CN114784286B - Battery anode material, preparation method thereof and lithium ion battery - Google Patents

Battery anode material, preparation method thereof and lithium ion battery Download PDF

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CN114784286B
CN114784286B CN202210683806.XA CN202210683806A CN114784286B CN 114784286 B CN114784286 B CN 114784286B CN 202210683806 A CN202210683806 A CN 202210683806A CN 114784286 B CN114784286 B CN 114784286B
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battery
mass
coating agent
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CN114784286A (en
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张瑞欣
臧成杰
张永虎
张硕
郑春龙
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Tianpeng Lithium Energy Technology Huai'an Co ltd
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Tianpeng Lithium Energy Technology Huai'an 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
    • H01M4/36—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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to the technical field of lithium ion batteries, in particular to a battery anode material, a preparation method thereof and a lithium ion battery. The battery anode material comprises a matrix and a coating layer coated on the surface of the matrix; the chemical formula of the matrix is Li a Ni x M y N z O 2 Wherein a is more than or equal to 1 and less than or equal to 1.2, x is more than or equal to 0.8 and less than 1, y is more than 0 and less than 0.2, z is more than 0 and less than 0.1, and x + y + z = 1; m comprises Co and/or Mn, N comprises at least one of Al, Zr, Sr, W, Mg, Na and Ti; the coating layer is lithium nickel iron aluminate. According to the invention, the lithium nickel aluminate is coated on the surface of the matrix, so that the ionic/electronic conductivity of the interface of the anode material is improved, and the surface of the anode material is protected, so that the thermal stability of the anode material is effectively improved, and the residual alkali quantity on the surface of the anode material is effectively reduced.

Description

Battery anode material, preparation method thereof and lithium ion battery
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a battery anode material, a preparation method thereof and a lithium ion battery.
Background
With the rapid development of lithium ion battery technology, the application field of the lithium ion battery is also expanding, and the lithium ion battery becomes one of the most active factors in people's life from portable electronic equipment, small household energy storage equipment to larger-scale electric vehicles. In order to further accelerate the penetration of lithium ion batteries in modern life, it is of great importance to provide a lithium ion battery that is cheaper, safer, more durable and has a higher capacity.
The use of positive electrode materials as an important component of lithium ion batteries is the focus of current research. While the nickel-rich material in the positive electrode material stands out by its outstanding high energy density. However, as the nickel content increases, disadvantages arise for their use, wherein the cycle performance and the thermal safety can be improved. In contrast, in the prior art, the nickel-rich material is often coated and modified to solve the above technical problems.
However, since the conventional coating temperature is lower than the sintering temperature of the nickel-rich material, or in order to perform multi-layer coating, the coating process in the prior art often requires secondary sintering or tertiary sintering, which not only complicates the production process but also increases the processing cost.
In addition, the nickel-rich material in the prior art has high residual alkali in the primary sintering process, and the direct use of the nickel-rich material can increase the processing difficulty of the lithium battery positive plate, so that the excessive residual alkali is usually removed by water washing, and the complexity of the process is increased.
In addition, most of the conventional coating materials are inert materials, which is not favorable for the capacity exertion of the nickel-rich material.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a battery anode material, by coating lithium nickel aluminate on the surface of a matrix, the ionic/electronic conductivity of the interface of the anode material is improved, and simultaneously, the surface of the anode material is protected, so that the thermal stability of the anode material is effectively improved, and the residual alkali amount on the surface of the anode material is effectively reduced.
The second purpose of the invention is to provide the preparation method of the battery anode material, which is characterized in that the doping and coating of the nickel-rich matrix material are simultaneously completed by one-time sintering, and the preparation method has the advantages of simple operation, short process flow, low preparation cost, low residual alkali content of the prepared battery anode material and the like.
A third object of the present invention is to provide a lithium ion battery.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a battery anode material which comprises a matrix and a coating layer coated on the surface of the matrix.
The chemical formula of the matrix is Li a Ni x M y N z O 2 Which isIn the formula, a is more than or equal to 1 and less than or equal to 1.2, x is more than or equal to 0.8 and less than 1, y is more than 0 and less than 0.2, z is more than 0 and less than 0.1, and x + y + z = 1; m comprises Co and/or Mn, and N comprises at least one of Al, Zr, Sr, W, Mg, Na and Ti.
The coating layer is lithium nickel iron aluminate.
According to the invention, the lithium nickel aluminate is coated on the surface of the matrix, so that the ionic/electronic conductivity of the interface of the anode material is improved, and the surface of the anode material is protected, so that the thermal stability of the anode material is effectively improved. In addition, the coating layer can effectively reduce the residual alkali amount on the surface of the cathode material.
Wherein, N is used as doping element, and can be one of Al, Zr, Sr, W, Mg, Na and Ti, or any mixture of multiple elements.
The N as the doping element not only has the function of stabilizing the structure of the battery anode material, but also has the function of inhibiting the cladding layer from diffusing to the bulk phase.
The lithium nickel aluminate of the coating layer has excellent electrochemical activity and thermal stability, thereby being beneficial to improving the capacity, the cycle performance and the safety performance of the battery anode material.
