WO2022188181A1 - Positive electrode material, electrochemical apparatus comprising same, and electronic device - Google Patents

Positive electrode material, electrochemical apparatus comprising same, and electronic device Download PDF

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Publication number
WO2022188181A1
WO2022188181A1 PCT/CN2021/080597 CN2021080597W WO2022188181A1 WO 2022188181 A1 WO2022188181 A1 WO 2022188181A1 CN 2021080597 W CN2021080597 W CN 2021080597W WO 2022188181 A1 WO2022188181 A1 WO 2022188181A1
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Prior art keywords
positive electrode
electrode material
lithium
present application
transition metal
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PCT/CN2021/080597
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French (fr)
Chinese (zh)
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谷风
程世杨
郎野
徐磊敏
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宁德新能源科技有限公司
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Priority to CN202180006454.8A priority Critical patent/CN114730869A/en
Priority to PCT/CN2021/080597 priority patent/WO2022188181A1/en
Publication of WO2022188181A1 publication Critical patent/WO2022188181A1/en

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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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application relates to the technical field of energy storage materials, in particular to a positive electrode material, an electrochemical device and an electronic device comprising the same.
  • Electrochemical devices such as lithium-ion batteries have the characteristics of high theoretical specific capacity and high safety performance, and have gradually become the main power source in the 3C field (computer, communication, consumer electronics product field) and the power field (EV field).
  • the cathode material as an important part of the lithium-ion battery, has a significant impact on its performance, so it is particularly important to continuously optimize and improve the cathode material.
  • the mainstream cathode material used in the 3C field is generally lithium cobalt oxide
  • the mainstream cathode material used in the EV field is a nickel-cobalt-manganese ternary material, both of which are layered transition metal oxides. move freely in the interlayer.
  • Cathode materials In order to pursue high energy density, increasing the nickel content of the cathode material to increase its reversible gram capacity has become one of the ways to optimize the cathode material. Therefore, in order to pursue higher capacity and higher energy density, the continuous optimization of high-nickel ternary cathode materials has attracted more and more attention.
  • the "Li-O" interlayer spacing where lithium ions are located decreases, the lithium ion migration barrier increases, and the kinetics becomes poor; on the other hand, due to the divalent nickel ion radius Close to the radius of lithium ions, it is easy to mix lithium and nickel during the synthesis process, resulting in reduced material capacity and poor kinetics.
  • the purpose of the present application is to provide a positive electrode material, an electrochemical device comprising the positive electrode material, and an electronic device comprising the electrochemical device, in an attempt to solve at least one problem existing in the related field at least to some extent.
  • a positive electrode material having a crystal structure belonging to space group Cmc2 1 .
  • the 003 crystal plane diffraction peak is located in the range of 12° to 18.5°.
  • the intensity ratio I (003) /I (104) of the diffraction peak of the 003 crystal plane and the diffraction peak of the 104 crystal plane satisfies: I (003) /1 (104) ⁇ 1.8. According to further embodiments of the present application, 1.8 ⁇ I (003) /I (104) ⁇ 2.6.
  • the unit cell parameters of the cathode material According to further embodiments of the present application, the range of the unit cell parameter a is to
  • the unit cell parameters of the cathode material According to further embodiments of the present application, the range of the unit cell parameter c is to
  • the unit cell parameter c/unit cell parameter a of the cathode material is greater than or equal to 4.95. According to further embodiments of the present application, the unit cell parameter c/unit cell parameter a ranges from 4.95 to 6.68.
  • the cathode material includes a lithium transition metal oxide, wherein the interlayer distance between Li and O ranges from to
  • the cathode material includes a lithium transition metal oxide
  • the lithium transition metal oxide contains a transition metal element Me
  • the transition metal element Me includes Ni element, based on the molar amount of transition metal element Me, the mole of Ni element Percentage ⁇ 50%.
  • the positive electrode material includes secondary particles composed of primary particles, the average particle diameter of the primary particles is 0.1 ⁇ m to 1.5 ⁇ m, and the average particle diameter of the secondary particles is 1 ⁇ m to 30 ⁇ m.
  • the cathode material includes Li x Ni y Co z Mn k Z q O ba Ta , wherein Z includes B, Mg, Al, Si, P, S, Ti, Cr, Fe, Cu, at least one of Zn, Ga, Y, Zr, Mo, Ag, W, In, Sn, Pb, Sb, Sr, and Ce, T is a halogen, and x, y, z, k, q, a, and b are respectively Satisfy: 0.2 ⁇ x ⁇ 1.2, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, 0 ⁇ k ⁇ 1, 0 ⁇ q ⁇ 1, 1 ⁇ b ⁇ 2, and 0 ⁇ a ⁇ 1; preferably, 0.6 ⁇ x ⁇ 1.2, 0.5 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 0.5, 0 ⁇ k ⁇ 0.5, 0 ⁇ q ⁇ 0.5, 1.5 ⁇ b ⁇ 2, and 0 ⁇ a ⁇ 0.5.
  • the present application provides an electrochemical device comprising the positive electrode material as previously described in the present application.
  • the application provides an electronic device comprising the electrochemical device as previously described in the application.
  • the crystal structure of the positive electrode material provided by the present application has a specific space group, which is conducive to the diffusion of metal ions such as lithium ions in the bulk phase of the material, and can improve the kinetic performance of the positive electrode material, and It can effectively improve the capacity performance, Coulomb efficiency and cycle performance of the cathode material.
  • Example 1 is a schematic diagram of the interlayer distance between Li and O of the positive electrode material provided in Example 1 of the present application;
  • FIG. 3 is a schematic diagram of Li/Ni mutual occupancy of positive electrode materials provided by an exemplary embodiment of the present application
  • FIG. 4 is an X-ray diffraction pattern (XRD pattern) of the cathode material provided in Example 1 of the present application.
  • a list of items joined by the terms "at least one of,” “at least one of,” “at least one of,” or other similar terms may mean the listed items any combination of .
  • the phrase "at least one of A, B” means A only; B only; or A and B.
  • the phrase "at least one of A, B, C” means A only; or B only; C only; A and B (excluding C); A and C (excluding B); B and C (excluding A); or all of A, B, and C.
  • Item A may contain a single element or multiple elements.
  • Item B may contain a single element or multiple elements.
  • Item C may contain a single element or multiple elements.
  • a high nickel ternary cathode material is one of several cathode materials used in electrochemical devices such as lithium ion batteries.
  • High-nickel ternary cathode materials have problems such as kinetic properties that need to be improved or lithium-nickel mixing and other problems are prone to occur during the synthesis process.
  • optimization is generally carried out from the following aspects: by reducing the particle size of the particles; by doping the lithium layer with an element with a large ionic radius; by The way to coat fast ion conductors on the surface.
  • the compaction density of the material will be reduced, thereby affecting the energy density of the material; in addition, the smaller the particle size, the larger the specific surface area BET of the material, and the adverse effect of the material and the electrolyte.
  • the response will increase.
  • Doping the lithium layer with an element with a large ionic radius is a common method to expand the distance between the lithium layers, but this method has high requirements for doping elements and doping process, and the doping amount is relatively small, so it can play a limited role.
  • the method of coating fast ion conductors on the surface is an auxiliary solution, which cannot fundamentally solve the diffusion problem of metal ions such as lithium ions in the bulk phase of the positive electrode material, and has a poor effect on improving the kinetics of the material.
  • the present application provides a positive electrode material.
  • the cathode material has a crystal structure belonging to space group Cmc2 1 .
  • the crystal structure of the positive electrode material provided in the embodiment of the present application has a specific space group, and the space group is Cmc2 1 , which increases the range of the lithium interlayer spacing, which is more conducive to the diffusion of lithium ions in the bulk phase of the material, and has a more stable structure, which can improve the performance of the positive electrode.
  • the kinetic properties of the material can be effectively improved, and the capacity performance, Coulomb efficiency and cycle performance of the cathode material can be effectively improved.
  • the 003 crystal plane diffraction peak is located in the range of 12° to 18.5°.
  • the kinetic properties of the cathode material are better, and the structure of the cathode material is stable, which shows that the discharge specific capacity, the first cycle Coulomb efficiency and the cycle performance of the cathode material are better.
  • the intensity ratio of the 003 crystal plane diffraction peak and the 104 crystal plane diffraction peak I (003) /I (104) satisfies: I (003 ) /I (104) ⁇ 1.8.
  • the intensity ratio of the 003 crystal plane diffraction peak to the 104 crystal plane diffraction peak I (003) /I (104) satisfies: I (003) /I (104 ) ⁇ 2.0.
  • the intensity ratio of the 003 crystal plane diffraction peak to the 104 crystal plane diffraction peak I (003) /I (104) satisfies: 1.8 ⁇ I (003) /I (104) ⁇ 2.6.
  • the cathode material according to the embodiment of the present application has a crystal structure belonging to the space group Cmc2 1 , and the intensity ratio of the diffraction peaks of the 003 crystal plane and the 104 crystal plane in the XRD pattern satisfies: I ( 003) /I (104 ) /I (104) ⁇ 1.8, thus, the diffusivity of Li between the Li layer and the transition metal layer in the material can be improved, the occupancy rate of Li in the transition metal layer is appropriate, and the crystal structure is more thermodynamically stable. , so that the positive electrode material is suitable for realizing high-capacity devices, and similarly, it can be considered that the positive electrode material is also suitable for realizing electrochemical devices with excellent cycle performance.
  • the range of the unit cell parameter a of the cathode material is ⁇ In some embodiments, the range of the unit cell parameter c is ⁇ In some embodiments, the range of unit cell parameter c/unit cell parameter a is > 4.95. In some embodiments, the range of the unit cell parameter a of the cathode material is to In some embodiments, the range of the unit cell parameter c is to In some embodiments, the unit cell parameter c/unit cell parameter a ranges from 4.95 to 6.68.
  • the structure of the positive electrode material is more stable, and the cycle performance of the positive electrode material is better; It is more conducive to the extraction and insertion of lithium ions, and can better improve the discharge specific capacity and Coulomb efficiency of the cathode material.
  • the cathode material includes a lithium transition metal oxide, wherein the interlayer distance between Li and O is in the range of to In some embodiments, the cathode material includes a lithium transition metal oxide, wherein the interlayer distance between Li and O is in the range of to In some embodiments, the cathode material includes a lithium transition metal oxide, wherein the interlayer distance between Li and O is in the range of to The increase of the lithium interlayer spacing is more conducive to the diffusion of lithium ions, which can make the lithium ions migrate more smoothly, thereby improving the discharge specific capacity and Coulomb efficiency of the cathode material, and improving the cycle performance of the cathode material.
  • the positive electrode material includes a lithium transition metal oxide, the lithium transition metal oxide contains a transition metal element Me, the transition metal element Me includes Ni element, and based on the molar amount of the transition metal element Me, the mole percentage of Ni element is ⁇ 50%. In some embodiments, the positive electrode material includes a lithium transition metal oxide, the lithium transition metal oxide contains a transition metal element Me, the transition metal element Me includes Ni element, and based on the molar amount of the transition metal element Me, the mole percentage of Ni element ⁇ 70%.
  • the positive electrode material includes a lithium transition metal oxide
  • the lithium transition metal oxide contains a transition metal element Me
  • the transition metal element Me includes Ni element
  • the mole percentage of Ni element is greater than or equal to 80. %.
  • the positive electrode material is a high-nickel ternary positive electrode material, that is, the molar percentage of Ni element (relative to the total metal elements other than Li) is not less than 50%.
  • the positive electrode material contains S element, and based on the mass of the positive electrode material, the mass percentage of the S element is ⁇ 0.1%.
  • the positive electrode material includes secondary particles composed of primary particles, the average particle diameter of the primary particles is 0.1 ⁇ m to 1.5 ⁇ m, and the average particle diameter of the secondary particles is 1 ⁇ m to 30 ⁇ m.
  • the particle size of the cathode material will affect the capacity, rate capability and cycling performance of electrochemical devices.
  • the particle size of the primary particles is suitable, which is beneficial to improve the cycle performance and rate performance of the positive electrode material.
  • the positive electrode active material can also be made to exert higher capacity, thereby improving the energy density of the battery.
  • the electrochemical device can have both good kinetic performance and high energy density at the same time, which is beneficial to improve the comprehensive performance of the material and the electrochemical device.
  • the secondary particles have an average particle size of 5 ⁇ m to 20 ⁇ m. In some embodiments, the secondary particles have an average particle size of 10 ⁇ m to 20 ⁇ m.
  • the cathode material includes Li x Ni y Co z Mn k Z q O ba Ta , wherein Z includes B, Mg, Al, Si, P, S, Ti, Cr, Fe, Cu, At least one of Zn, Ga, Y, Zr, Mo, Ag, W, In, Sn, Pb, Sb and Ce, T is halogen, and x, y, z, k, q, a and b satisfy: 0.2 ⁇ x ⁇ 1.2, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, 0 ⁇ k ⁇ 1, 0 ⁇ q ⁇ 1, 1 ⁇ b ⁇ 2, and 0 ⁇ a ⁇ 1.
  • the cathode material may include at least one of lithium-containing transition metal oxides such as lithium cobalt oxide, lithium nickel cobalt manganate (ternary cathode material), and lithium manganate.
