water with the conductivity of less than 8 mu s/cm, ammonium persulfate and sodium perfluorooctanoate into a reaction kettle under the protection of inert gas, wherein the mass of the ammonium persulfate and the mass of the sodium perfluorooctanoate are respectively 0.001-1% and 0.001-0.3% of that of the deionized water;
B) introducing monomer vinylidene fluoride and monomer ethylene into the reaction kettle until the pressure is 1.0-7.0 MPa, wherein the mole fraction of the monomer vinylidene fluoride is 40-70%, and the mole fraction of the monomer ethylene is 60-30%;
C) heating to 35-110 ℃, reacting for 10-30 h, continuously introducing the monomer vinylidene fluoride and the monomer ethylene which have the same proportion as the monomer vinylidene fluoride and the monomer ethylene in the step B) in the reaction process, and reducing the pressure to 1.0-3.0 MPa after the reaction is finished;
D) the reaction product is coagulated, washed, separated, dried and crushed to obtain the adhesive.
Polyvinylidene fluoride (PVDF) is generally used as a positive binder in the prior art, but PVDF molecular chains have higher regularity, the arrangement of molecular chains is tight, and stronger hydrogen bonds exist, so that the flexibility of the PVDF positive binder is limited, and the slurry is easy to gel, the pole piece is easy to become brittle, and the binding property is not strong.
The binder used by the invention is polymerized by monomer vinylidene fluoride and monomer ethylene, realizes the purpose of replacing fluorine atoms by hydrogen atoms, and can obtain different polymers with hydrogen atoms replacing fluorine atoms by controlling different ethylene contents. When fluorine atoms are replaced by hydrogen atoms, the crystallinity of PVDF molecules is reduced, thereby achieving the purpose of improving flexibility. In addition, the reduction of fluorine atoms and the increase of hydrogen atoms reduce the probability of HF elimination reaction and reduce the crystallinity of the binder, thereby effectively avoiding the gelation of the anode slurry and improving the performance of the anode sheet.
Meanwhile, monomer ethylene is adopted to participate in the reaction, so that the use amount of vinylidene fluoride is reduced, the material cost can be reduced, and the damage of fluorine in the vinylidene fluoride to equipment can be reduced; in addition, because the less the fluorine atoms are in a certain substitution range, the stronger the adhesiveness is, the adhesiveness of the adhesive is stronger, and other PVDF does not need to be compounded to increase the adhesiveness.
Preferably, the mass ratio of the cobalt-free high-nickel cathode material to the conductive agent to the binder is (18-20): 1: 1.
therefore, the invention has the following beneficial effects:
(1) the zirconium-doped cobalt-free high-nickel layered cathode material can effectively improve the cycle performance and rate performance of the cathode plate; (2) prepared by using a coprecipitation method in the preparation process of a cobalt-free high-nickel cathode material (Ni)1-xMnx)Zry(OH)2The precursor realizes the synergistic effect of each process by accurately regulating and controlling the process parameters of each step, the prepared precursor has complete appearance and uniform size, the tested Zr content is basically consistent with the doping amount, and the structural stability and the high-temperature stability are good;
(3) the used binder is formed by polymerizing the monomer vinylidene fluoride and the monomer ethylene, so that the flexibility of the binder is improved, the crystallinity of the binder is reduced, the gelation of the anode slurry is effectively avoided, and the performance of the anode sheet is improved.
Drawings
FIG. 1 shows (Ni) produced in example 11-xMnx)Zry(OH)2SEM image of precursor magnification factor 10000.
FIG. 2 shows (Ni) produced in example 11-xMnx)Zry(OH)2Precursor body is putSEM image at large magnification 2000 x.
FIG. 3 is (Ni) obtained in example 11-xMnx)Zry(OH)2SEM image of precursor magnification 1000 times.
Fig. 4 is a cycle test chart of a button cell composed of the positive electrode sheets in example 1 and comparative example 1.
Detailed Description
The invention is further described with reference to the following detailed description and accompanying drawings.
Example 1:
the lithium ion battery positive plate using the cobalt-free high-nickel positive electrode material comprises a positive electrode current collector copper foil and a positive electrode active material layer loaded on the copper foil, wherein the components of the positive electrode active material layer comprise the cobalt-free high-nickel positive electrode material, acetylene black and a binder in a mass ratio of 19:1: 1.