In some specific embodiments of the invention, the matrix has the formula Li a Ni x M y N z O 2 A in (b) can also be selected from 1.01, 1.02, 1.03, 1.04, 1.05, 1.06, 1.07, 1.08, 1.09, 1.10, 1.11, 1.12, 1.13, 1.14, 1.15, 1.16, 1.17, 1.18 or 1.19.
In some specific embodiments of the invention, the matrix is of the formula Li a Ni x M y N z O 2 X in (b) may also be selected from 0.82, 0.84, 0.86, 0.88, 0.90, 0.92, 0.94, 0.96 or 0.98.
In some specific embodiments of the invention, the matrix is of the formula Li a Ni x M y N z O 2 Y in (b) may also be selected from 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18 or 0.19.
In some specific embodiments of the invention, theChemical formula of matrix Li a Ni x M y N z O 2 Z in (b) can also be selected from 0.005, 0.01, 0.015, 0.02, 0.025, 0.03, 0.035, 0.04, 0.045, 0.05, 0.055, 0.06, 0.065, 0.07, 0.075, 0.08, 0.085 or 0.09.
Preferably, the coating layer has a thickness of 5nm to 30nm, including but not limited to any one of 6nm, 8nm, 10nm, 12nm, 14nm, 16nm, 18nm, 20nm, 22nm, 24nm, 26nm, and 28nm or a range therebetween; more preferably, the thickness of the coating layer is 10nm to 25 nm.
Preferably, the mass of the coating layer is 0.1% to 0.8% of the mass of the base body, including but not limited to any one of the dot values of 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7% or a range value between any two; more preferably 0.3% to 0.6%.
Preferably, the matrix is a layered structure matrix. That is, the crystal structure of the matrix is a layered structure.
The energy density of the battery anode material can be improved by adopting the matrix with the crystal structure as the layered structure.
Preferably, the coating layer is a layer structure. That is, the crystal structure of the clad layer is a layered structure.
The energy density of the battery anode material can be improved by adopting the coating layer with the layered structure.
Preferably, the D50 particle size of the battery positive electrode material is 3-20 μm, including but not limited to any one of 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 16 μm, 18 μm or a range value between any two; more preferably 5 to 18 μm.
In some specific embodiments of the present invention, the particles of the battery positive electrode material are spherical or spheroidal in shape.
The invention also provides a preparation method of the battery anode material, which comprises the following steps:
and adding a first coating agent and a second coating agent into a mixture containing the precursor material, the lithium source and the doping agent (namely, uniformly mixing the precursor material, the lithium source and the doping agent, then adding the first coating agent and the second coating agent into the mixture), mixing and sintering to obtain the battery cathode material.
Wherein the chemical formula of the precursor material is Ni p M q (OH) 2 (ii) a Wherein p is more than 0.8 and less than 1, q is more than 0 and less than 0.2, and p + q = 1; m comprises Co and/or Mn (M can be selected from one of Co and Mn, or can be selected from Co and Mn at the same time).
The dopant includes at least one of an Al source, a Zr source, a Sr source, a W source, a Mg source, a Na source, and a Ti source.
The first coating agent comprises NiFe 2 O 4 。
The second coating agent includes an aluminum-containing compound.
The invention can uniformly and tightly load the dopant on the surface of the precursor material by mixing the dopant, the precursor material and the lithium source in advance. And then adding a first coating agent and a second coating agent into the mixture, and mixing to load the first coating agent and the second coating agent on the surface of the dopant.
In the subsequent sintering process, the dopant not only plays a role in stabilizing the structure of the battery anode material, but also plays a role in inhibiting the diffusion of the cladding layer to the bulk phase, so that the lithium nickel iron aluminate forms a cladding effect on the surface of the battery anode material.
Meanwhile, the first coating agent can also absorb CO generated in the sintering process in addition to serving as a coating source 2 Convert it to O 2 Thereby effectively reducing the residual alkali content of the battery anode material.
Namely, the invention simultaneously completes the doping and coating of the battery anode material through one-time sintering process, and the battery anode material has the advantages of low residual alkali, high capacity, good cycle performance and safety performance.
In addition, the preparation method has the advantages of simple operation, short process flow, low preparation cost and the like.
In some specific embodiments of the invention, the precursor material has the chemical formula Ni p M q (OH) 2 P in (1) may also beTo select 0.82, 0.83, 0.84, 0.86, 0.88, 0.90, 0.92, 0.94, 0.96 or 0.98.
In some specific embodiments of the invention, the precursor material has the chemical formula Ni p M q (OH) 2 Q in (b) may also be selected from 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.175, 0.18, 0.185 or 0.19.
In some specific embodiments of the invention, the Al source comprises an Al-containing compound.
In some specific embodiments of the invention, the Zr source comprises a Zr-containing compound.
In some specific embodiments of the invention, the Sr source comprises a Sr-containing compound.
In some specific embodiments of the invention, the source of W comprises a compound comprising W.