  • the cathode material includes a high nickel ternary cathode material.
  • the preparation of high-nickel ternary cathode materials is obtained by mixing ⁇ -phase R 3 m precursor Ni 1-xy Co x M y (OH) 2 and lithium salt LiOH ⁇ H 2 O and sintering in oxygen atmosphere.
  • Ni in the precursor has a valence of +2, and it is difficult to be completely oxidized to a valence of +3. Since the ionic radius of Ni 2+ and the radius of Li + are very close, it is easy to mix lithium and nickel during the synthesis process. As a result, part of the lithium of the material cannot be exerted, thereby reducing the capacity of the material.
  • the high-nickel material lithium layer will be formed because the precursor used is ⁇ -Ni 1-xy Co x M y (OH) 2 .
  • the smaller spacing makes it difficult for lithium ions to diffuse, reducing the kinetic performance.
  • the positive electrode material can be a high-nickel ternary positive electrode material, and the high-nickel ternary positive electrode material can be prepared by the following method: using ⁇ -Ni 1-xy Co x M y (OH) 2 as a ternary
  • the precursor of the positive electrode material is mixed with ⁇ -Ni 1-xy Co x M y (OH) 2 as a lithium salt, and the positive electrode material with the crystal structure belonging to the space group Cmc2 1 can be obtained by solid-phase sintering,
  • the obtained cathode material has a larger interlayer distance, for example, the interlayer distance between Li and O ranges from to Since the distance between the lithium layers is much larger than the Ni-O bond length, it inhibits the easy formation of Li/Ni mutual occupation by Ni in the lithium layer, and alleviates the poor kinetic properties, high-rate discharge temperature, and lithium Nickel mixed row and other issues.
  • the positive electrode material is not limited to this, and the preparation method of the positive electrode material is
  • the present application provides an electrochemical device comprising a positive electrode, a negative electrode, an electrolyte, and a separator disposed between the positive electrode and the negative electrode.
  • the electrochemical device of the present application can be a lithium ion battery or a lithium metal battery, and can also be any other suitable electrochemical device.
  • the electrochemical device in the embodiments of the present application includes any device that undergoes an electrochemical reaction, and specific examples thereof include all kinds of primary batteries, secondary batteries, fuel cells, Solar cells or capacitors.
  • the electrochemical device is a lithium secondary battery including, but not limited to, a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery.
  • the electrochemical device of the present application is an electrochemical device including a positive electrode having a positive electrode active material capable of occluding and releasing metal ions, and a negative electrode having a negative electrode active material capable of absorbing and releasing metal ions. of any of the above cathode materials. Therefore, since the electrochemical device of the embodiment of the present application includes the above-mentioned positive electrode material, it can alleviate the problems of poor kinetic performance of the positive electrode material in the existing electrochemical device and the mixed arrangement of lithium and nickel during the synthesis process, which can improve the efficiency of the electrochemical device. Kinetic and cycling performance of chemical devices.
  • the positive electrode material used in the electrochemical device of the present application is any of the above-mentioned positive electrode materials of the present application.
  • the positive electrode material used in the electrochemical device of the present application may further include other positive electrode materials within the scope of not departing from the gist of the present application.
  • the positive electrode includes a positive electrode current collector and a positive electrode active material layer disposed on at least one surface of the positive electrode current collector, wherein the positive electrode active material layer includes the aforementioned positive electrode material.
  • the positive active material layer further includes a binder.
  • the binder can improve the bonding of the positive electrode material particles to each other, and can improve the bonding of the positive electrode material to the positive electrode current collector.
  • the binder includes, but is not limited to, polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polyvinyl Ethoxylated polymers, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy Resin and nylon, etc.
  • the binder includes at least one of polyvinylidene fluoride (PVDF), carboxymethyl cellulose, and styrene-butadiene rubber.
  • PVDF polyvinylidene fluoride
  • carboxymethyl cellulose carboxymethyl cellulose
  • styrene-butadiene rubber styrene-butadiene rubber
  • the positive electrode active material layer further includes a conductive agent, thereby imparting conductivity to the electrode.
  • the conductive agent may include any conductive material as long as it does not cause unwanted chemical changes.
  • conductive agents include, but are not limited to, carbon-based materials, metal-based materials, conductive polymers, and mixtures thereof.
  • the carbon-based material may be selected from natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fiber, or any combination thereof;
  • the metal-based material may be selected from metal powder, metal fiber, copper, Nickel, aluminum, silver, or any combination thereof;
  • the conductive polymer may be selected from polyphenylene derivatives.
  • the conductive agent includes at least one of conductive carbon black, acetylene black, graphene, ketjen black, and conductive nanotubes.
  • the binder and the conductive agent in the above-mentioned positive electrode active material layer are not specifically limited, and can be selected according to actual needs.
  • the positive electrode current collector may be a positive electrode current collector commonly used in the art.
  • the positive electrode current collector is metal, such as but not limited to aluminum foil or nickel foil.
  • the structure of the positive electrode is a positive electrode plate structure known in the art that can be used in an electrochemical device.
  • the method of making the positive electrode is known to those skilled in the art as a method of making a positive electrode that can be used in an electrochemical device.
  • a positive electrode can be obtained by mixing a positive electrode material, a conductive agent, and a binder in a solvent to prepare a slurry, and coating the slurry on a current collector.
  • the solvent may include water, N-methylpyrrolidone, etc., but is not limited thereto.
  • the negative electrode includes a negative electrode current collector and a negative electrode active material layer disposed on at least one surface of the negative electrode current collector.
  • the anode active material layer includes an anode active material, and the anode active material may include a material that reversibly intercalates/deintercalates lithium ions, lithium metal, lithium metal alloy, or transition metal oxide.
  • the negative electrode active material includes at least one of carbon material or silicon material, the carbon material includes at least one of graphite and hard carbon, and the silicon material includes silicon, silicon oxide compound, silicon carbon compound or silicon alloy at least one of.
  • a lithium-containing metal sheet layer is used as the negative electrode active material layer.
  • the negative electrode current collector includes two opposite surfaces in the thickness direction of the negative electrode current collector, and the lithium-containing metal sheet layer is laminated on either or both of the two surfaces of the negative electrode current collector.
  • the lithium-containing metal sheet layer may be formed on the negative electrode current collector by at least one of mechanical rolling, vapor deposition, and electroless plating.
  • the negative electrode current collector may be a negative electrode current collector commonly used in the art.
  • the negative electrode current collector can be made of materials such as metal foils or porous metal plates, for example, foils or porous plates of metals such as copper, nickel, titanium or iron or their alloys, such as copper foil.
  • the negative electrode active material layer includes a negative electrode active material, a binder and a conductive agent.
  • the negative electrode active material can reversibly intercalate and deintercalate lithium ions.
  • the specific types of negative electrode active materials are not specifically limited, and can be selected according to requirements.
  • the structure of the negative electrode and the preparation method of the negative electrode are known in the art for the structure of the negative electrode plate that can be used in an electrochemical device and the preparation method for the negative electrode for the electrochemical device known in the art .
  • the electrolyte that can be used in the embodiments of the present application may be an electrolyte known in the prior art. Electrolytes can be divided into aqueous electrolytes and non-aqueous electrolytes. Compared with aqueous electrolytes, electrochemical devices using non-aqueous electrolytes can work in a wider voltage window, thereby achieving higher energy density.
  • the non-aqueous electrolyte includes an organic solvent and an electrolyte.
  • Electrolytes that can be used in the electrolyte of the embodiments of the present application include, but are not limited to: inorganic lithium salts, such as LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiSbF 6 , LiSO 3 F, LiN(FSO 2 ) 2 , etc.; Fluorine-containing organolithium salts such as LiCF 3 SO 3 , LiN(FSO 2 )(CF 3 SO 2 ), LiN(CF 3 SO 2 ) 2 , LiN(C 2 F 5 SO 2 ) 2 , cyclic 1,3- Lithium hexafluoropropanedisulfonimide, cyclic lithium 1,2-tetrafluoroethanedisulfonimide, LiPF 4 (CF 3 ) 2 , LiN(CF 3 SO 2 )(C 4 F 9 SO 2 ) , LiC(CF 3 SO 2 ) 3 , LiPF 4 (CF 3 SO 2 ) 2
  • organic solvent that can be used in the electrolyte in the embodiments of the present application can be any organic solvent known in the prior art.
  • organic solvents include, but are not limited to, carbonate compounds, ester-based compounds, ether-based compounds, ketone-based compounds, alcohol-based compounds, aprotic solvents, or combinations thereof.
  • examples of the carbonate compound include, but are not limited to, a chain carbonate compound, a cyclic carbonate compound, a fluorocarbonate compound, or a combination thereof.
  • the organic solvent includes ethylene carbonate (EC), propylene carbonate (PC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), propylene carbonate at least one of ester, propyl propionate and ethyl propionate.
  • EC ethylene carbonate
  • PC propylene carbonate
  • DEC diethyl carbonate
  • EMC ethyl methyl carbonate
  • DMC dimethyl carbonate
  • propylene carbonate at least one of ester, propyl propionate and ethyl propionate propylene carbonate at least one of ester, propyl propionate and ethyl propionate.
  • the separator can be any material suitable for the separator of electrochemical energy storage device in the art, for example, can be including but not limited to polyethylene, polypropylene, polyvinylidene fluoride, aramid, polyethylene terephthalate A combination of one or more of ester, polytetrafluoroethylene, polyacrylonitrile, polyimide, polyamide, polyester and natural fibers.
  • the release film is, for example, a single layer or multiple layers of one or more of glass fiber, non-woven fabric, polyethylene (PE), polypropylene (PP), and polyvinylidene fluoride (PVDF). film.
  • the present application provides an electronic device comprising the aforementioned electrochemical device.
  • the problems of poor kinetic performance, high discharge temperature increase, and lithium-nickel mixed discharge of the existing positive electrode material can be alleviated, and the discharge specific capacity and the first-cycle Coulomb efficiency of the electrochemical device can be improved. and cycle performance, making the electrochemical device thus fabricated suitable for electronic equipment in various fields.
  • the use of the electrochemical device of the present application is not particularly limited, and it can be used in any electronic device known in the art.
  • the electronic devices include, but are not limited to, notebook computers, pen-type computers, mobile computers, e-book players, portable telephones, portable fax machines, portable copiers, portable printers, headphone headsets, video recorders, LCD televisions , portable cleaners, portable CD players, mini-discs, transceivers, electronic notepads, calculators, memory cards, portable recorders, radios, backup power supplies, motors, cars, motorcycles, power-assisted bicycles, bicycles, lighting fixtures, toys , game consoles, clocks, power tools, flash, cameras, large household batteries and lithium-ion capacitors, etc.
  • the electrochemical device of the present application is applicable not only to the electronic devices exemplified above, but also to energy storage power stations, marine vehicles, and air vehicles.
  • Airborne vehicles include airborne vehicles within the atmosphere and airborne vehicles outside the atmosphere.
  • the cathode materials in Examples and Comparative Examples were prepared into lithium secondary batteries by the following preparation methods.
  • separator a polyethylene porous membrane was used as the separator, and the separator was a disc with a diameter of 18 mm.
  • the lithium secondary battery was charged to 4.3V at a rate of 0.1C, then charged at a constant voltage to 0.05C, and then discharged to 2.8V at a rate of 0.1C to obtain the first charge capacity and first discharge capacity.
  • Discharge specific capacity (mAh/g) first discharge capacity (mAh)/positive electrode material mass (g) of the positive electrode.
  • First efficiency (%) first discharge capacity (mAh)/first charge capacity (mAh) ⁇ 100%.
  • the cut-off voltage was raised to 4.5V by means of accelerated cycling.
  • the lithium secondary battery that has completed the discharge specific capacity test is charged to 4.5V at a rate of 0.5C at 25°C, then charged to 0.05C at a constant voltage, and then discharged to 2.8V at a rate of 0.5C. This cycle is repeated 50 times, and then The lithium secondary battery capacity after 50 cycles was calculated.
  • Cycle capacity retention rate (discharge capacity at the 50th cycle (mAh)/discharge capacity at the first cycle (mAh)) ⁇ 100%.
  • the measurement method of the average particle diameter of the secondary particles is the same as that of the primary particles.
  • the particle size value in the reaction slurry reaches 8 ⁇ m, stop the kettle, extract the volume of the supernatant to be 1/4 of the total volume of the reaction slurry, start to concentrate and stir, stop stirring when the large particles reach 10 ⁇ m, and set the temperature at 58°C.
  • the crystal phase structure of the positive electrode material is an R3m layered structure, the molar percentage of nickel element is 80%, and the average particle size D v 50 is 10 ⁇ m. .
  • the particle size value in the reaction slurry reaches 8 ⁇ m, stop the kettle, extract the volume of the supernatant to be 1/4 of the total volume of the reaction slurry, start to concentrate and stir, stop stirring when the large particles reach 10 ⁇ m, and set the temperature at 58°C.
  • the agglomerates of nickel cobalt lithium manganate with a diameter D v 50 of 10 ⁇ m are obtained, that is, a positive electrode material is obtained.
  • the crystal phase structure of the positive electrode material is a Cmc2 1 layered structure, the molar percentage of nickel element is 80%, and the average particle size D v 50 is 10 ⁇ m.