The molecular formula of the cobalt-free high-nickel cathode material is Li (Ni)0.9Mn0.1)Zr0.0023O2The preparation method of the cobalt-free high-nickel cathode material comprises the following steps:
(1) mixing the components in a volume ratio of 5: 1, mixing deionized water and concentrated ammonia water with the mass concentration of 26%, adding the mixture into a coprecipitation reaction kettle, and uniformly stirring at the speed of 600r/min at the temperature of 60 ℃ to obtain reaction base liquid;
(2) mixing NiSO4·6H2O、MnSO4·5H2O and ZrCl4Dissolving Ni atoms, Mn atoms and Zr atoms in water according to the molar ratio to form a mixed salt solution, wherein the total concentration of all substances in the mixed salt solution is 2.0 mol/L;
(3) respectively adding the mixed salt solution, 2.0mol/L NaOH solution and strong ammonia water into a coprecipitation reaction kettle under the protection of nitrogen to be mixed with reaction bottom liquid, so that the pH value of a reaction system is 11.7, and the feeding speed of the NaOH solution is 0.5 mL/min; the feeding speed of the mixed salt solution is 0.25mL/min, and the mixed salt solution is stirred and reacts for 20 hours at the temperature of 60 ℃ under the protection of nitrogen;
(4) aging the reaction product in an aging reaction kettle for 5h, vacuum filtering, and drying at 100 ℃ to obtain (Ni)0.9Mn0.1)Zr0.0023(OH)2A precursor;
(5) will (Ni)0.9Mn0.1)Zr0.0023(OH)2Precursor and LiOH. H2Mixing O according to a molar ratio, and calcining in an oxygen-rich atmosphere to obtain the cobalt-free high-nickel cathode material, wherein the calcining method comprises the following steps: the temperature is raised from the room temperature to 600 ℃ at the speed of 5 ℃/min, the mixture is calcined for 6 hours at constant temperature, and then the mixture is heated to 800 ℃ and calcined for 8 hours at constant temperature.
The preparation method of the adhesive comprises the following steps:
A) adding deionized water with the conductivity of 2 mu s/cm, ammonium persulfate and sodium perfluorooctanoate into a reaction kettle under the protection of nitrogen, wherein the mass of the ammonium persulfate and the mass of the sodium perfluorooctanoate are respectively 0.5 percent and 0.3 percent of that of the deionized water;
B) introducing monomer vinylidene fluoride and monomer ethylene into the reaction kettle until the pressure is 5.0MPa, wherein the mole fraction of the monomer vinylidene fluoride is 60 percent, and the mole fraction of the monomer ethylene is 40 percent;
C) heating to 80 ℃, reacting for 20 hours, continuously introducing the monomer vinylidene fluoride and the monomer ethylene which have the same proportion as the monomer vinylidene fluoride and the monomer ethylene in the step B) in the reaction process, and reducing the pressure to 2.0MPa after the reaction is finished;
D) the reaction product is coagulated, washed, separated, dried and crushed to obtain the adhesive.
Example 2:
the lithium ion battery positive plate using the cobalt-free high-nickel positive electrode material comprises a positive electrode current collector copper foil and a positive electrode active material layer loaded on the copper foil, wherein the positive electrode active material layer comprises the cobalt-free high-nickel positive electrode material, a single-walled carbon nanotube and a binder in a mass ratio of 18:1: 1.