In some specific embodiments of the invention, the Mg source comprises a Mg-containing compound.
In some specific embodiments of the invention, the Na source comprises a Na-containing compound.
In some specific embodiments of the invention, the Ti source comprises a Ti-containing compound.
Preferably, the Al source comprises Al 2 O 3 、Al(OH) 3 And AlOOH.
Preferably, the Zr source comprises ZrO 2 And Li 2 ZrO 3 At least one of (1).
Preferably, the Sr source comprises SrO, Sr (OH) 2 And SrO 2 At least one of (1).
Preferably, the W source comprises WO 3 、Li 2 WO 4 And a W-containing heteropoly acid.
Wherein, the heteropoly acid is oxygen-containing polyacid which is bridged by hetero atoms and polyatomic atoms through oxygen atom coordination according to a certain structure. The solid heteropoly acid compound consists of heteropolyanions, cations and water or organic molecules.
In the present invention, the W-containing heteropoly acid means a heteropoly acid containing W element, and any of the conventional, commercially available W-containing heteropoly acids can be used.
Preferably, the Mg source comprises MgO, Mg (OH) 2 And MgCO 3 At least one of (a).
Preferably, the Na source comprises Na 2 CO 3 And NaHCO 3 At least one of (1).
Preferably, the Ti source comprises TiO 2 、Ti(SO 4 ) 2 And Ti (OH) 4 At least one of (1).
With the above-mentioned dopant, not only the structure of the battery positive electrode material can be stabilized, but also the diffusion of the clad layer into the bulk phase can be suppressed.
Preferably, the lithium source comprises Li 2 CO 3 、LiOH、LiHCO 3 、CH 3 COOLi and LiNO 3 At least one of (a).
In some specific embodiments of the invention, the LiOH is selected from lithium hydroxide monohydrate, i.e., LiOH H 2 O。
Preferably, the aluminum-containing compound comprises Al 2 O 3 、Al(OH) 3 AlOOH and LiAlO 2 At least one of (1).
Preferably, the molar ratio of the precursor material to the lithium source is 1:1 to 1.5, including but not limited to any one of 1:1.1, 1:1.2, 1:1.3, 1:1.4, or a range of values therebetween; more preferably 1: 1.05 to 1.2.
Preferably, the mass of the dopant is 0.5% to 5% of the sum of the mass of the precursor material and the lithium source, including but not limited to the point value of any one of 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.65%, 1.8%, 2%, 2.3%, 2.5%, 2.8%, 3%, 3.3%, 3.5%, 3.8%, 4%, 4.2%, 4.5%, 4.8%, or a range value between any two; more preferably 0.6% to 2%.
The dosage of the dopant can have certain influence on the performance of the battery anode material. The use of the dosage range is beneficial to improving the performance of the battery anode material.
Preferably, the mass of the first coating agent is 0.05% to 0.4% of the sum of the mass of the precursor material and the mass of the lithium source, including but not limited to the point value of any one of 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.12%, 0.15%, 0.18%, 0.2%, 0.22%, 0.25%, 0.28%, 0.3%, 0.33%, 0.35%, 0.38%, or the range value between any two; more preferably 0.1% to 0.3%.
Preferably, the mass of the second coating agent is 0.05% to 0.4% of the sum of the mass of the precursor material and the lithium source, including but not limited to the point value of any one of 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.12%, 0.15%, 0.18%, 0.2%, 0.22%, 0.25%, 0.28%, 0.3%, 0.33%, 0.35%, 0.37%, 0.38%, or a range value between any two; more preferably 0.1% to 0.3%.
Preferably, the sintering temperature is 700 ℃ to 900 ℃, including but not limited to any one of 710 ℃, 720 ℃, 730 ℃, 740 ℃, 750 ℃, 760 ℃, 770 ℃, 780 ℃, 790 ℃, 800 ℃, 830 ℃, 850 ℃, 870 ℃, 890 ℃ or any range value therebetween; more preferably 720 ℃ to 850 ℃.
Preferably, the heating rate of heating to the sintering temperature is 3 ℃/min-10 ℃/min, including but not limited to any one of the point values of 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min or the range value between any two of the point values; more preferably 5 to 8 ℃/min.
Preferably, the sintering holding time is 15 h-30 h, including but not limited to any one of 17h, 19h, 20h, 22h, 24h, 25h, 27h and 29h or any value in a range between the two; more preferably 20 to 28 hours.
Preferably, the method for preparing the mixed material containing the precursor material, the lithium source and the dopant comprises the following steps: mixing the precursor material, the lithium source and the dopant once at a rotation speed of 2000-3000 rpm, wherein the rotation speed in the once mixing process comprises but is not limited to the point value of any one of 2100rpm, 2200rpm, 2300rpm, 2400rpm, 2500rpm, 2600rpm, 2700rpm, 2800rpm and 2900rpm or the range value between any two of the values; more preferably, the rotation speed is 2500rpm to 2800 rpm.
The invention can uniformly and tightly load the dopant on the surface of the precursor material by mixing the dopant, the precursor material and the lithium source at a high speed in advance.