  • Example 2 The difference from Example 1 is that the concentration of ammonia water was adjusted to 2.5g/L, the pH value was 8, and the aging time was 22h under stirring.
  • Example 3 The difference from Example 1 is that the concentration of ammonia water was adjusted to 3g/L, the pH value was 8.5, and the aging time was 20h under stirring.
  • Example 4 The difference from Example 1 is that the concentration of ammonia water was adjusted to 3.5g/L, the pH value was 9, and the aging time was 18h under stirring.
  • Example 5 The difference from Example 1 is that the concentration of ammonia water was adjusted to 4g/L, the pH value was 9.5, and the aging time was 16h under stirring.
  • Example 6 The difference from Example 1 is that the ammonia concentration was adjusted to 4.5g/L, the pH value was 10, and the aging time was 14h under stirring.
  • Example 7 The difference from Example 1 is that the ammonia concentration was adjusted to 5g/L, the pH value was 10.5, and the aging time was 12h under stirring.
  • Example 1 of the cathode material with the crystal structure of space group Cmc2 1 compared to Comparative Example 1 of the cathode material with the R3m layered structure prepared by using traditional precursors, Its capacity retention rate at high voltage is greatly improved, and the discharge specific capacity and first-time efficiency are also improved.
  • the -O layer spacing is much larger than the Ni-O bond length, which inhibits the formation of Li/Ni mutual occupation of Ni in the lithium layer, and solves the problems of poor ternary material kinetics, high-rate discharge temperature rise, and lithium-nickel mixed arrangement.
  • the battery using the cathode material has better capacity performance, first efficiency and cycle performance.
  • the 003 crystal plane of the positive electrode material can be regulated by controlling the ammonia concentration, pH value, aging time and doping of large ionic radius elements for preparing the ⁇ -phase precursor.
  • Example 11 to Example 21 The difference from Example 9 is that the types of doping elements introduced are different: Mg, Ca, Ba, Al, Y, Zr, B, W, Ta, Nb, La;
  • Table 2 shows the relevant performance parameters of the positive electrode materials in Examples 9 to 21 and the performance of the corresponding batteries; it can be seen from Examples 9 to 21 that in the process of preparing the positive electrode materials, the Doping elements with large ionic radius and adjusting their doping amount can increase the Li-O interlayer spacing.
  • the positive electrode material has better crystallinity and less Li/Ni mutual occupancy, and solves the problems of poor kinetics of ternary materials, high discharge temperature increase, and lithium-nickel mixing, so that the battery using the positive electrode material has better performance. capacity performance, first-time efficiency and cycle performance.
  • Example 22 to Example 28 The difference from Example 1 is that the molar content of Ni element in the positive electrode material is different.
  • positive electrode materials with different molar percentages of Ni elements are obtained.
  • Examples 29 to 34 differ from Example 1 in that the average particle size of the positive electrode material is different.
  • the process of preparing the positive electrode material by controlling the reaction time of the ⁇ -phase precursor, positive electrode materials with different average particle sizes are obtained.
  • Example 29 The difference from Example 1 is that when the particle size value in the reaction slurry reaches 0.8 ⁇ m, the kettle is stopped, concentrated, and stirred, and the stirring is stopped when the large particles reach 1 ⁇ m;
  • Example 30 The difference from Example 1 is that when the particle size value in the reaction slurry reaches 2.4 ⁇ m, the kettle is stopped, concentrated, and stirred, and the stirring is stopped when the large particles reach 3 ⁇ m;
  • Example 31 The difference from Example 1 is that when the particle size value in the reaction slurry reaches 4 ⁇ m, stop the kettle, concentrate, stir, and stop stirring when the large particles reach 5 ⁇ m;
  • Example 32 The difference from Example 1 is that when the particle size value in the reaction slurry reaches 9.6 ⁇ m, the kettle is stopped, concentrated, and stirred, and the stirring is stopped when the large particles reach 12 ⁇ m;
  • Example 33 The difference from Example 1 is that when the particle size value in the reaction slurry reaches 16 ⁇ m, the kettle is stopped, concentrated, and stirred, and the stirring is stopped when the large particles reach 20 ⁇ m;
  • Example 34 The difference from Example 1 is that when the particle size value in the reaction slurry reaches 24 ⁇ m, the kettle is stopped, concentrated, and stirred, and the stirring is stopped when the large particles reach 30 ⁇ m;
  • Table 4 shows the relevant performance parameters of the positive electrode materials in Examples 29 to 34 and the performance of the corresponding batteries.
  • FIG. 1 shows a schematic diagram of the interlayer distance between Li and O of the positive electrode material provided in Example 1 of the present application
  • FIG. 2 shows a schematic diagram of the interlayer distance between Li and O of the positive electrode material provided in Comparative Example 1 of the present application. 1 and 2, it can be seen that the interlayer distance between Li and O of the positive electrode material of Example 1 of the present application is much larger than the interlayer distance of Li and O of the positive electrode material of Comparative Example 1.
  • FIG. 3 shows a schematic diagram of the mutual occupancy of the cathode material Li/Ni provided in the embodiment of the present application.
  • FIG. 4 shows the X-ray diffraction pattern (XRD pattern) of the cathode material provided in Example 1 of the present application.
  • XRD pattern X-ray diffraction pattern

Abstract

The present application relates to the technical field of energy storage materials, and in particular, to a positive electrode material, an electrochemical apparatus comprising same, and an electronic device. The present application provides a positive electrode material, which has a crystal structure belonging to a space group Cmc21. The crystal structure of the positive electrode material provided by the present application has a specific space group, so that the diffusion of lithium ions of a material body phase is facilitated, the kinetic performance of the positive electrode material can be improved, and the capacity performance, coulombic efficiency and cycle performance of the positive electrode material can be effectively improved.

Description

正极材料、包含其的电化学装置和电子设备Cathode material, electrochemical device and electronic device containing the same 技术领域technical field
本申请涉及储能材料技术领域，具体涉及一种正极材料、包含其的电化学装置和电子设备。The present application relates to the technical field of energy storage materials, in particular to a positive electrode material, an electrochemical device and an electronic device comprising the same.
背景技术Background technique
电化学装置(例如，锂离子电池)具有理论比容量高、安全性能高等特点，已逐渐成为3C领域(电脑、通信、消费电子类产品领域)及动力领域(EV领域)的主要动力来源。其中正极材料作为锂离子电池的重要组成部分对其性能有着显著的影响，因而对正极材料的不断优化及改进显得尤为重要。目前3C领域使用的主流正极材料一般为钴酸锂，EV领域使用的主流正极材料为镍钴锰三元材料，这两种材料均为层状过渡金属氧化物，锂离子在过渡金属-氧之间的夹层中自由移动。Electrochemical devices (such as lithium-ion batteries) have the characteristics of high theoretical specific capacity and high safety performance, and have gradually become the main power source in the 3C field (computer, communication, consumer electronics product field) and the power field (EV field). Among them, the cathode material, as an important part of the lithium-ion battery, has a significant impact on its performance, so it is particularly important to continuously optimize and improve the cathode material. At present, the mainstream cathode material used in the 3C field is generally lithium cobalt oxide, and the mainstream cathode material used in the EV field is a nickel-cobalt-manganese ternary material, both of which are layered transition metal oxides. move freely in the interlayer.
正极材料为了追求高能量密度，采用提高正极材料的镍含量以提高其可逆克容量的方式成为优化正极材料的方式之一。因此，为了追求更高容量和更高能量密度，高镍三元正极材料的不断优化越来越得到大家的重视。对于高镍正极材料，随着镍含量的增加，一方面锂离子所在的“Li-O”层间距降低，锂离子迁移势垒增加，动力学变差；另一方面，因为二价镍离子半径与锂离子半径接近，在合成过程中很容易出现锂镍混排，导致材料容量降低、动力学变差。Cathode materials In order to pursue high energy density, increasing the nickel content of the cathode material to increase its reversible gram capacity has become one of the ways to optimize the cathode material. Therefore, in order to pursue higher capacity and higher energy density, the continuous optimization of high-nickel ternary cathode materials has attracted more and more attention. For high-nickel cathode materials, with the increase of nickel content, on the one hand, the "Li-O" interlayer spacing where lithium ions are located decreases, the lithium ion migration barrier increases, and the kinetics becomes poor; on the other hand, due to the divalent nickel ion radius Close to the radius of lithium ions, it is easy to mix lithium and nickel during the synthesis process, resulting in reduced material capacity and poor kinetics.
发明内容SUMMARY OF THE INVENTION
本申请的目的在于提供一种正极材料、包含该正极材料的电化学装置和包含该电化学装置的电子设备，以试图在至少某种程度上解决至少一种存在于相关领域中的问题。The purpose of the present application is to provide a positive electrode material, an electrochemical device comprising the positive electrode material, and an electronic device comprising the electrochemical device, in an attempt to solve at least one problem existing in the related field at least to some extent.
根据本申请的一个层面，提供一种正极材料，该正极材料具有属于空间群Cmc2 1的晶体结构。 According to one aspect of the present application, there is provided a positive electrode material having a crystal structure belonging to space group Cmc2 1 .
根据本申请的一些实施例，在正极材料的X射线衍射谱图中，003晶面衍射峰位于12°至18.5°范围内。According to some embodiments of the present application, in the X-ray diffraction spectrum of the cathode material, the 003 crystal plane diffraction peak is located in the range of 12° to 18.5°.
根据本申请的一些实施例，在正极材料的X射线衍射谱图中，003晶面衍射峰与104晶面衍射峰的强度比I (003)/I (104)满足：I (003)/I (104)≥1.8。根据本申请的又一些实施例，1.8≤I (003)/I (104)≤2.6。 According to some embodiments of the present application, in the X-ray diffraction spectrum of the cathode material, the intensity ratio I (003) /I (104) of the diffraction peak of the 003 crystal plane and the diffraction peak of the 104 crystal plane satisfies: I (003) /1 (104) ≥1.8. According to further embodiments of the present application, 1.8≤I (003) /I (104) ≤2.6.
根据本申请的一些实施例，正极材料的晶胞参数
Figure PCTCN2021080597-appb-000001
根据本申请的又一些实施例，晶胞参数a的范围为
Figure PCTCN2021080597-appb-000002
至
Figure PCTCN2021080597-appb-000003
According to some embodiments of the present application, the unit cell parameters of the cathode material
Figure PCTCN2021080597-appb-000001
According to further embodiments of the present application, the range of the unit cell parameter a is
Figure PCTCN2021080597-appb-000002
to
Figure PCTCN2021080597-appb-000003
根据本申请的一些实施例，正极材料的晶胞参数
Figure PCTCN2021080597-appb-000004
根据本申请的又一些实施例，晶胞参数c的范围为
Figure PCTCN2021080597-appb-000005
至
Figure PCTCN2021080597-appb-000006
According to some embodiments of the present application, the unit cell parameters of the cathode material
Figure PCTCN2021080597-appb-000004
According to further embodiments of the present application, the range of the unit cell parameter c is
Figure PCTCN2021080597-appb-000005
to
Figure PCTCN2021080597-appb-000006
根据本申请的一些实施例，正极材料的晶胞参数c/晶胞参数a≥4.95。根据本申请的又一些实施例，晶胞参数c/晶胞参数a的范围为4.95至6.68。According to some embodiments of the present application, the unit cell parameter c/unit cell parameter a of the cathode material is greater than or equal to 4.95. According to further embodiments of the present application, the unit cell parameter c/unit cell parameter a ranges from 4.95 to 6.68.
根据本申请的一些实施例，正极材料包括锂过渡金属氧化物，其中Li与O的层间距范围为
Figure PCTCN2021080597-appb-000007
至
Figure PCTCN2021080597-appb-000008
According to some embodiments of the present application, the cathode material includes a lithium transition metal oxide, wherein the interlayer distance between Li and O ranges from
Figure PCTCN2021080597-appb-000007
to
Figure PCTCN2021080597-appb-000008
根据本申请的一些实施例，正极材料包括锂过渡金属氧化物，锂过渡金属氧化物中含有过渡金属元素Me，过渡金属元素Me包括Ni元素，基于过渡金属元素Me的摩尔量，Ni元素的摩尔百分比≥50％。According to some embodiments of the present application, the cathode material includes a lithium transition metal oxide, the lithium transition metal oxide contains a transition metal element Me, and the transition metal element Me includes Ni element, based on the molar amount of transition metal element Me, the mole of Ni element Percentage ≥ 50%.
根据本申请的一些实施例，正极材料包括由一次颗粒组成的二次颗粒，一次颗粒的平均粒径为0.1μm至1.5μm，二次颗粒的平均粒径为1μm至30μm。According to some embodiments of the present application, the positive electrode material includes secondary particles composed of primary particles, the average particle diameter of the primary particles is 0.1 μm to 1.5 μm, and the average particle diameter of the secondary particles is 1 μm to 30 μm.