The molecular formula of the cobalt-free high-nickel cathode material is Li (Ni)0.7Mn0.3)Zr0.002O2The preparation method of the cobalt-free high-nickel cathode material comprises the following steps:
(1) mixing the components in a volume ratio of 4.5: 1, mixing deionized water and 25% strong ammonia water, adding the mixture into a coprecipitation reaction kettle, and uniformly stirring at the speed of 900r/min at 40 ℃ to obtain reaction base liquid;
(2) mixing NiSO4·6H2O、MnSO4·5H2O and ZrCl4Dissolving Ni, Mn and Zr atoms in water according to the mol ratio to form mixed salt solutionThe total concentration of all substances in the solution is 1.5 mol/L;
(3) respectively adding the mixed salt solution, 1.5mol/L NaOH solution and concentrated ammonia water into a coprecipitation reaction kettle under the protection of nitrogen to be mixed with reaction bottom liquid, so that the pH value of a reaction system is 11, and the feeding speed of the NaOH solution is 0.45 mL/min; the feeding speed of the mixed salt solution is 0.2mL/min, and the mixed salt solution is stirred and reacts for 24 hours at 40 ℃ under the protection of nitrogen;
(4) aging the reaction product in an aging reaction kettle for 4 hours, vacuum filtering, and drying at 110 ℃ to obtain (Ni)0.7Mn0.3)Zr0.002(OH)2A precursor;
(5) will (Ni)0.7Mn0.3)Zr0.002(OH)2Precursor and LiOH. H2Mixing O according to a molar ratio, and calcining in an oxygen-rich atmosphere to obtain the cobalt-free high-nickel cathode material, wherein the calcining method comprises the following steps: the temperature is raised from the room temperature to 550 ℃ at the speed of 4 ℃/min, the mixture is calcined for 7 hours at constant temperature, and then the temperature is raised to 850 ℃ and the calcination is carried out for 7 hours at constant temperature.
The preparation method of the adhesive comprises the following steps:
A) adding deionized water with the conductivity of 3 mu s/cm, ammonium persulfate and sodium perfluorooctanoate into a reaction kettle under the protection of nitrogen, wherein the mass of the ammonium persulfate and the mass of the sodium perfluorooctanoate are respectively 0.001 percent and 0.001 percent of that of the deionized water;
B) introducing monomer vinylidene fluoride and monomer ethylene into the reaction kettle until the pressure is 1.0MPa, wherein the mole fraction of the monomer vinylidene fluoride is 40 percent, and the mole fraction of the monomer ethylene is 60 percent;
C) heating to 35 ℃, reacting for 30 hours, continuously introducing the monomer vinylidene fluoride and the monomer ethylene which have the same proportion as the monomer vinylidene fluoride and the monomer ethylene in the step B) in the reaction process, and reducing the pressure to 1.0MPa after the reaction is finished;
D) the reaction product is coagulated, washed, separated, dried and crushed to obtain the adhesive.
Example 3:
the lithium ion battery positive plate using the cobalt-free high-nickel positive electrode material comprises a positive electrode current collector copper foil and a positive electrode active material layer loaded on the copper foil, wherein the positive electrode active material layer comprises the cobalt-free high-nickel positive electrode material, a single-walled carbon nanotube and a binder in a mass ratio of 20:1: 1.
The molecular formula of the cobalt-free high-nickel cathode material is Li (Ni)0.5Mn0.5)Zr0.003O2The preparation method of the cobalt-free high-nickel cathode material comprises the following steps:
(1) mixing the components in a volume ratio of 5.5: 1, mixing deionized water and 28 mass percent concentrated ammonia water, adding the mixture into a coprecipitation reaction kettle, and uniformly stirring the mixture at the speed of 500r/min at the temperature of 80 ℃ to obtain reaction base liquid;
(2) mixing NiSO4·6H2O、MnSO4·5H2O and ZrCl4Dissolving Ni atoms, Mn atoms and Zr atoms in water according to the molar ratio to form a mixed salt solution, wherein the total concentration of all substances in the mixed salt solution is 2.5 mol/L;
(3) respectively adding the mixed salt solution, 2.5mol/L NaOH solution and strong ammonia water into a coprecipitation reaction kettle under the protection of nitrogen to be mixed with reaction bottom liquid, so that the pH value of a reaction system is 12, and the feeding speed of the NaOH solution is 0.55 mL/min; the feeding speed of the mixed salt solution is 0.3mL/min, and the mixed salt solution is stirred and reacts for 18 hours at 80 ℃ under the protection of nitrogen;
(4) aging the reaction product in an aging reaction kettle for 6h, vacuum filtering, and drying at 90 deg.C to obtain (Ni)0.5Mn0.5)Zr0.003(OH)2A precursor;
(5) will (Ni)0.5Mn0.5)Zr0.003(OH)2Precursor and LiOH. H2Mixing O according to a molar ratio, and calcining in an oxygen-rich atmosphere to obtain the cobalt-free high-nickel cathode material, wherein the calcining method comprises the following steps: the temperature is raised from the room temperature to 650 ℃ at the speed of 6 ℃/min, the mixture is calcined for 5 hours at constant temperature, and then the mixture is heated to 750 ℃ and calcined for 9 hours at constant temperature.