Preferably, the time of the primary mixing is 10min to 30min, including but not limited to the point value of any one of 11min, 12min, 13min, 14min, 15min, 16min, 18min, 20min, 23min, 25min, 27min, 29min or the range value between any two of the above values; more preferably 15min to 25 min.
Preferably, after the first coating agent and the second coating agent are added, performing secondary mixing at a rotation speed of 1000 rpm-2000 rpm, wherein the rotation speed during the secondary mixing process comprises but is not limited to the point value of any one of 1100rpm, 1200rpm, 1300rpm, 1400rpm, 1500rpm, 1600rpm, 1700rpm, 1800rpm and 1900rpm or the range value between any two of the points; more preferably, the rotation speed is 1500rpm to 1800 rpm.
The invention can load the coating agent on the surface of the doping agent by a second high-speed mixing mode.
Preferably, the time of the secondary mixing is 5 min-10 min, including but not limited to the point value of any one of 6min, 7min, 8min and 9min or the range value between any two; more preferably 6min to 8 min.
In some embodiments, the primary mixing and/or the secondary mixing is performed using a high speed mixing device.
Preferably, the primary mixing and the secondary mixing are both performed using high speed mixing equipment.
In some embodiments, the primary mixing and/or the secondary mixing is performed in a drying and CO removal process 2 Is carried out in an air atmosphere of (2).
Preferably, the primary mixing and the secondary mixing are both drying and CO removal 2 Is carried out in an air atmosphere of (2).
In some specific embodiments of the present invention, the particle diameter of D50 of the spherical (spheroidal) particles obtained after the first mixing is 3 μm to 20 μm, including but not limited to any one of 4 μm, 5 μm, 7 μm, 9 μm, 10 μm, 12 μm, 14 μm, 16 μm, and 18 μm or a range therebetween; more preferably 5 to 18 μm.
In some specific embodiments of the present invention, the particle diameter of D50 of the spherical (spheroidal) particles obtained after the second mixing is 3 μm to 20 μm, including but not limited to any one of 4 μm, 5 μm, 7 μm, 9 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm or a range therebetween; more preferably 5 to 18 μm.
Preferably, the sintering is performed in an oxygen-containing atmosphere. The oxygen-containing atmosphere refers to an atmosphere containing oxygen.
Preferably, the volume fraction of oxygen in the oxygen-containing atmosphere is greater than or equal to 80%, including but not limited to the point of any one of 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 92%, 94%, 95%, 97%, 98%, 99%, or a range between any two; more preferably 85% or more.
In some specific embodiments of the present invention, the oxygen-containing atmosphere is a mixed gas containing air and oxygen, wherein the volume fraction of oxygen is greater than or equal to 80%, preferably greater than or equal to 85%, more preferably greater than or equal to 90%, and even more preferably greater than or equal to 95%.
Preferably, the D50 particle size of the precursor material is 3-20 μm, including but not limited to any one of 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 18 μm or a range therebetween; more preferably 5 to 18 μm.
Preferably, the dopant has a particle size of < 200nm, including but not limited to values of any one of 190nm, 180nm, 170nm, 160nm, 150nm, 140nm, 130nm, 120nm, 110nm, 100nm, 90nm, 80nm, 70nm, 60nm, 50nm, 40nm, 30nm, 20nm, 10nm, or ranges between any two; more preferably 150nm or less.
Preferably, the D50 particle size of the first coating agent is < 100nm, including but not limited to values of any one of 90nm, 80nm, 70nm, 60nm, 50nm, 40nm, 30nm, 20nm, 10nm, or ranges between any two.
Preferably, the first coating agent has a D50 particle size of 50nm or less, including but not limited to values of any one of 45nm, 40nm, 35nm, 30nm, 25nm, 20nm, 15nm, 10nm, 5nm, 3nm, 1nm, or ranges between any two.
Preferably, the particle size of the second coating agent is < 200nm, including but not limited to any one of 190nm, 180nm, 170nm, 160nm, 150nm, 140nm, 130nm, 120nm, 110nm, 100nm, 90nm, 80nm, 70nm, 60nm, 50nm, 40nm, 30nm, 20nm, 10nm, or a range value between any two; more preferably 150nm or less.
Preferably, the first coating agent has a purity of no less than 99%, including but not limited to the dot values of any one of 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9%, or a range of values between any two; more preferably not less than 99.5%.
The invention also provides a lithium ion battery which comprises the battery anode material or the battery anode material prepared by the preparation method of the battery anode material.
The lithium ion battery has the advantages of good cycle performance, high thermal safety performance, high capacity, low processing difficulty, low cost and the like.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the battery anode material provided by the invention, the surface of the substrate is coated with the specific type of coating lithium nickel aluminate, so that the ion/electron conductivity of the interface of the anode material is improved, and the surface of the anode material is protected, so that the thermal stability of the anode material is effectively improved; in addition, the coating layer can effectively reduce the residual alkali amount on the surface of the cathode material.
(2) According to the preparation method of the battery anode material, the doping and coating of the battery anode material are simultaneously completed through one-time sintering process, and the battery anode material has the advantage of low residual alkali.