根据本申请的一些实施例，正极材料包括Li xNi yCo zMn kZ qO b-aT a，其中，Z包括B、Mg、Al、Si、P、S、Ti、Cr、Fe、Cu、Zn、Ga、Y、Zr、Mo、Ag、W、In、Sn、Pb、Sb、Sr和Ce中的至少一种，T为卤素，并且x、y、z、k、q、a和b分别满足：0.2＜x≤1.2、0＜y≤1、0≤z≤1、0≤k≤1、0≤q≤1、1≤b≤2以及0≤a≤1；优选地，0.6≤x≤1.2、0.5≤y≤1、0≤z≤0.5、0≤k≤0.5、0≤q≤0.5、1.5≤b≤2以及0≤a≤0.5。 According to some embodiments of the present application, the cathode material includes Li x Ni y Co z Mn k Z q O ba Ta , wherein Z includes B, Mg, Al, Si, P, S, Ti, Cr, Fe, Cu, at least one of Zn, Ga, Y, Zr, Mo, Ag, W, In, Sn, Pb, Sb, Sr, and Ce, T is a halogen, and x, y, z, k, q, a, and b are respectively Satisfy: 0.2<x≤1.2, 0<y≤1, 0≤z≤1, 0≤k≤1, 0≤q≤1, 1≤b≤2, and 0≤a≤1; preferably, 0.6≤x ≤1.2, 0.5≤y≤1, 0≤z≤0.5, 0≤k≤0.5, 0≤q≤0.5, 1.5≤b≤2, and 0≤a≤0.5.
根据本申请的另一层面，本申请提供一种电化学装置，所述电化学装置包括根据本申请前述的正极材料。According to another aspect of the present application, the present application provides an electrochemical device comprising the positive electrode material as previously described in the present application.
根据本申请的另一层面，本申请提供一种电子设备，所述电子设备包括根据本申请前述的电化学装置。According to another aspect of the application, the application provides an electronic device comprising the electrochemical device as previously described in the application.
本申请的技术方案至少具有以下有益的效果：本申请提供的正极材料的晶体结构具有特定的空间群，利于材料体相的金属离子比如锂离子的扩散，能够提高正极材料的动力学性能，并可以有效提高正极材料的容量性能、库伦效率及循环性能。The technical solution of the present application has at least the following beneficial effects: the crystal structure of the positive electrode material provided by the present application has a specific space group, which is conducive to the diffusion of metal ions such as lithium ions in the bulk phase of the material, and can improve the kinetic performance of the positive electrode material, and It can effectively improve the capacity performance, Coulomb efficiency and cycle performance of the cathode material.
本申请实施例的额外层面及优点将部分地在后续说明中描述、显示、或是经由本申请实施例的实施而阐释。Additional aspects and advantages of the embodiments of the present application will be described, shown, or explained in part through the implementation of the embodiments of the present application in the subsequent description.
附图说明Description of drawings
在下文中将简要地说明为了描述本申请实施例或现有技术所必要的附图以便于描述本申请的实施例。显而易见地，下文描述中的附图仅只是本申请中的部分实施例。对本领域技术人员而言，依然可以根据这些附图中所例示的结构来获得其他实施例的附图。Hereinafter, drawings necessary to describe the embodiments of the present application or the related art will be briefly described in order to facilitate the description of the embodiments of the present application. Obviously, the drawings in the following description are only some embodiments of the present application. For those skilled in the art, drawings of other embodiments can still be obtained according to the structures illustrated in these drawings.
图1为本申请实施例1提供的正极材料的Li与O的层间距的示意图；1 is a schematic diagram of the interlayer distance between Li and O of the positive electrode material provided in Example 1 of the present application;
图2为本申请对比例1提供的正极材料的Li与O的层间距的示意图；2 is a schematic diagram of the interlayer distance between Li and O of the positive electrode material provided in Comparative Example 1 of the present application;
图3为本申请示例性的一种实施方式提供的正极材料Li/Ni互占位的示意图；FIG. 3 is a schematic diagram of Li/Ni mutual occupancy of positive electrode materials provided by an exemplary embodiment of the present application;
图4为本申请实施例1提供的正极材料的X射线衍射谱图(XRD图)。FIG. 4 is an X-ray diffraction pattern (XRD pattern) of the cathode material provided in Example 1 of the present application.
具体实施方式Detailed ways
本申请的实施例将会被详细的描示在下文中。本申请的实施例不应该被解释为对本申请的限制。Embodiments of the present application will be described in detail below. The embodiments of the present application should not be construed as limitations of the present application.
在具体实施方式及权利要求书中，由术语“中的至少一者”、“中的至少一个”、“中的至少一种”或其他相似术语所连接的项目的列表可意味着所列项目的任何组合。例如，如果列出项目A、B，那么短语“A、B中的至少一者”意味着仅A；仅B；或A及B。在另一实例中，如果列出项目A、B、C，那么短语“A、B、C中的至少一者”意味着仅A；或仅B；仅C；A及B(排除C)；A及C(排除B)；B及C(排除A)；或A、B及C的全部。项目A可包含单个元件或多个元件。项目B可包含单个元件或多个元件。项目C可包含单个元件或多个元件。In the Detailed Description and the Claims, a list of items joined by the terms "at least one of," "at least one of," "at least one of," or other similar terms may mean the listed items any combination of . For example, if items A, B are listed, the phrase "at least one of A, B" means A only; B only; or A and B. In another example, if items A, B, C are listed, the phrase "at least one of A, B, C" means A only; or B only; C only; A and B (excluding C); A and C (excluding B); B and C (excluding A); or all of A, B, and C. Item A may contain a single element or multiple elements. Item B may contain a single element or multiple elements. Item C may contain a single element or multiple elements.
另外，有时在本文中以范围格式呈现量、比率和其它数值。应理解，此类范围格式是用于便利及简洁起见，且应灵活地理解，不仅包含明确地指定为范围限制的数值，而且包含涵盖于所述范围内的所有个别数值或子范围，如同明确地指定每一数值及子范围一般。In addition, amounts, ratios, and other numerical values are sometimes presented herein in a range format. It is to be understood that such range format is used for convenience and brevity, and that it is to be understood flexibly to include not only the numerical values expressly designated as the limits of the range, but also all individual numerical values or subranges subsumed within the stated range, as if expressly Specify each numerical value and subrange generically.
一、正极材料1. Positive electrode material
高镍三元正极材料为若干种用于电化学装置如锂离子电池中的正极材料中的一种材料。高镍三元正极材料具有动力学性能有待改善或在合成过程中容易出现锂镍混排等问题。相关技术中，为改善高镍三元正极材料的动力学性能，一般会从以下几个方面进行优化：通过降低颗粒粒径的方式；通过在锂层掺杂离子半径大的元素的方式；通过在表面包覆快离子导体的方式。然而，通过降低颗粒粒径的方式，会降低材料的压实密度，从而影响材料的能量密度；此外，颗粒粒径越小，意味着材料的比表面积BET会越大，材料和电解液的副反应会增加。通过在锂层掺杂离子半径大的元素的方式属于常见的扩大锂层间距的方法，但是该方法对掺杂元素、掺杂工艺要求高，并且掺杂量比较小，所能发挥的作用有限。通过在表面包覆快离子导体的方式属于一种辅助解决方案，并不能从根本上解决正极材料体相的金属离子如锂离子的扩散问题，对于改善材料的动力学所起的效果较差。A high nickel ternary cathode material is one of several cathode materials used in electrochemical devices such as lithium ion batteries. High-nickel ternary cathode materials have problems such as kinetic properties that need to be improved or lithium-nickel mixing and other problems are prone to occur during the synthesis process. In the related art, in order to improve the dynamic performance of high-nickel ternary cathode materials, optimization is generally carried out from the following aspects: by reducing the particle size of the particles; by doping the lithium layer with an element with a large ionic radius; by The way to coat fast ion conductors on the surface. However, by reducing the particle size, the compaction density of the material will be reduced, thereby affecting the energy density of the material; in addition, the smaller the particle size, the larger the specific surface area BET of the material, and the adverse effect of the material and the electrolyte. The response will increase. Doping the lithium layer with an element with a large ionic radius is a common method to expand the distance between the lithium layers, but this method has high requirements for doping elements and doping process, and the doping amount is relatively small, so it can play a limited role. . The method of coating fast ion conductors on the surface is an auxiliary solution, which cannot fundamentally solve the diffusion problem of metal ions such as lithium ions in the bulk phase of the positive electrode material, and has a poor effect on improving the kinetics of the material.
至少基于对现有技术的上述洞察，并鉴于正极材料对电化学装置的电化学性能的影响至关重要，本申请对正极材料的结构性能展开了进一步的大量研究，以期改善电化学装置的电化学性能，尤其改善电化学装置的放电比容量、首圈库伦效率和循环性能，致力于获得一种电化学性能更优异的电化学装置。Based on at least the above insights into the prior art, and given that the impact of cathode materials on the electrochemical performance of electrochemical devices is crucial, the present application conducts further extensive research on the structural properties of cathode materials with a view to improving the electrical properties of electrochemical devices. Chemical properties, especially improving the discharge specific capacity, first-cycle Coulombic efficiency and cycle performance of electrochemical devices, are devoted to obtaining an electrochemical device with better electrochemical performance.
在本申请的一个方面，本申请提供了一种正极材料。根据本申请的一些实施例，所述正极材料具有属于空间群Cmc2 1的晶体结构。 In one aspect of the present application, the present application provides a positive electrode material. According to some embodiments of the present application, the cathode material has a crystal structure belonging to space group Cmc2 1 .
本申请实施例提供的正极材料的晶体结构具有特定的空间群，其空间群为Cmc2 1，增大了锂层间距范围，更利于材料体相的锂离子的扩散，结 构更加稳定，能够提高正极材料的动力学性能，并可以有效提高正极材料的容量性能、库伦效率及循环性能。 The crystal structure of the positive electrode material provided in the embodiment of the present application has a specific space group, and the space group is Cmc2 1 , which increases the range of the lithium interlayer spacing, which is more conducive to the diffusion of lithium ions in the bulk phase of the material, and has a more stable structure, which can improve the performance of the positive electrode. The kinetic properties of the material can be effectively improved, and the capacity performance, Coulomb efficiency and cycle performance of the cathode material can be effectively improved.
在一些实施例中，在所述正极材料的X射线衍射(XRD)谱图中，003晶面衍射峰位于12°至18.5°范围内。当003晶面衍射峰在此范围内时，正极材料的动力学性能更优异，且正极材料的结构稳定，表现为正极材料的放电比容量、首圈库伦效率和循环性能更好。In some embodiments, in the X-ray diffraction (XRD) spectrum of the cathode material, the 003 crystal plane diffraction peak is located in the range of 12° to 18.5°. When the diffraction peak of the 003 crystal plane is within this range, the kinetic properties of the cathode material are better, and the structure of the cathode material is stable, which shows that the discharge specific capacity, the first cycle Coulomb efficiency and the cycle performance of the cathode material are better.
在一些实施例中，在所述正极材料的X射线衍射(XRD)谱图中，003晶面衍射峰与104晶面衍射峰的强度比I (003)/I (104)满足：I (003)/I (104)≥1.8。在一些实施例中，在所述正极材料的XRD谱图中，003晶面衍射峰与104晶面衍射峰的强度比I (003)/I (104)满足：I (003)/I (104)≥2.0。在一些实施例中，在所述正极材料的XRD谱图中，003晶面衍射峰与104晶面衍射峰的强度比I (003)/I (104)满足：1.8≤I (003)/I (104)≤2.6。 In some embodiments, in the X-ray diffraction (XRD) spectrum of the cathode material, the intensity ratio of the 003 crystal plane diffraction peak and the 104 crystal plane diffraction peak, I (003) /I (104) satisfies: I (003 ) /I (104) ≥ 1.8. In some embodiments, in the XRD spectrum of the cathode material, the intensity ratio of the 003 crystal plane diffraction peak to the 104 crystal plane diffraction peak, I (003) /I (104) satisfies: I (003) /I (104 ) ≥2.0. In some embodiments, in the XRD spectrum of the cathode material, the intensity ratio of the 003 crystal plane diffraction peak to the 104 crystal plane diffraction peak I (003) /I (104) satisfies: 1.8≤I (003) /I (104) ≤2.6.
根据本申请实施例的正极材料具有属于空间群Cmc2 1的晶体结构，且XRD图谱中的003晶面和104晶面衍射峰的强度比I (003)/I (104)满足：I (003)/I (104)≥1.8，由此，材料中的Li层和过渡金属层之间的Li的扩散性可以得以提高，Li在过渡金属层中的占有率适宜，晶体结构在热力学上更为稳定，从而正极材料适于实现高容量的装置，同样，可以认为正极材料也适于实现循环性能优良的电化学装置。 The cathode material according to the embodiment of the present application has a crystal structure belonging to the space group Cmc2 1 , and the intensity ratio of the diffraction peaks of the 003 crystal plane and the 104 crystal plane in the XRD pattern satisfies: I ( 003) /I (104 ) /I (104) ≥1.8, thus, the diffusivity of Li between the Li layer and the transition metal layer in the material can be improved, the occupancy rate of Li in the transition metal layer is appropriate, and the crystal structure is more thermodynamically stable. , so that the positive electrode material is suitable for realizing high-capacity devices, and similarly, it can be considered that the positive electrode material is also suitable for realizing electrochemical devices with excellent cycle performance.