The preparation method of the adhesive comprises the following steps:
A) adding deionized water with the conductivity of 2 mu s/cm, ammonium persulfate and sodium perfluorooctanoate into a reaction kettle under the protection of nitrogen, wherein the mass of the ammonium persulfate and the mass of the sodium perfluorooctanoate are respectively 1 percent and 0.3 percent of that of the deionized water;
B) introducing monomer vinylidene fluoride and monomer ethylene into the reaction kettle until the pressure is 7.0MPa, wherein the mole fraction of the monomer vinylidene fluoride is 70 percent, and the mole fraction of the monomer ethylene is 30 percent;
C) heating to 110 ℃, reacting for 10 hours, continuously introducing the monomer vinylidene fluoride and the monomer ethylene which have the same proportion as the monomer vinylidene fluoride and the monomer ethylene in the step B) in the reaction process, and reducing the pressure to 3.0MPa after the reaction is finished;
D) the reaction product is coagulated, washed, separated, dried and crushed to obtain the adhesive.
Comparative example 1:
the molecular formula of the cobalt-free high-nickel cathode material in comparative example 1 is Li (Ni)0.9Mn0.1)O2The preparation method of the cobalt-free high-nickel cathode material comprises the following steps:
(1) mixing the components in a volume ratio of 5: 1, mixing deionized water and concentrated ammonia water with the mass concentration of 26%, adding the mixture into a coprecipitation reaction kettle, and uniformly stirring at the speed of 600r/min at the temperature of 60 ℃ to obtain reaction base liquid;
(2) mixing NiSO4·6H2O、MnSO4·5H2Dissolving O in water according to the molar ratio of Ni atoms to Mn atoms to form a mixed salt solution, wherein the total concentration of all substances in the mixed salt solution is 2.0 mol/L;
(3) respectively adding the mixed salt solution, 2.0mol/L NaOH solution and strong ammonia water into a coprecipitation reaction kettle under the protection of nitrogen to be mixed with reaction bottom liquid, so that the pH value of a reaction system is 11.7, and the feeding speed of the NaOH solution is 0.5 mL/min; the feeding speed of the mixed salt solution is 0.25mL/min, and the mixed salt solution is stirred and reacts for 20 hours at the temperature of 60 ℃ under the protection of nitrogen;
(4) aging the reaction product in an aging reaction kettle for 5h, vacuum filtering, and drying at 100 ℃ to obtain (Ni)0.9Mn0.1)(OH)2A precursor;
(5) will (Ni)0.9Mn0.1)(OH)2Precursor and LiOH. H2Mixing O according to a molar ratio, and calcining in an oxygen-rich atmosphere to obtain the cobalt-free high-nickel cathode material, wherein the calcining method comprises the following steps: the temperature is raised from the room temperature to 600 ℃ at the speed of 5 ℃/min, the mixture is calcined for 6 hours at constant temperature, and then the mixture is heated to 800 ℃ and calcined for 8 hours at constant temperature.
The rest is the same as in example 1.