(3) The lithium ion battery provided by the invention has the advantages of good cycle performance, high thermal safety performance, high capacity, low processing difficulty, low cost and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is an SEM image of a positive electrode material for a battery provided in example 1 of the present invention;
fig. 2 is an XPS chart of a positive electrode material for a battery provided in example 1 of the present invention;
fig. 3 is another XPS chart of the positive electrode material for a battery provided in example 1 of the present invention;
fig. 4 is yet another XPS chart of the positive electrode material for a battery provided in example 1 of the present invention;
fig. 5 is a XPS chart of a positive electrode material for a battery according to example 1 of the present invention;
FIG. 6 is a DSC chart provided by the present invention;
FIG. 7 is a graph of the retention rate of the cycling capacity provided by the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The preparation method of the battery cathode material provided by the embodiment comprises the following steps:
(1) 100mol of precursor material Ni 0.90 Co 0.10 (OH) 2 (D50 particle size 8-12 μm), 105mol of LiOH. H as lithium source 2 O and dopant Al 2 O 3 And ZrO 2 Placing in a high-speed mixing device, mixing at 3000rpm for 20min to obtain a mixed material;
wherein, the dopant Al 2 O 3 (particle size < 180 nm) 1% by mass of the sum of the mass of the precursor material and the mass of the lithium source, and ZrO 2 The mass of the particles (particle size < 180 nm) is 0.5% of the sum of the mass of the precursor material and the lithium source.
(2) Adding a first coating agent NiFe into the mixture obtained in the step (1) 2 O 4 (D50 grain size < 80 nm) and a second coating agent Al 2 O 3 (the grain diameter is less than 180 nm), and the secondary mixing is carried out at the rotating speed of 1500rpm, and the mixing time is 8 min; after being uniformly mixed, the mixture is placed in a mixed gas containing air and oxygen (the volume fraction of the oxygen in the mixed gas is 95 percent) for sintering to obtain a battery anode material;
wherein, the first cladding agent NiFe 2 O 4 The mass of (a) is 0.2% of the sum of the masses of the precursor material and the lithium source; second cladding agent Al 2 O 3 The mass of (a) is 0.1% of the sum of the masses of the precursor material and the lithium source; the sintering temperature is 720 ℃, the heating rate of heating to the sintering temperature is 5 ℃/min, and the sintering heat preservation time is 22 h.
The battery anode material comprises a matrix and a coating layer coated on the surface of the matrix, wherein the chemical formula of the matrix is Li 1.05 Ni 0.872 Co 0.097 Al 0.026 Zr 0.005 O 2 The coating layer is lithium nickel iron aluminate.
The thickness of the coating layer is 10nm through detection; the D50 particle size of the battery anode material is 8-12 μm.
Example 2
The preparation method of the battery cathode material provided by the embodiment comprises the following steps:
(1) 100mol of precursor material Ni 0.85 Mn 0.15 (OH) 2 (D50 particle size 13-18 μm), 106mol of LiOH. H as lithium source 2 Placing O and dopants AlOOH and SrO in high-speed mixing equipment, mixing at 2500rpm for 25min to obtain a mixed material;
wherein, the mass of the dopant AlOOH (the grain diameter is less than 150 nm) is 1.5 percent of the mass sum of the precursor material and the lithium source, and the mass of the dopant SrO (the grain diameter is less than 150 nm) is 0.2 percent of the mass sum of the precursor material and the lithium source.
(2) Adding a first coating agent NiFe into the mixture obtained in the step (1) 2 O 4 (D50 particle size < 50 nm) and a second coating agent Al 2 O 3 (the grain diameter is less than 150 nm), and the secondary mixing is carried out at the rotating speed of 1500rpm, and the mixing time is 10 min; after being uniformly mixed, the mixture is placed in a mixed gas containing air and oxygen (the volume fraction of the oxygen in the mixed gas is 95 percent) for sintering to obtain a battery anode material;
wherein, the first cladding agent NiFe 2 O 4 The mass of (a) is 0.3% of the sum of the masses of the precursor material and the lithium source; second cladding agent Al 2 O 3 The mass of (b) is 0.15% of the sum of the masses of the precursor material and the lithium source; the sintering temperature is 740 ℃, the heating rate of heating to the sintering temperature is 8 ℃/min, and the sintering heat preservation time is 20 h.
The battery anode material comprises a matrix and a coating layer coated on the surface of the matrix, wherein the chemical formula of the matrix is Li 1.06 Ni 0.820 Mn 0.145 Al 0.033 Sr 0.003 O 2 The coating layer is lithium nickel iron aluminate.
The thickness of the coating layer is 20nm through detection; the D50 particle size of the battery anode material is 13-18 μm.
Example 3
The preparation method of the battery cathode material provided by the embodiment is basically the same as that of the embodiment 1, except that the doping agent A in the step (1) is addedl 2 O 3 Is replaced by 2% of the sum of the mass of the precursor material and the mass of the lithium source, and the dopant ZrO in step (1) is added 2 Is replaced by 2% of the sum of the masses of the precursor material and the lithium source.