在一些实施例中，所述正极材料的晶胞参数a的范围为≥
Figure PCTCN2021080597-appb-000009
在一些实施例中，晶胞参数c的范围为≥
Figure PCTCN2021080597-appb-000010
在一些实施例中，晶胞参数c/晶胞参数a的范围为≥4.95。在一些实施例中，所述正极材料的晶胞参数a的范围为
Figure PCTCN2021080597-appb-000011
至
Figure PCTCN2021080597-appb-000012
在一些实施例中，晶胞参数c的范围为
Figure PCTCN2021080597-appb-000013
至
Figure PCTCN2021080597-appb-000014
在一些实施例中，晶胞参数c/晶胞参数a的范围为4.95至6.68。当正极材料的晶胞参数a、晶胞参数c以及晶胞参数c与晶胞参数a的比值在上述范围内时，正极材料的结构更为稳定，表现为正极材料的循环性能更好；同时更利于锂离子的脱出和嵌入，可更好地提高正极材料的放电比容量及库伦效率。 In some embodiments, the range of the unit cell parameter a of the cathode material is ≥
Figure PCTCN2021080597-appb-000009
In some embodiments, the range of the unit cell parameter c is ≥
Figure PCTCN2021080597-appb-000010
In some embodiments, the range of unit cell parameter c/unit cell parameter a is > 4.95. In some embodiments, the range of the unit cell parameter a of the cathode material is
Figure PCTCN2021080597-appb-000011
to
Figure PCTCN2021080597-appb-000012
In some embodiments, the range of the unit cell parameter c is
Figure PCTCN2021080597-appb-000013
to
Figure PCTCN2021080597-appb-000014
In some embodiments, the unit cell parameter c/unit cell parameter a ranges from 4.95 to 6.68. When the unit cell parameter a, the unit cell parameter c and the ratio of the unit cell parameter c to the unit cell parameter a of the positive electrode material are within the above ranges, the structure of the positive electrode material is more stable, and the cycle performance of the positive electrode material is better; It is more conducive to the extraction and insertion of lithium ions, and can better improve the discharge specific capacity and Coulomb efficiency of the cathode material.
在一些实施例中，所述正极材料包括锂过渡金属氧化物，其中Li与O的层间距范围为
Figure PCTCN2021080597-appb-000015
至
Figure PCTCN2021080597-appb-000016
在一些实施例中，所述正极材料包括锂过渡金属氧化物，其中Li与O的层间距范围为
Figure PCTCN2021080597-appb-000017
至
Figure PCTCN2021080597-appb-000018
在一些实施例中，所述正极材料包括锂过渡金属氧化物，其中Li与O的层间距范围为
Figure PCTCN2021080597-appb-000019
至
Figure PCTCN2021080597-appb-000020
锂层间距的增大，更利于锂离子的扩散，能使得锂离子更顺畅的迁移，从而可提高正极材料的放电比容量及库伦效率，改善正极材料的循环性能。 In some embodiments, the cathode material includes a lithium transition metal oxide, wherein the interlayer distance between Li and O is in the range of
Figure PCTCN2021080597-appb-000015
to
Figure PCTCN2021080597-appb-000016
In some embodiments, the cathode material includes a lithium transition metal oxide, wherein the interlayer distance between Li and O is in the range of
Figure PCTCN2021080597-appb-000017
to
Figure PCTCN2021080597-appb-000018
In some embodiments, the cathode material includes a lithium transition metal oxide, wherein the interlayer distance between Li and O is in the range of
Figure PCTCN2021080597-appb-000019
to
Figure PCTCN2021080597-appb-000020
The increase of the lithium interlayer spacing is more conducive to the diffusion of lithium ions, which can make the lithium ions migrate more smoothly, thereby improving the discharge specific capacity and Coulomb efficiency of the cathode material, and improving the cycle performance of the cathode material.
在一些实施例中，正极材料包括锂过渡金属氧化物，锂过渡金属氧化物中含有过渡金属元素Me，过渡金属元素Me包括Ni元素，基于过渡金属元素Me的摩尔量，Ni元素的摩尔百分比≥50％。在一些实施例中，正极材料包括锂过渡金属氧化物，锂过渡金属氧化物中含有过渡金属元素Me，过渡金属元素Me包括Ni元素，基于过渡金属元素Me的摩尔量， Ni元素的摩尔百分比≥70％。一些实施例中，正极材料包括锂过渡金属氧化物，锂过渡金属氧化物中含有过渡金属元素Me，过渡金属元素Me包括Ni元素，基于过渡金属元素Me的摩尔量，Ni元素的摩尔百分比≥80％。In some embodiments, the positive electrode material includes a lithium transition metal oxide, the lithium transition metal oxide contains a transition metal element Me, the transition metal element Me includes Ni element, and based on the molar amount of the transition metal element Me, the mole percentage of Ni element is ≥ 50%. In some embodiments, the positive electrode material includes a lithium transition metal oxide, the lithium transition metal oxide contains a transition metal element Me, the transition metal element Me includes Ni element, and based on the molar amount of the transition metal element Me, the mole percentage of Ni element ≥ 70%. In some embodiments, the positive electrode material includes a lithium transition metal oxide, the lithium transition metal oxide contains a transition metal element Me, the transition metal element Me includes Ni element, and based on the molar amount of the transition metal element Me, the mole percentage of Ni element is greater than or equal to 80. %.
在一些实施例中，该正极材料为高镍三元正极材料，即Ni元素的摩尔百分比(相对除Li以外的总金属元素)不低于50％。In some embodiments, the positive electrode material is a high-nickel ternary positive electrode material, that is, the molar percentage of Ni element (relative to the total metal elements other than Li) is not less than 50%.
在一些实施例中，所述正极材料中含有S元素，基于所述正极材料的质量，所述S元素的质量百分含量为≥0.1％。In some embodiments, the positive electrode material contains S element, and based on the mass of the positive electrode material, the mass percentage of the S element is ≥0.1%.
在一些实施例中，所述正极材料包括由一次颗粒组成的二次颗粒，所述一次颗粒的平均粒径为0.1μm至1.5μm，所述二次颗粒的平均粒径为1μm至30μm。In some embodiments, the positive electrode material includes secondary particles composed of primary particles, the average particle diameter of the primary particles is 0.1 μm to 1.5 μm, and the average particle diameter of the secondary particles is 1 μm to 30 μm.
正极材料的颗粒大小将影响电化学装置的容量、倍率性能和循环性能。通常来说，包括由一次颗粒形成的二次颗粒的正极材料中，一次颗粒的粒径大小适宜，有利于提高正极材料的循环性能及倍率性能。并且，还能够使正极活性材料获得较高的容量发挥，从而提高电池的能量密度。The particle size of the cathode material will affect the capacity, rate capability and cycling performance of electrochemical devices. Generally speaking, in the positive electrode material including the secondary particles formed by the primary particles, the particle size of the primary particles is suitable, which is beneficial to improve the cycle performance and rate performance of the positive electrode material. In addition, the positive electrode active material can also be made to exert higher capacity, thereby improving the energy density of the battery.
正极材料的平均粒径在适当的范围内，可以使电化学装置同时兼具良好的动力学性能和较高的能量密度，有利于提高材料及电化学装置的综合性能。When the average particle size of the positive electrode material is in an appropriate range, the electrochemical device can have both good kinetic performance and high energy density at the same time, which is beneficial to improve the comprehensive performance of the material and the electrochemical device.
在一些实施例中，所述二次颗粒的平均粒径为5μm至20μm。在一些实施例中，所述二次颗粒的平均粒径为10μm至20μm。In some embodiments, the secondary particles have an average particle size of 5 μm to 20 μm. In some embodiments, the secondary particles have an average particle size of 10 μm to 20 μm.
在一些实施例中，所述正极材料包括Li xNi yCo zMn kZ qO b-aT a，其中，Z包括B、Mg、Al、Si、P、S、Ti、Cr、Fe、Cu、Zn、Ga、Y、Zr、Mo、Ag、W、In、Sn、Pb、Sb和Ce中的至少一种，T为卤素，并且x、y、z、k、q、a和b分别满足：0.2＜x≤1.2、0＜y≤1、0≤z≤1、0≤k≤1、0≤q≤1、1≤b≤2以及0≤a≤1。优选地，在一些实施例中，0.6≤x≤1.2、0.5≤y≤1、0≤z≤0.5、0≤k≤0.5、0≤q≤0.5、1.5≤b≤2以及0≤a≤0.5。 In some embodiments, the cathode material includes Li x Ni y Co z Mn k Z q O ba Ta , wherein Z includes B, Mg, Al, Si, P, S, Ti, Cr, Fe, Cu, At least one of Zn, Ga, Y, Zr, Mo, Ag, W, In, Sn, Pb, Sb and Ce, T is halogen, and x, y, z, k, q, a and b satisfy: 0.2<x≤1.2, 0<y≤1, 0≤z≤1, 0≤k≤1, 0≤q≤1, 1≤b≤2, and 0≤a≤1. Preferably, in some embodiments, 0.6≤x≤1.2, 0.5≤y≤1, 0≤z≤0.5, 0≤k≤0.5, 0≤q≤0.5, 1.5≤b≤2, and 0≤a≤0.5 .
在一些实施例中，正极材料可以包括钴酸锂、镍钴锰酸锂(三元正极材料)、锰酸锂等含锂过渡金属氧化物中的至少一种。在一些实施例中，正极材料包括高镍三元正极材料。In some embodiments, the cathode material may include at least one of lithium-containing transition metal oxides such as lithium cobalt oxide, lithium nickel cobalt manganate (ternary cathode material), and lithium manganate. In some embodiments, the cathode material includes a high nickel ternary cathode material.
通常的，高镍三元正极材料的制备，是通过使用β相R 3m前驱体Ni 1-x-yCo xMn y(OH) 2和锂盐LiOH·H 2O混合后在氧气气氛下烧结得到。然而，在制备过程中前驱体中的Ni为+2价，很难完全被氧化为+3价，由于Ni 2+离子半径和Li +半径非常接近，在合成过程中容易出现锂镍混排，导致材料一部分锂不能发挥出来，从而降低材料容量。此外，即使通过调控合成工艺条件，得到标准化学计量比的高镍正极材料，也会由于所采用的前驱体为β-Ni 1-x-yCo xMn y(OH) 2，使得高镍材料锂层间距较小，锂离子扩散困难，降低了动力学性能。 Usually, the preparation of high-nickel ternary cathode materials is obtained by mixing β-phase R 3 m precursor Ni 1-xy Co x M y (OH) 2 and lithium salt LiOH·H 2 O and sintering in oxygen atmosphere. . However, during the preparation process, Ni in the precursor has a valence of +2, and it is difficult to be completely oxidized to a valence of +3. Since the ionic radius of Ni 2+ and the radius of Li + are very close, it is easy to mix lithium and nickel during the synthesis process. As a result, part of the lithium of the material cannot be exerted, thereby reducing the capacity of the material. In addition, even if the standard stoichiometric ratio of high-nickel cathode material is obtained by adjusting the synthesis process conditions, the high-nickel material lithium layer will be formed because the precursor used is β-Ni 1-xy Co x M y (OH) 2 . The smaller spacing makes it difficult for lithium ions to diffuse, reducing the kinetic performance.
根据本申请的实施例，正极材料可以为高镍三元正极材料，该高镍三元正极材料可以通过以下方法制备得到：将α-Ni 1-x-yCo xMn y(OH) 2作为三元正极材料的前驱体，使α-Ni 1-x-yCo xMn y(OH) 2作为与锂盐混合后，通过固相 烧结的方式，可以得到具有属于空间群Cmc2 1的晶体结构的正极材料，并且所得到的正极材料具有更大的层间距，比如Li与O的层间距范围为
Figure PCTCN2021080597-appb-000021
至
Figure PCTCN2021080597-appb-000022
由于锂层间距远大于Ni-O键长，抑制了Ni容易在锂层形成Li/Ni互占位，缓解了现有的三元材料存在的动力学性能差、大倍率放电温升高、锂镍混排等问题。当然，该正极材料并不限于此，正极材料的制备方法也并不限于此，而是还可以采用的其他方法进行制备。 According to the embodiment of the present application, the positive electrode material can be a high-nickel ternary positive electrode material, and the high-nickel ternary positive electrode material can be prepared by the following method: using α-Ni 1-xy Co x M y (OH) 2 as a ternary The precursor of the positive electrode material is mixed with α-Ni 1-xy Co x M y (OH) 2 as a lithium salt, and the positive electrode material with the crystal structure belonging to the space group Cmc2 1 can be obtained by solid-phase sintering, And the obtained cathode material has a larger interlayer distance, for example, the interlayer distance between Li and O ranges from
Figure PCTCN2021080597-appb-000021
to
Figure PCTCN2021080597-appb-000022
Since the distance between the lithium layers is much larger than the Ni-O bond length, it inhibits the easy formation of Li/Ni mutual occupation by Ni in the lithium layer, and alleviates the poor kinetic properties, high-rate discharge temperature, and lithium Nickel mixed row and other issues. Of course, the positive electrode material is not limited to this, and the preparation method of the positive electrode material is not limited to this, but can also be prepared by other methods.