Comparative example 2:
the molecular formula of the cobalt-free high-nickel cathode material in comparative example 2 is Li (Ni)0.9Mn0.1)Zr0.0023O2Is free of cobaltThe preparation method of the high-nickel anode material comprises the following steps:
(1) mixing the components in a volume ratio of 5: 1, mixing deionized water and concentrated ammonia water with the mass concentration of 26%, adding the mixture into a coprecipitation reaction kettle, and uniformly stirring at the speed of 600r/min at the temperature of 60 ℃ to obtain reaction base liquid;
(2) mixing NiSO4·6H2O、MnSO4·5H2Dissolving O in water according to the molar ratio of Ni atoms to Mn atoms to form a mixed salt solution, wherein the total concentration of all substances in the mixed salt solution is 2.0 mol/L;
(3) respectively adding the mixed salt solution, 2.0mol/L NaOH solution and strong ammonia water into a coprecipitation reaction kettle under the protection of nitrogen to be mixed with reaction bottom liquid, so that the pH value of a reaction system is 11.7, and the feeding speed of the NaOH solution is 0.5 mL/min; the feeding speed of the mixed salt solution is 0.25mL/min, and the mixed salt solution is stirred and reacts for 20 hours at the temperature of 60 ℃ under the protection of nitrogen;
(4) aging the reaction product in an aging reaction kettle for 5h, vacuum filtering, and drying at 100 ℃ to obtain (Ni)0.9Mn0.1)(OH)2A precursor;
(5) will (Ni)0.9Mn0.1)(OH)2Precursor and LiOH. H2O and ZrO2Mixing the components according to the molar ratio of Ni, Li and Zr, and calcining the mixture in an oxygen-rich atmosphere to obtain the cobalt-free high-nickel anode material, wherein the calcining method comprises the following steps: the temperature is raised from the room temperature to 600 ℃ at the speed of 5 ℃/min, the mixture is calcined for 6 hours at constant temperature, and then the mixture is heated to 800 ℃ and calcined for 8 hours at constant temperature.
The rest is the same as in example 1.
Comparative example 3:
the binder in comparative example 3 was PVDF, and the rest was the same as in example 1.
For (Ni) prepared in the above examples and comparative examples1-xMnx)Zry(OH)2SEM test is carried out on the precursor, and ICP test is carried out on the anode material, and the results are shown in figures 1-3 and table 1.
Table 1: and testing the result of positive electrode material ICP.
Figure BDA0002649129770000081
As can be seen from FIGS. 1 to 3 and Table 1, (Ni) prepared in examples 1 to 3 by the method of the present invention1- xMnx)Zr(OH)2The precursor has complete appearance and uniform size, and the test result of each atomic mole fraction in the prepared anode material is basically consistent with the doping amount. While comparative example 2 was prepared by coprecipitation method (Ni)1-xMnx)(OH)2Adding ZrO into the precursor during sintering2Doping is carried out, and the difference between the actual mole fraction of Zr in the prepared anode material and the doping amount is large. The anode material prepared by the method of the invention is proved to be capable of uniformly mixing Zr element with the precursor on the molecular level, so that the anode material obtained by sintering can present better performance.
The positive electrode sheets prepared in the above examples and comparative examples were assembled into button cells, and the electrical properties and cycle properties thereof were measured, with the results shown in fig. 4 and table 2.
Wherein, the negative electrode in the button cell is a lithium sheet; the electrolyte is as follows: 1mol/L LiPF6Dissolved in Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC) (EC: EMC: DMC ═ 1: 1:1 wt%); voltage: 2.7-4.25V; the capacity and cycle test current density was 0.5C.
Table 2: and (5) testing the performance of the battery.
Item Example 1 Example 2 Examples3 Comparative example 1 Comparative example 2 Comparative example 3
First discharge capacity (mAh g)-1) 209.7 208.9 208.1 210.9 209.6 207.8
Capacity Retention (%) for 150 cycles 90.3 91.0 91.5 84.9 88.8 89.2
As can be seen from fig. 4 and table 2, after the button cell is formed by using the positive electrode sheet of the present invention in examples 1 to 3, the capacity of the cell is large and the cycle performance is good; in the comparative example 1, the cycle performance of the battery is obviously reduced by adopting the Zr-free anode material; in comparative example 2, the cycle performance of the battery was also reduced without using the method of the present invention to prepare the Zr-doped positive electrode material; in comparative example 3, the capacity and cycle performance of the battery were reduced without using the binder of the present invention. The performance of the lithium ion battery can be effectively improved by using the cathode material and the binder.

Claims (10)

1. A lithium ion battery positive plate using a cobalt-free high-nickel positive electrode material is characterized by comprising a positive electrode current collector and a positive electrode current collector loaded on the positive electrode current collectorThe positive electrode active material layer comprises a cobalt-free high nickel positive electrode material having a molecular formula of Li (Ni), a conductive agent, and a binder1-xMnx)ZryO2Wherein x is more than or equal to 0.1 and less than or equal to 0.5, and y is more than or equal to 0.002 and less than or equal to 0.003.