The chemical formula of a matrix in the battery anode material is Li 1.05 Ni 0.837 Co 0.093 Al 0.050 Zr 0.021 O 2 。
Example 4
The preparation method of the battery cathode material provided by the embodiment is basically the same as that of the embodiment 1, except that the dopant Al in the step (1) is used 2 O 3 Is replaced by 0.5% of the sum of the masses of the precursor material and the lithium source, and the dopant ZrO in step (1) is 2 Is replaced by 0.1% of the sum of the masses of the precursor material and the lithium source.
The chemical formula of a matrix in the battery anode material is Li 1.05 Ni 0.887 Co 0.099 Al 0.013 Zr 0.001 O 2 。
Example 5
The preparation method of the battery cathode material provided by the embodiment comprises the following steps:
(1) 100mol of precursor material Ni 0.82 Co 0.10 Mn 0.08 (OH) 2 (D50 particle size is 3-6 μm), 120mol lithium source LiHCO 3 And dopant WO 3 And Mg (OH) 2 Placing in a high-speed mixing device, mixing for 30min at 2000rpm to obtain a mixed material;
among them, the dopant WO 3 (particle size < 100 nm) 0.5% by mass of the sum of the precursor material and the lithium source, and a dopant Mg (OH) 2 The mass of the precursor material (particle size < 100 nm) was 0.5% of the sum of the masses of the precursor material and the lithium source.
(2) Adding a first coating agent NiFe into the mixture obtained in the step (1) 2 O 4 (D50 particle size < 30 nm) and a second coating agent Al (OH) 3 (particle size < 100 nm), and mixing at 1800rpmThe time is 5 min; after being uniformly mixed, the mixture is placed in a mixed gas containing air and oxygen (the volume fraction of the oxygen in the mixed gas is 80 percent) for sintering to obtain a battery anode material;
wherein, the first cladding agent NiFe 2 O 4 The mass of (a) is 0.1% of the sum of the masses of the precursor material and the lithium source; second cladding agent Al 2 O 3 The mass of (a) is 0.3% of the sum of the masses of the precursor material and the lithium source; the sintering temperature is 850 ℃, the heating rate of heating to the sintering temperature is 10 ℃/min, and the sintering heat preservation time is 28 h.
The battery anode material comprises a matrix and a coating layer coated on the surface of the matrix, wherein the chemical formula of the matrix is Li 1.2 Ni 0.805 Co 0.098 Mn 0.079 Mg 0.015 W 0.004 O 2 The coating layer is lithium nickel iron aluminate.
The thickness of the coating layer is 15nm through detection; the D50 particle size of the battery anode material is 3-6 μm.
Example 6
The preparation method of the battery cathode material provided by the embodiment is basically the same as that of the embodiment 1, except that the dopant Al in the step (1) is used 2 O 3 Substitution to Na 2 CO 3 (but keeping its mass unchanged); and doping agent ZrO in the step (1) 2 Substituted by TiO 2 (but keeping its mass unchanged).
The chemical formula of a matrix in the battery anode material is Li 1.05 Ni 0.870 Co 0.097 Na 0.025 Ti 0.008 O 2 。
Comparative example 1
The preparation method of the battery positive electrode material provided by the comparative example comprises the following steps:
(1) exactly the same as the step (1) in example 1.
(2) Placing the mixed material obtained in the step (1) in a mixed gas containing air and oxygen (the volume fraction of the oxygen in the mixed gas is 95%) for sintering to obtain a battery anode material; wherein the sintering temperature is 720 ℃, the heating rate of heating to the sintering temperature is 5 ℃/min, and the sintering heat preservation time is 22 h.
That is, in this comparative example, NiFe was not added as the first coating agent 2 O 4 And a second coating agent Al 2 O 3 。
Comparative example 2
The preparation method of the battery positive electrode material provided by the comparative example comprises the following steps:
(1) exactly the same as the step (1) in example 1.
(2) Adding a second coating agent Al into the mixture obtained in the step (1) 2 O 3 (the grain diameter is less than 180 nm), and the secondary mixing is carried out at the rotating speed of 1500rpm, and the mixing time is 8 min; after being uniformly mixed, the mixture is placed in a mixed gas containing air and oxygen (the volume fraction of the oxygen in the mixed gas is 95 percent) for sintering to obtain a battery anode material;
wherein the second cladding agent Al 2 O 3 The mass of (a) is 0.1% of the sum of the masses of the precursor material and the lithium source; the sintering temperature is 720 ℃, the heating rate of heating to the sintering temperature is 5 ℃/min, and the sintering heat preservation time is 22 h.
That is, NiFe, which is an additional primary coating agent, was not added to this comparative example 2 O 4 。
Comparative example 3
The preparation method of the positive electrode material for the battery provided by the comparative example is substantially the same as that of example 1, except that, in the step (1), the dopant Al is not added 2 O 3 And ZrO 2 。
Comparative example 4
The preparation method of the positive electrode material for the battery provided by the comparative example is substantially the same as that of example 1, except that the dopant Al in step (1) is added 2 O 3 The mass of (b) is replaced by 4% of the sum of the mass of the precursor material and the mass of the lithium source, and the dopant ZrO 2 The mass of (particle size < 180 nm) was replaced by 4% of the sum of the mass of the precursor material and the lithium source.