除非特别规定，本说明书中涉及的各种参数具有本领域公知的通用含义，可以按本领域公知的方法进行测定，在此不再详细描述。Unless otherwise specified, various parameters involved in this specification have general meanings known in the art, and can be determined by methods known in the art, and will not be described in detail here.
二、电化学装置2. Electrochemical device
在一些实施例中，本申请提供一种电化学装置，其包括正极、负极、电解液及设置于正极和负极之间的隔离膜。In some embodiments, the present application provides an electrochemical device comprising a positive electrode, a negative electrode, an electrolyte, and a separator disposed between the positive electrode and the negative electrode.
本申请的电化学装置可以为锂离子电池或锂金属电池，也可以为其他任何合适的电化学装置。例如，在不背离本申请公开的内容的基础上，本申请实施例中的电化学装置包括发生电化学反应的任何装置，它的具体实例包括所有种类的一次电池、二次电池、燃料电池、太阳能电池或电容器。特别地，该电化学装置是锂二次电池，锂二次电池包括但不限于锂金属二次电池、锂离子二次电池、锂聚合物二次电池或锂离子聚合物二次电池。本申请的电化学装置是具备具有能够吸留、放出金属离子的正极活性物质的正极以及具备能够吸留、放出金属离子的负极活性物质的负极的电化学装置，其主要特点在于，包括本申请的上述任何正极材料。从而，本申请实施例的电化学装置由于包含上述正极材料，使其能够缓解现有的电化学装置中正极材料动力学性能较差、合成过程中会出现锂镍混排的问题，可以提高电化学装置的动力学性能和循环性能。The electrochemical device of the present application can be a lithium ion battery or a lithium metal battery, and can also be any other suitable electrochemical device. For example, without departing from the content disclosed in the present application, the electrochemical device in the embodiments of the present application includes any device that undergoes an electrochemical reaction, and specific examples thereof include all kinds of primary batteries, secondary batteries, fuel cells, Solar cells or capacitors. In particular, the electrochemical device is a lithium secondary battery including, but not limited to, a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery. The electrochemical device of the present application is an electrochemical device including a positive electrode having a positive electrode active material capable of occluding and releasing metal ions, and a negative electrode having a negative electrode active material capable of absorbing and releasing metal ions. of any of the above cathode materials. Therefore, since the electrochemical device of the embodiment of the present application includes the above-mentioned positive electrode material, it can alleviate the problems of poor kinetic performance of the positive electrode material in the existing electrochemical device and the mixed arrangement of lithium and nickel during the synthesis process, which can improve the efficiency of the electrochemical device. Kinetic and cycling performance of chemical devices.
本申请的电化学装置中使用的正极材料为本申请的上述任何正极材料。此外，本申请的电化学装置中使用的正极材料还可包含不脱离本申请的主旨的范围内的其它正极材料。The positive electrode material used in the electrochemical device of the present application is any of the above-mentioned positive electrode materials of the present application. In addition, the positive electrode material used in the electrochemical device of the present application may further include other positive electrode materials within the scope of not departing from the gist of the present application.
正极positive electrode
在一些实施例中，正极包括正极集流体和设置在正极集流体至少一个表面上的正极活性物质层，其中的正极活性物质层包括前述的正极材料。In some embodiments, the positive electrode includes a positive electrode current collector and a positive electrode active material layer disposed on at least one surface of the positive electrode current collector, wherein the positive electrode active material layer includes the aforementioned positive electrode material.
在一些实施例中，正极活性物质层还包括粘结剂。粘结剂可提高正极材料颗粒彼此间的结合，并且可提高正极材料与正极集流体的结合。在一些实施例中，所述粘结剂包括，但不限于，聚乙烯醇、羟丙基纤维素、二乙酰基纤维素、聚氯乙烯、羧化的聚氯乙烯、聚氟乙烯、含亚乙基氧的聚合物、聚乙烯吡咯烷酮、聚氨酯、聚四氟乙烯、聚偏1,1-二氟乙烯、聚乙烯、聚丙烯、丁苯橡胶、丙烯酸(酯)化的丁苯橡胶、环氧树脂和尼龙等。In some embodiments, the positive active material layer further includes a binder. The binder can improve the bonding of the positive electrode material particles to each other, and can improve the bonding of the positive electrode material to the positive electrode current collector. In some embodiments, the binder includes, but is not limited to, polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polyvinyl Ethoxylated polymers, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy Resin and nylon, etc.
在一些实施例中，所述粘结剂包括聚偏氟乙烯(PVDF)、羧甲基纤维素和丁苯橡胶中的至少一种。In some embodiments, the binder includes at least one of polyvinylidene fluoride (PVDF), carboxymethyl cellulose, and styrene-butadiene rubber.
在一些实施例中，正极活性物质层还包括导电剂，从而赋予电极导电性。该导电剂可以包括任何导电材料，只要它不引起不想要的化学变化。 在一些实施例中，导电剂包括，但不限于，基于碳的材料、基于金属的材料、导电聚合物和它们的混合物。在一些实施例中，基于碳的材料可以选自天然石墨、人造石墨、碳黑、乙炔黑、科琴黑、碳纤维或其任意组合；基于金属的材料可以选自金属粉、金属纤维、铜、镍、铝、银或其任意组合；导电聚合物可以选自聚亚苯基衍生物。In some embodiments, the positive electrode active material layer further includes a conductive agent, thereby imparting conductivity to the electrode. The conductive agent may include any conductive material as long as it does not cause unwanted chemical changes. In some embodiments, conductive agents include, but are not limited to, carbon-based materials, metal-based materials, conductive polymers, and mixtures thereof. In some embodiments, the carbon-based material may be selected from natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fiber, or any combination thereof; the metal-based material may be selected from metal powder, metal fiber, copper, Nickel, aluminum, silver, or any combination thereof; the conductive polymer may be selected from polyphenylene derivatives.
在一些实施例中，导电剂包括导电碳黑、乙炔黑、石墨烯、科琴黑和导电纳米管中的至少一种。In some embodiments, the conductive agent includes at least one of conductive carbon black, acetylene black, graphene, ketjen black, and conductive nanotubes.
上述正极活性物质层中的粘结剂和导电剂以及两者的种类和含量不受具体的限制，可根据实际需求进行选择。The binder and the conductive agent in the above-mentioned positive electrode active material layer, as well as the types and contents of the two are not specifically limited, and can be selected according to actual needs.
在一些实施例中，正极集流体可以为本领域常用的正极集流体。该正极集流体为金属，金属例如包括但不限于铝箔或镍箔。In some embodiments, the positive electrode current collector may be a positive electrode current collector commonly used in the art. The positive electrode current collector is metal, such as but not limited to aluminum foil or nickel foil.
在一些实施例中，正极的结构为本领域技术公知的可被用于电化学装置的正极极片结构。In some embodiments, the structure of the positive electrode is a positive electrode plate structure known in the art that can be used in an electrochemical device.
在一些实施例中，正极的制备方法是本领域技术公知的可被用于电化学装置的正极的制备方法。例如，正极可以通过如下方法获得：在溶剂中将正极材料、导电剂和粘结剂混合，以制备浆料，并将该浆料涂覆在集流体上。在一些实施例中，溶剂可以包括水、N-甲基吡咯烷酮等，但不限于此。In some embodiments, the method of making the positive electrode is known to those skilled in the art as a method of making a positive electrode that can be used in an electrochemical device. For example, a positive electrode can be obtained by mixing a positive electrode material, a conductive agent, and a binder in a solvent to prepare a slurry, and coating the slurry on a current collector. In some embodiments, the solvent may include water, N-methylpyrrolidone, etc., but is not limited thereto.
负极negative electrode
在一些实施例中，所述负极包括负极集流体和设置在负极集流体至少一个表面上的负极活性物质层。在一些实施例中，负极活性物质层包括负极活性材料，负极活性材料可以包括可逆地嵌入/脱嵌锂离子的材料、锂金属、锂金属合金或过渡金属氧化物。在一些实施例中，负极活性材料包括碳材料或硅材料中的至少一种，碳材料包括石墨、硬碳中的至少一种，硅材料包括硅、硅氧化合物、硅碳化合物或硅合金中的至少一种。在一些实施例中，以含锂金属片层作为负极活性物质层。例如，负极集流体在自身厚度方向上包括相对的两个表面，含锂金属片层层叠设置于负极集流体的两个表面中的任意一者或两者上。所述含锂金属片层可以是通过机械辊轧、气相沉积法、化学镀中的至少一种手段形成于负极集流体上。In some embodiments, the negative electrode includes a negative electrode current collector and a negative electrode active material layer disposed on at least one surface of the negative electrode current collector. In some embodiments, the anode active material layer includes an anode active material, and the anode active material may include a material that reversibly intercalates/deintercalates lithium ions, lithium metal, lithium metal alloy, or transition metal oxide. In some embodiments, the negative electrode active material includes at least one of carbon material or silicon material, the carbon material includes at least one of graphite and hard carbon, and the silicon material includes silicon, silicon oxide compound, silicon carbon compound or silicon alloy at least one of. In some embodiments, a lithium-containing metal sheet layer is used as the negative electrode active material layer. For example, the negative electrode current collector includes two opposite surfaces in the thickness direction of the negative electrode current collector, and the lithium-containing metal sheet layer is laminated on either or both of the two surfaces of the negative electrode current collector. The lithium-containing metal sheet layer may be formed on the negative electrode current collector by at least one of mechanical rolling, vapor deposition, and electroless plating.
在一些实施例中，所述负极集流体可以是本领域常用的负极集流体。负极集流体可以使用金属箔材或多孔金属板等材料，例如使用铜、镍、钛或铁等金属或它们的合金的箔材或多孔板，如铜箔。In some embodiments, the negative electrode current collector may be a negative electrode current collector commonly used in the art. The negative electrode current collector can be made of materials such as metal foils or porous metal plates, for example, foils or porous plates of metals such as copper, nickel, titanium or iron or their alloys, such as copper foil.
在另一些实施例中，所述负极活性物质层包含负极活性材料、粘结剂和导电剂。负极活性材料能够可逆地嵌入和脱出锂离子。根据本申请的一些实施例，负极活性材料的具体种类均不受到具体的限制，可根据需求进行选择。In other embodiments, the negative electrode active material layer includes a negative electrode active material, a binder and a conductive agent. The negative electrode active material can reversibly intercalate and deintercalate lithium ions. According to some embodiments of the present application, the specific types of negative electrode active materials are not specifically limited, and can be selected according to requirements.
在一些实施例中，负极的结构及负极的制备方法是本领域技术公知的可被用于电化学装置的负极极片结构及本领域技术公知的可被用于电化学装置的负极的制备方法。In some embodiments, the structure of the negative electrode and the preparation method of the negative electrode are known in the art for the structure of the negative electrode plate that can be used in an electrochemical device and the preparation method for the negative electrode for the electrochemical device known in the art .
电解液Electrolyte
可用于本申请实施例的电解液可以为现有技术中已知的电解液。电解液可以分为水系电解液和非水系电解液，其中相较于水系电解液，采用非水系电解液的电化学装置可以在较宽的电压窗口下工作，从而达到较高的能量密度。在一些实施例中，非水系电解液包括有机溶剂和电解质。The electrolyte that can be used in the embodiments of the present application may be an electrolyte known in the prior art. Electrolytes can be divided into aqueous electrolytes and non-aqueous electrolytes. Compared with aqueous electrolytes, electrochemical devices using non-aqueous electrolytes can work in a wider voltage window, thereby achieving higher energy density. In some embodiments, the non-aqueous electrolyte includes an organic solvent and an electrolyte.
可用于本申请实施例的电解液中的电解质包括、但不限于：无机锂盐，例如LiClO 4、LiAsF 6、LiPF 6、LiBF 4、LiSbF 6、LiSO 3F、LiN(FSO 2) 2等；含氟有机锂盐，例如LiCF 3SO 3、LiN(FSO 2)(CF 3SO 2)、LiN(CF 3SO 2) 2、LiN(C 2F 5SO 2) 2、环状1,3-六氟丙烷二磺酰亚胺锂、环状1,2-四氟乙烷二磺酰亚胺锂、LiPF 4(CF 3) 2、LiN(CF 3SO 2)(C 4F 9SO 2)、LiC(CF 3SO 2) 3、LiPF 4(CF 3SO 2) 2、LiPF 4(C 2F 5) 2、LiPF 4(C 2F 5SO 2) 2、LiBF 2(CF 3) 2、LiBF 2(C 2F 5) 2、LiBF 2(CF 3SO 2) 2、LiBF 2(C 2F 5SO 2) 2；含二羧酸配合物锂盐，例如双(草酸根合)硼酸锂、二氟草酸根合硼酸锂、三(草酸根合)磷酸锂、二氟双(草酸根合)磷酸锂、四氟(草酸根合)磷酸锂等。另外，上述电解质可以单独使用一种，也可以同时使用两种或两种以上。 Electrolytes that can be used in the electrolyte of the embodiments of the present application include, but are not limited to: inorganic lithium salts, such as LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiSbF 6 , LiSO 3 F, LiN(FSO 2 ) 2 , etc.; Fluorine-containing organolithium salts such as LiCF 3 SO 3 , LiN(FSO 2 )(CF 3 SO 2 ), LiN(CF 3 SO 2 ) 2 , LiN(C 2 F 5 SO 2 ) 2 , cyclic 1,3- Lithium hexafluoropropanedisulfonimide, cyclic lithium 1,2-tetrafluoroethanedisulfonimide, LiPF 4 (CF 3 ) 2 , LiN(CF 3 SO 2 )(C 4 F 9 SO 2 ) , LiC(CF 3 SO 2 ) 3 , LiPF 4 (CF 3 SO 2 ) 2 , LiPF 4 (C 2 F 5 ) 2 , LiPF 4 (C 2 F 5 SO 2 ) 2 , LiBF 2 (CF 3 ) 2 , LiBF 2 (C 2 F 5 ) 2 , LiBF 2 (CF 3 SO 2 ) 2 , LiBF 2 (C 2 F 5 SO 2 ) 2 ; lithium salts containing dicarboxylic acid complexes, such as lithium bis(oxalato)borate , Lithium difluorooxalatoborate, tris (oxalato) lithium phosphate, difluorobis (oxalato) lithium phosphate, tetrafluoro (oxalato) lithium phosphate, etc. In addition, the said electrolyte may be used individually by 1 type, and may use 2 or more types together.