2. The positive plate of the lithium ion battery using the cobalt-free high-nickel positive electrode material as claimed in claim 1, wherein the preparation method of the cobalt-free high-nickel positive electrode material comprises:
(1) the volume ratio is (4.5-5.5): 1, mixing deionized water and 25-28% concentrated ammonia water, adding the mixture into a coprecipitation reaction kettle, and uniformly stirring at 40-80 ℃ to obtain a reaction base solution;
(2) mixing NiSO4·6H2O、MnSO4·5H2O and ZrCl4Dissolving Ni, Mn and Zr atoms in water according to the molar ratio to form a mixed salt solution;
(3) respectively adding the mixed salt solution, the NaOH solution and the concentrated ammonia water into a coprecipitation reaction kettle under the protection of nitrogen to be mixed with the reaction base solution, so that the pH of a reaction system is 11-12, and stirring and reacting for 18-24 hours at 40-80 ℃ under the protection of nitrogen;
(4) aging the reaction product in an aging reaction kettle for 4-6 h, vacuum filtering and drying to obtain (Ni)1-xMnx)Zry(OH)2A precursor;
(5) will (Ni)1-xMnx)Zry(OH)2Precursor and LiOH. H2And mixing the O according to the molar ratio, and calcining in an oxygen-rich atmosphere to obtain the cobalt-free high-nickel cathode material.
3. The positive plate of the lithium ion battery using the cobalt-free high-nickel positive electrode material as claimed in claim 2, wherein the stirring speed in the step (1) is 500 to 900 r/min.
4. The positive plate of the lithium ion battery using the cobalt-free high-nickel positive electrode material as claimed in claim 2, wherein the total concentration of each substance in the mixed salt solution in the step (2) is 1.5-2.5 mol/L.
5. The positive plate of the lithium ion battery using the cobalt-free high-nickel positive electrode material as claimed in claim 2, wherein the concentration of the NaOH solution in the step (3) is 1.5-2.5 mol/L, and the feeding speed is 0.45-0.55 mL/min; the feeding speed of the mixed salt solution is 0.2-0.3 mL/min.
6. The positive plate of the lithium ion battery using the cobalt-free high-nickel positive electrode material as claimed in claim 2, wherein the drying temperature in the step (4) is 90-110 ℃.
7. The positive plate of the lithium ion battery using the cobalt-free high-nickel positive electrode material as claimed in claim 2, wherein the calcination method in the step (5) is as follows: heating from room temperature to 550-650 ℃ at a speed of 4-6 ℃/min, calcining for 5-7 h at constant temperature, and heating to 750-850 ℃ for 7-9 h at constant temperature.
8. The positive plate of the lithium ion battery using the cobalt-free high-nickel positive electrode material as claimed in claim 1, wherein the conductive agent is selected from one or a combination of acetylene black and single-walled carbon nanotubes.
9. The positive plate of the lithium ion battery using the cobalt-free high-nickel positive electrode material as claimed in claim 1, wherein the binder is prepared by the following steps:
A) adding deionized water with the conductivity of less than 8 mu s/cm, ammonium persulfate and sodium perfluorooctanoate into a reaction kettle under the protection of inert gas, wherein the mass of the ammonium persulfate and the mass of the sodium perfluorooctanoate are respectively 0.001-1% and 0.001-0.3% of that of the deionized water;
B) introducing monomer vinylidene fluoride and monomer ethylene into the reaction kettle until the pressure is 1.0-7.0 MPa, wherein the mole fraction of the monomer vinylidene fluoride is 40-70%, and the mole fraction of the monomer ethylene is 60-30%;
C) heating to 35-110 ℃, reacting for 10-30 h, continuously introducing the monomer vinylidene fluoride and the monomer ethylene which have the same proportion as the monomer vinylidene fluoride and the monomer ethylene in the step B) in the reaction process, and reducing the pressure to 1.0-3.0 MPa after the reaction is finished;
D) the reaction product is coagulated, washed, separated, dried and crushed to obtain the adhesive.
10. The positive plate of the lithium ion battery using the cobalt-free high-nickel positive electrode material as claimed in claim 1, 2, 8 or 9, wherein the cobalt-free high-nickel positive electrode material, the conductive agent and the binder are in a mass ratio of (18-20): 1: 1.
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