Comparative example 5
The preparation method of the positive electrode material for a battery provided in this comparative example is substantially the same as that of example 1 except that the sintering temperature in step (2) is replaced with 1100 ℃.
Experimental example 1
The amount of residual alkali (referring to the mass ratio of residual alkali in the battery positive electrode material) of the battery positive electrode materials prepared in the above examples and comparative examples was measured, and the results are shown in table 1 below.
TABLE 1 residual alkali content results for each set of battery positive electrode materials
Group of Residual alkali amount (wt.%)
Example 1 0.62
Example 2 0.45
Example 3 0.48
Example 4 0.63
Example 5 0.87
Example 6 0.66
Comparative example 1 1.22
Comparative example 2 1.17
Comparative example 3 0.64
Comparative example 4 0.58
Comparative example 5 0.90
As can be seen from table 1 above, the battery cathode material prepared in example 1 had a significantly lower residual alkali amount than comparative examples 1 and 2.
Therefore, the invention can reduce the residual alkali content of the battery anode material and improve the surface stability of the battery anode material by coating the lithium nickel aluminate on the surface of the matrix.
Meanwhile, SEM examination was performed on the battery cathode material obtained in example 1, and the results are shown in fig. 1. The positive electrode material for the battery obtained in example 1 was subjected to XPS (X-ray photoelectron spectroscopy) detection, and the results are shown in fig. 2 (Al element), fig. 3 (Fe element), fig. 4 (Ni element), and fig. 5 (Zr element), respectively.
As can be seen from figure 1, the battery cathode material prepared by the method is uniform secondary particles with D50 of 8-12 um.
As can be seen from fig. 2, fig. 3, fig. 4 and fig. 5, the surface of the battery cathode material prepared by the invention can detect Ni, Fe and Al elements, which indicates that lithium nickel iron aluminate is formed on the surface of the material, and the content of Fe and Al elements and the content of Zr elements on the surface of the material are reduced and increased after argon ion beam sputtering, which indicates that lithium nickel iron aluminate is enriched on the surface of the material in the form of a coating layer.
In addition, DSC (differential scanning calorimetry) tests were performed on the positive electrode materials of the batteries manufactured in example 1, example 4 and comparative example 1, and the results are shown in fig. 6. As can be seen from fig. 6, the thermal stability of the battery positive electrode materials of examples 1 and 4 was better than that of comparative example 1.
Specifically, it can be found by comparing the integrated areas of the first exothermic peaks that example 4 is smaller, which indicates that its exothermic amount is small. As can be seen by comparing the position of the second exothermic peak, the peak position temperature of example 4 is higher. These two data demonstrate that both example 1 and example 4 have better thermal stability than comparative example 1. The effect of example 4 is slightly worse than that of example 1 because the coating material is partially diffused inward due to the small amount of the dopant, so that the coating effect is slightly deteriorated.
Experimental example 2
The positive electrode materials of the batteries prepared in the embodiments and the respective proportions are respectively used as positive active materials to prepare positive electrode pieces, and metal Li is used as a negative electrode to respectively assemble a plurality of groups of 2032 button batteries. The resulting cells from each group were then tested for electrochemical performance: the voltage is 2.5V-4.25V, the current is 0.2C, the first charge-discharge specific capacity is measured, the first effect is obtained, and the data result is shown in the following table 2.
Meanwhile, the cycle capacity retention rates of the assembled batteries of example 1, comparative example 1 and comparative example 2 were respectively tested, and the results are shown in fig. 7.
As can be seen from fig. 7, the cycle performance of example 1 is more excellent than that of both comparative example 1 and comparative example 2.
Table 2 electrochemical performance test results of each battery group
Group of Specific capacity for first charge (mAh/g) Specific capacity of first discharge (mAh/g) First effect (%)
Example 1 234.5 213.5 91.0
Example 2 219.8 198.3 90.2
Example 3 233.1 209.4 89.8
Example 4 235.4 214.3 91.3
Example 5 221.3 198.1 89.5
Example 6 233.9 212.6 90.9
Comparative example 1 227.3 196.2 86.3
Comparative example 2 227.0 195.0 85.9
Comparative example 3 234.1 212.3 90.7
Comparative example 4 215.2 185.3 86.1
Comparative example 5 229.2 200.8 87.6
It can be seen from the test results of comparative example 1 and comparative example 4 that the mass ratio of the dopant is too large, which results in a decrease in the first discharge specific capacity and the first effect.
As can be seen from the test results of comparative example 1 and comparative examples 1-2, the lithium nickel iron aluminate coated on the surface of the matrix can improve the first charge/discharge specific capacity and the first effect.