可用于本申请实施例的电解液中的有机溶剂可为现有技术中已知的任何有机溶剂。在一些实施例中，有机溶剂，包括，但不限于：碳酸酯化合物、基于酯的化合物、基于醚的化合物、基于酮的化合物、基于醇的化合物、非质子溶剂或它们的组合。其中，碳酸酯化合物的实例包括，但不限于，链状碳酸酯化合物、环状碳酸酯化合物、氟代碳酸酯化合物或它们的组合。在一些实施例中，有机溶剂包括碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)、碳酸二甲酯(DMC)、碳酸亚丙酯、丙酸丙酯和丙酸乙酯中的至少一种。The organic solvent that can be used in the electrolyte in the embodiments of the present application can be any organic solvent known in the prior art. In some embodiments, organic solvents include, but are not limited to, carbonate compounds, ester-based compounds, ether-based compounds, ketone-based compounds, alcohol-based compounds, aprotic solvents, or combinations thereof. Among them, examples of the carbonate compound include, but are not limited to, a chain carbonate compound, a cyclic carbonate compound, a fluorocarbonate compound, or a combination thereof. In some embodiments, the organic solvent includes ethylene carbonate (EC), propylene carbonate (PC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), propylene carbonate at least one of ester, propyl propionate and ethyl propionate.
隔离膜isolation film
隔离膜可以是本领域各种适用于电化学储能装置隔离膜的材料，例如，可以是包括但不限于聚乙烯、聚丙烯、聚偏氟乙烯、芳纶、聚对苯二甲酸乙二醇酯、聚四氟乙烯、聚丙烯腈、聚酰亚胺，聚酰胺、聚酯和天然纤维中的一种或多种的组合。The separator can be any material suitable for the separator of electrochemical energy storage device in the art, for example, can be including but not limited to polyethylene, polypropylene, polyvinylidene fluoride, aramid, polyethylene terephthalate A combination of one or more of ester, polytetrafluoroethylene, polyacrylonitrile, polyimide, polyamide, polyester and natural fibers.
本申请实施例对隔离膜的材料和形状没有特别的限制，可以选用任意公知的具有电化学稳定性和化学稳定性的多孔结构隔离膜。在一些实施例中，隔离膜例如为玻璃纤维、无纺布、聚乙烯(PE)、聚丙烯(PP)及聚偏二氟乙烯(PVDF)中的一种或多种的单层或多层薄膜。There is no particular limitation on the material and shape of the separator in the embodiments of the present application, and any well-known porous-structure separator with electrochemical stability and chemical stability can be selected. In some embodiments, the release film is, for example, a single layer or multiple layers of one or more of glass fiber, non-woven fabric, polyethylene (PE), polypropylene (PP), and polyvinylidene fluoride (PVDF). film.
三、应用3. Application
在一些实施例中，本申请提供一种电子设备，其包括前述的电化学装置。In some embodiments, the present application provides an electronic device comprising the aforementioned electrochemical device.
根据本申请实施例的正极材料，可以缓解现有正极材料的动力学性能较差、大倍率放电温升高、锂镍混排的问题，能够改善电化学装置的放电比容量、首圈库伦效率及循环性能，使得由此制造的电化学装置适用于各种领域的电子设备。According to the positive electrode material of the embodiment of the present application, the problems of poor kinetic performance, high discharge temperature increase, and lithium-nickel mixed discharge of the existing positive electrode material can be alleviated, and the discharge specific capacity and the first-cycle Coulomb efficiency of the electrochemical device can be improved. and cycle performance, making the electrochemical device thus fabricated suitable for electronic equipment in various fields.
本申请的电化学装置的用途没有特别限定，其可用于现有技术中已知的任何电子设备。例如，该电子设备包括，但不限于，笔记本电脑、笔输入型计算机、移动电脑、电子书播放器、便携式电话、便携式传真机、便携式复印机、便携式打印机、头戴式立体声耳机、录像机、液晶电视、手提式清洁器、便携CD机、迷你光盘、收发机、电子记事本、计算器、存储卡、便携式录音机、收音机、备用电源、电机、汽车、摩托车、助力自行车、自行车、照明器具、玩具、游戏机、钟表、电动工具、闪光灯、照相机、家庭用大型蓄电池和锂离子电容器等。另外，本申请的电化学装置除了适用于上述例举的电子装置外，还适用于储能电站、海运运载工具、空运运载工具。空运运载装置包含在大气层内的空运运载装置和大气层外的空运运载装置。The use of the electrochemical device of the present application is not particularly limited, and it can be used in any electronic device known in the art. For example, the electronic devices include, but are not limited to, notebook computers, pen-type computers, mobile computers, e-book players, portable telephones, portable fax machines, portable copiers, portable printers, headphone headsets, video recorders, LCD televisions , portable cleaners, portable CD players, mini-discs, transceivers, electronic notepads, calculators, memory cards, portable recorders, radios, backup power supplies, motors, cars, motorcycles, power-assisted bicycles, bicycles, lighting fixtures, toys , game consoles, clocks, power tools, flash, cameras, large household batteries and lithium-ion capacitors, etc. In addition, the electrochemical device of the present application is applicable not only to the electronic devices exemplified above, but also to energy storage power stations, marine vehicles, and air vehicles. Airborne vehicles include airborne vehicles within the atmosphere and airborne vehicles outside the atmosphere.
下述实施例更具体地描述了本发明公开的内容，这些实施例仅仅用于阐述性说明，只要不脱离其主旨，本申请并不限于这些实施例，因为在本发明公开内容的范围内进行各种修改和变化对本领域技术人员来说是明显的。除非另有声明，以下实施例、对比例中使用的所有试剂都可商购获得或是按照常规方法进行合成获得，并且可直接使用而无需进一步处理，以及实施例中使用的仪器均可商购获得。The following examples more specifically describe the present disclosure, these examples are for illustrative purposes only, and the present application is not limited to these examples, as it is within the scope of the present disclosure, as long as it does not depart from the gist thereof. Various modifications and changes will be apparent to those skilled in the art. Unless otherwise stated, all reagents used in the following examples and comparative examples are either commercially available or synthesized according to conventional methods, and can be used directly without further processing, and the instruments used in the examples are commercially available get.
四、实施例Fourth, the embodiment
锂二次电池的制备Preparation of Lithium Secondary Batteries
采用以下制备方法将实施例和对比例中的正极材料制备成锂二次电池。The cathode materials in Examples and Comparative Examples were prepared into lithium secondary batteries by the following preparation methods.
(1)正极的制备：将以下实施例和对比例所制备的正极材料、导电剂乙炔黑、粘合剂聚偏二氟乙烯(PVDF)按重量比90：10：10在N-甲基吡咯烷酮中充分搅拌混合均匀制成正极浆料，然后将所得正极浆料均匀涂布在正极集电体铝箔上，之后经烘干、冷压、分条、裁片，得到正极。所得到的正极为直径为14mm的圆片。(1) Preparation of positive electrode: The positive electrode materials, conductive agent acetylene black, and binder polyvinylidene fluoride (PVDF) prepared in the following examples and comparative examples were mixed in N-methylpyrrolidone in a weight ratio of 90:10:10 The positive electrode slurry is then uniformly coated on the positive electrode current collector aluminum foil, and then dried, cold-pressed, slitted, and cut into pieces to obtain the positive electrode slurry. The obtained positive electrode was a disk with a diameter of 14 mm.
(2)负极的制备：采用直径为18mm的金属锂片作为负极。(2) Preparation of negative electrode: A metal lithium sheet with a diameter of 18 mm was used as the negative electrode.
(3)隔离膜的制备：以聚乙烯多孔膜作为隔离膜，隔离膜为直径为18mm的圆片。(3) Preparation of separator: a polyethylene porous membrane was used as the separator, and the separator was a disc with a diameter of 18 mm.
(4)电解液的制备：在干燥的氩气气氛手套箱中，将碳酸乙烯酯(EC)、碳酸二乙酯(DEC)和碳酸丙烯酯(PC)按照3：4：3的质量比混合均匀，再将充分干燥的锂盐LiPF 6溶解于上述非水溶剂中形成电解液，其中LiPF 6的含量为1mol/L。 (4) Preparation of electrolyte: In a dry argon atmosphere glove box, ethylene carbonate (EC), diethyl carbonate (DEC) and propylene carbonate (PC) were mixed in a mass ratio of 3:4:3 uniform, and then fully dried lithium salt LiPF 6 is dissolved in the above non-aqueous solvent to form an electrolyte solution, wherein the content of LiPF 6 is 1 mol/L.
(5)锂二次电池的组装：将得到的正极、隔离膜、负极、电解液、电池壳及其余相关配件，移入到含水量小于11ppm的手套箱中；按照从下到上的叠放顺序组装电池并注入电解液；在封装机上封装，得到锂二次电池。(5) Assembly of lithium secondary battery: Move the obtained positive electrode, separator, negative electrode, electrolyte, battery case and other related accessories into a glove box with a water content of less than 11 ppm; in the order of stacking from bottom to top The battery is assembled and the electrolyte is injected; it is packaged on a packaging machine to obtain a lithium secondary battery.
放电比容量测试和首次效率测试Discharge specific capacity test and first efficiency test
将锂二次电池以0.1C的倍率充电至4.3V，之后恒压充电至0.05C，再 以0.1C的倍率放电至2.8V，从而得到首次充电容量和首次放电容量。The lithium secondary battery was charged to 4.3V at a rate of 0.1C, then charged at a constant voltage to 0.05C, and then discharged to 2.8V at a rate of 0.1C to obtain the first charge capacity and first discharge capacity.
放电比容量(mAh/g)＝首次放电容量(mAh)/正极的正极材料质量(g)。Discharge specific capacity (mAh/g)=first discharge capacity (mAh)/positive electrode material mass (g) of the positive electrode.
首次效率(％)＝首次放电容量(mAh)/首次充电容量(mAh)×100％。First efficiency (%)=first discharge capacity (mAh)/first charge capacity (mAh)×100%.
循环容量保持率测试Cyclic Capacity Retention Test
采用加速循环的方式，将截止电压提升至4.5V。将完成放电比容量测试的锂二次电池在25℃下以0.5C的倍率充电至4.5V，之后恒压充电至0.05C，再以0.5C的倍率放电至2.8V，如此循环50次，然后计算50次循环后的锂二次电池容量。The cut-off voltage was raised to 4.5V by means of accelerated cycling. The lithium secondary battery that has completed the discharge specific capacity test is charged to 4.5V at a rate of 0.5C at 25°C, then charged to 0.05C at a constant voltage, and then discharged to 2.8V at a rate of 0.5C. This cycle is repeated 50 times, and then The lithium secondary battery capacity after 50 cycles was calculated.
循环容量保持率＝(第50次循环的放电容量(mAh)/首次循环的放电容量(mAh))×100％。Cycle capacity retention rate=(discharge capacity at the 50th cycle (mAh)/discharge capacity at the first cycle (mAh))×100%.
一次颗粒和二次颗粒平均粒径的测量方法Method for measuring the average particle size of primary and secondary particles
以一次颗粒为例，将样品铺展在测试样品台上，通过扫描电子显微镜拍摄样品不同区域的照片，然后，使用图像解析软件，从SEM照片中随机地选出20个形状完整且无遮挡的一次颗粒，求出这些一次颗粒各自的面积，接着，假设一次颗粒是球形，通过以下公式求出各自的粒径R(直径)：R＝2×(S/π) 1/2；其中，S为一次颗粒的面积；对5张SEM图像进行求出上述一次颗粒粒径R的处理，并将所得100(20×5)个一次颗粒的粒径进行算数平均，从而求得所述一次颗粒的平均粒径。 Taking the primary particles as an example, spread the sample on the test sample stage, and take pictures of different areas of the sample through a scanning electron microscope. Then, using the image analysis software, randomly select 20 primary particles with complete shapes and no occlusion from the SEM photos. particles, obtain the respective areas of these primary particles, and then, assuming that the primary particles are spherical, obtain the respective particle diameters R (diameter) by the following formula: R=2×(S/π) 1/2 ; where S is The area of primary particles; the process of obtaining the above-mentioned primary particle diameter R is performed on 5 SEM images, and the particle diameters of the obtained 100 (20×5) primary particles are arithmetically averaged to obtain the average of the primary particles particle size.