While particular embodiments of the present invention have been illustrated and described, it will be appreciated that the above embodiments are merely illustrative of the technical solution of the present invention and are not restrictive; those of ordinary skill in the art will understand that: modifications may be made to the above-described embodiments, or equivalents may be substituted for some or all of the features thereof without departing from the spirit and scope of the present invention; the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention; it is therefore intended to cover in the appended claims all such alternatives and modifications that are within the scope of the invention.

Claims (9)

1. The battery positive electrode material is characterized by comprising a matrix and a coating layer coated on the surface of the matrix;
the chemical formula of the matrix is Li a Ni x M y N z O 2 Wherein a is more than or equal to 1 and less than or equal to 1.2, x is more than or equal to 0.8 and less than 1, y is more than 0 and less than 0.2, z is more than 0 and less than 0.1, and x + y + z = 1; m comprises Co and/or Mn, N comprises at least one of Al, Zr, Sr, W, Mg, Na and Ti;
the coating layer is lithium nickel iron aluminate;
the preparation method of the battery anode material comprises the following steps:
adding a first coating agent and a second coating agent into a mixture containing a precursor material, a lithium source and a doping agent, mixing and sintering to obtain a battery anode material;
wherein the chemical formula of the precursor material is Ni p M q (OH) 2 (ii) a Wherein p is more than 0.8 and less than 1, q is more than 0 and less than 0.2, and p + q = 1; m comprises Co and/or Mn;
the dopant comprises at least one of an Al source, a Zr source, a Sr source, a W source, a Mg source, a Na source and a Ti source;
the first coating agent comprises NiFe 2 O 4 ；
The second coating agent includes an aluminum-containing compound.
2. The battery positive electrode material according to claim 1, characterized by comprising at least one of the following features (1) to (5):
(1) the thickness of the coating layer is 5 nm-30 nm;
(2) the mass of the coating layer is 0.1-0.8% of that of the matrix;
(3) the substrate is a substrate with a layered structure;
(4) the coating layer is of a laminated structure;
(5) the D50 particle size of the battery anode material is 3-20 μm.
3. The battery positive electrode material according to claim 1, characterized by comprising at least one of the following features (1) to (9):
(1) the Al source comprises Al 2 O 3 、Al(OH) 3 And AlOOH;
(2) the Zr source comprises ZrO 2 And Li 2 ZrO 3 At least one of;
(3) the Sr source comprises SrO, Sr (OH) 2 And SrO 2 At least one of;
(4) the W source comprises WO 3 、Li 2 WO 4 And at least one of a W-containing heteropoly acid;
(5) the Mg source comprises MgO and Mg (OH) 2 And MgCO 3 At least one of;
(6) the Na source comprises Na 2 CO 3 And NaHCO 3 At least one of;
(7) the Ti source comprises TiO 2 、Ti(SO 4 ) 2 And Ti (OH) 4 At least one of;
(8) the lithium source includes Li 2 CO 3 、LiOH、LiHCO 3 、CH 3 COOLi and LiNO 3 At least one of;
(9) the aluminum-containing compound comprises Al 2 O 3 、Al(OH) 3 AlOOH and LiAlO 2 At least one of (1).
4. The battery positive electrode material according to claim 1, characterized by comprising at least one of the following features (1) to (4):
(1) the molar ratio of the precursor material to the lithium source is 1:1 to 1.5;
(2) the mass of the dopant is 0.5% -5% of the sum of the mass of the precursor material and the mass of the lithium source;
(3) the mass of the first coating agent is 0.05% -0.4% of the sum of the mass of the precursor material and the mass of the lithium source;
(4) the mass of the second coating agent is 0.05% -0.4% of the sum of the mass of the precursor material and the mass of the lithium source.
5. The battery positive electrode material according to claim 1, characterized by comprising at least one of the following features (1) to (3):
(1) the sintering temperature is 700-900 ℃;
(2) the heating rate of heating to the sintering temperature is 3-10 ℃/min;
(3) and the sintering heat preservation time is 15-30 h.
6. The battery positive electrode material according to claim 1, characterized by comprising at least one of the following features (1) to (2):
(1) the preparation method of the mixed material containing the precursor material, the lithium source and the dopant comprises the following steps: mixing the precursor material, the lithium source and the dopant for the first time under the condition that the rotating speed is 2000-3000 rpm, wherein the time of the first mixing is 10-30 min;
(2) and after the first coating agent and the second coating agent are added, carrying out secondary mixing at the rotating speed of 1000-2000 rpm for 5-10 min.
7. The battery positive electrode material according to claim 1, wherein the sintering is performed in an oxygen-containing atmosphere.
8. The battery positive electrode material according to claim 1, characterized by comprising at least one of the following features (1) to (5):
(1) the D50 particle size of the precursor material is 3-20 μm;
(2) the grain size of the dopant is less than 200 nm;
(3) the D50 particle size of the first coating agent is less than 100 nm;
(4) the grain size of the second coating agent is less than 200 nm;
(5) the purity of the first coating agent is not less than 99%.
9. A lithium ion battery comprising the positive electrode material for a battery according to any one of claims 1 to 8.
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