二次颗粒平均粒径的测量方法同一次颗粒。The measurement method of the average particle diameter of the secondary particles is the same as that of the primary particles.
以下将详细描述本申请所提供的正极材料的具体实施例方式，以及各实施例和对比例的性能测试结果。Specific embodiments of the positive electrode material provided in the present application, as well as performance test results of each embodiment and comparative example will be described in detail below.
对比例1Comparative Example 1
对比例1：根据元素摩尔比Ni：Co：Mn＝80：10：10配置含有NiSO 4、CoSO 4、MnSO 4的混合溶液，将该混合溶液和沉淀剂(NaOH溶液)、络合剂(氨水)混合反应，在搅拌状态下调节氨水浓度为6g/L、pH值为12。当反应浆料中的粒度数值达到8μm，停釜，抽取上清液的体积为反应浆料总体积的1/4之后开始提浓，搅拌，在大颗粒达到10μm时停止搅拌，在58℃下陈化10h，即得到平均粒径D v50为10μm的β相镍钴锰前驱体TM(OH) 2(TM＝Ni/Co/Mn)，该前驱体的晶相结构为R3m层状结构；将所得到的β相镍钴锰前驱体TM(OH) 2和氢氧化锂研磨混合均匀，在750℃氧气气氛下煅烧10h，得到摩尔比Ni：Co：Mn＝80：10：10、平均粒径D v50为10μm的镍钴锰酸锂团聚体，也即得到正极材料，该正极材料的晶相结构为R3m层状结构，镍元素摩尔百分比为80％，平均粒径D v50为10μm。 Comparative Example 1: A mixed solution containing NiSO 4 , CoSO 4 , and MnSO 4 was prepared according to the element molar ratio Ni:Co:Mn=80:10:10, and the mixed solution, precipitating agent (NaOH solution), complexing agent (ammonia water) were prepared. ) mixed reaction, and the ammonia concentration was adjusted to 6g/L and the pH value was 12 under stirring. When the particle size value in the reaction slurry reaches 8 μm, stop the kettle, extract the volume of the supernatant to be 1/4 of the total volume of the reaction slurry, start to concentrate and stir, stop stirring when the large particles reach 10 μm, and set the temperature at 58°C. After aging for 10 h, the β-phase nickel-cobalt-manganese precursor TM(OH) 2 (TM=Ni/Co/Mn) with an average particle size D v 50 of 10 μm is obtained, and the crystal phase structure of the precursor is R3m layered structure; The obtained β-phase nickel-cobalt-manganese precursor TM(OH) 2 and lithium hydroxide were ground and mixed uniformly, and calcined in an oxygen atmosphere at 750 °C for 10 h to obtain a molar ratio of Ni:Co:Mn=80:10:10, an average particle size Nickel cobalt lithium manganate agglomerates with a diameter D v 50 of 10 μm are obtained, that is, a positive electrode material is obtained. The crystal phase structure of the positive electrode material is an R3m layered structure, the molar percentage of nickel element is 80%, and the average particle size D v 50 is 10 μm. .
实施例1至实施例8Example 1 to Example 8
实施例1：根据元素摩尔比Ni：Co：Mn＝80：10：10配置含有NiSO 4、CoSO 4、MnSO 4的混合溶液，将该混合溶液和沉淀剂(NaOH溶液)、络合剂(氨水)混合反应，在搅拌状态下调节氨水浓度为5.5g/L、pH值为11。当 反应浆料中的粒度数值达到8μm，停釜，抽取上清液的体积为反应浆料总体积的1/4之后开始提浓，搅拌，在大颗粒达到10μm时停止搅拌，在58℃下陈化10h，即得到平均粒径D v50为10μm的α相镍钴锰前驱体TM(OH) 2(TM＝Ni/Co/Mn)，该前驱体的晶相结构为R3m层状结构；将所得到的α相镍钴锰前驱体TM(OH) 2和氢氧化锂研磨混合均匀，在750℃氧气气氛下煅烧10h，得到摩尔比Ni：Co：Mn＝80：10：10、平均粒径D v50为10μm的镍钴锰酸锂团聚体，也即得到正极材料，该正极材料的晶相结构为Cmc2 1层状结构，镍元素摩尔百分比为80％，平均粒径D v50为10μm。 Example 1: According to the element molar ratio Ni:Co:Mn=80:10:10, a mixed solution containing NiSO 4 , CoSO 4 and MnSO 4 was prepared, and the mixed solution, precipitating agent (NaOH solution) and complexing agent (ammonia water) were prepared. ) mixed reaction, and the ammonia concentration was adjusted to 5.5 g/L and the pH value was 11 under stirring. When the particle size value in the reaction slurry reaches 8 μm, stop the kettle, extract the volume of the supernatant to be 1/4 of the total volume of the reaction slurry, start to concentrate and stir, stop stirring when the large particles reach 10 μm, and set the temperature at 58°C. After aging for 10h, an α-phase nickel-cobalt-manganese precursor TM(OH) 2 (TM=Ni/Co/Mn) with an average particle size D v 50 of 10 μm is obtained, and the crystal phase structure of the precursor is an R3m layered structure; The obtained α-phase nickel-cobalt-manganese precursor TM(OH) 2 and lithium hydroxide were ground and mixed uniformly, and calcined in an oxygen atmosphere at 750 ° C for 10 h to obtain a molar ratio of Ni:Co:Mn=80:10:10, an average particle size The agglomerates of nickel cobalt lithium manganate with a diameter D v 50 of 10 μm are obtained, that is, a positive electrode material is obtained. The crystal phase structure of the positive electrode material is a Cmc2 1 layered structure, the molar percentage of nickel element is 80%, and the average particle size D v 50 is 10μm.
实施例2：与实施例1的差异在于，在搅拌状态下调节氨水浓度为2.5g/L、pH值为8，陈化时间为22h。Example 2: The difference from Example 1 is that the concentration of ammonia water was adjusted to 2.5g/L, the pH value was 8, and the aging time was 22h under stirring.
实施例3：与实施例1的差异在于，在搅拌状态下调节氨水浓度为3g/L、pH值为8.5，陈化时间为20h。Example 3: The difference from Example 1 is that the concentration of ammonia water was adjusted to 3g/L, the pH value was 8.5, and the aging time was 20h under stirring.
实施例4：与实施例1的差异在于，在搅拌状态下调节氨水浓度为3.5g/L、pH值为9，陈化时间为18h。Example 4: The difference from Example 1 is that the concentration of ammonia water was adjusted to 3.5g/L, the pH value was 9, and the aging time was 18h under stirring.
实施例5：与实施例1的差异在于，在搅拌状态下调节氨水浓度为4g/L、pH值为9.5，陈化时间为16h。Example 5: The difference from Example 1 is that the concentration of ammonia water was adjusted to 4g/L, the pH value was 9.5, and the aging time was 16h under stirring.
实施例6：与实施例1的差异在于，在搅拌状态下调节氨水浓度为4.5g/L、pH值为10，陈化时间为14hExample 6: The difference from Example 1 is that the ammonia concentration was adjusted to 4.5g/L, the pH value was 10, and the aging time was 14h under stirring.
实施例7：与实施例1的差异在于，在搅拌状态下调节氨水浓度为5g/L、pH值为10.5，陈化时间为12hExample 7: The difference from Example 1 is that the ammonia concentration was adjusted to 5g/L, the pH value was 10.5, and the aging time was 12h under stirring.
实施例8：与实施例1的差异在于，在搅拌状态下调节氨水浓度为5.5g/L、pH值为11，前驱体和氢氧化锂研磨混合的同时引入Sr元素(摩尔比Sr/(Ni+Co+Mn)＝0.01％)，煅烧温度为730℃。Example 8: The difference from Example 1 is that the ammonia concentration was adjusted to 5.5 g/L and the pH value was 11 under stirring, and Sr element (molar ratio Sr/(Ni) was introduced while the precursor and lithium hydroxide were ground and mixed. +Co+Mn)=0.01%), and the calcination temperature is 730°C.
表1Table 1
Figure PCTCN2021080597-appb-000023
Figure PCTCN2021080597-appb-000023
Figure PCTCN2021080597-appb-000024
Figure PCTCN2021080597-appb-000024
从表1的数据中可以看出，具有空间群Cmc2 1的晶体结构的正极材料的实施例1，相比于使用传统前驱体制备的晶相结构为R3m层状结构正极材料的对比例1，其高电压下的容量保持率大幅提升，并且放电比容量和首次效率也得到提升。由此说明，采用α相的Ni 1-x-yCo xMn y(OH) 2作为三元正极材料的前驱体，可以获得Cmc2 1结构的具有更大Li-O层间距的正极材料，且由于Li-O层间距远大于Ni-O键长，抑制了Ni在锂层形成Li/Ni互占位，解决了三元材料动力学差、大倍率放电温升高、锂镍混排等问题，使得使用该正极材料的电池具有更好的容量性能、首次效率及循环性能。 As can be seen from the data in Table 1, Example 1 of the cathode material with the crystal structure of space group Cmc2 1 , compared to Comparative Example 1 of the cathode material with the R3m layered structure prepared by using traditional precursors, Its capacity retention rate at high voltage is greatly improved, and the discharge specific capacity and first-time efficiency are also improved. This shows that using α-phase Ni 1-xy Co x M ny (OH) 2 as the precursor of the ternary cathode material, a cathode material with a Cmc2 1 structure with a larger Li-O interlayer spacing can be obtained. The -O layer spacing is much larger than the Ni-O bond length, which inhibits the formation of Li/Ni mutual occupation of Ni in the lithium layer, and solves the problems of poor ternary material kinetics, high-rate discharge temperature rise, and lithium-nickel mixed arrangement. The battery using the cathode material has better capacity performance, first efficiency and cycle performance.
从实施例1至实施例8可知，在制备正极材料过程中，通过控制制备α相前驱体的氨水浓度、pH值、陈化时间以及掺入大离子半径元素，可调控正极材料的003晶面衍射峰与104晶面衍射峰的强度比I (003)/I (104)、晶胞参数c、c/a值、以及Li-O层间距。可以看出随着003衍射峰的2θ角降低，晶胞参数c逐渐增大，a轴变化较小，c/a增大，Li-O层间距增大，使得该正极材料结晶性更好、Li/Ni互占位更少。 It can be seen from Example 1 to Example 8 that in the process of preparing the positive electrode material, the 003 crystal plane of the positive electrode material can be regulated by controlling the ammonia concentration, pH value, aging time and doping of large ionic radius elements for preparing the α-phase precursor. The intensity ratio of the diffraction peak to the diffraction peak of the 104 crystal plane I (003) /I (104) , the unit cell parameter c, the c/a value, and the Li-O interlayer spacing. It can be seen that as the 2θ angle of the 003 diffraction peak decreases, the unit cell parameter c gradually increases, the a-axis changes less, the c/a increases, and the Li-O layer spacing increases, making the cathode material better crystallinity, Li/Ni occupies less space for each other.
实施例9至实施例21Example 9 to Example 21
实施例9：与实施例8的差异在于，Sr/(Ni+Co+Mn)摩尔比＝0.5％；Example 9: The difference from Example 8 is that the molar ratio of Sr/(Ni+Co+Mn)=0.5%;
实施例10：与实施例8的差异在于，在搅拌状态下调节氨水浓度为4g/L、pH值为9.5，陈化时间为16h。Sr/(Ni+Co+Mn)摩尔比＝5％；Example 10: The difference from Example 8 is that the concentration of ammonia water was adjusted to 4g/L, the pH value was 9.5, and the aging time was 16h under stirring. Sr/(Ni+Co+Mn) molar ratio=5%;
实施例11至实施例21：与实施例9的差异在于，引入的掺杂元素种类不同，分别为：Mg、Ca、Ba、Al、Y、Zr、B、W、Ta、Nb、La；Example 11 to Example 21: The difference from Example 9 is that the types of doping elements introduced are different: Mg, Ca, Ba, Al, Y, Zr, B, W, Ta, Nb, La;
表2示出了实施例9至实施例21中的正极材料的相关性能参数以及所对应的电池的性能；从实施例9至实施例21可知，在制备正极材料过程中，通过在锂层中掺入大离子半径元素、并调控其掺杂量，可提高Li-O 层间距。使得该正极材料结晶性更好、Li/Ni互占位更少，解决三元材料动力学差、大倍率放电温升高、锂镍混排等问题，使得使用该正极材料的电池具有更好的容量性能、首次效率和循环性能。Table 2 shows the relevant performance parameters of the positive electrode materials in Examples 9 to 21 and the performance of the corresponding batteries; it can be seen from Examples 9 to 21 that in the process of preparing the positive electrode materials, the Doping elements with large ionic radius and adjusting their doping amount can increase the Li-O interlayer spacing. The positive electrode material has better crystallinity and less Li/Ni mutual occupancy, and solves the problems of poor kinetics of ternary materials, high discharge temperature increase, and lithium-nickel mixing, so that the battery using the positive electrode material has better performance. capacity performance, first-time efficiency and cycle performance.
表2Table 2
Figure PCTCN2021080597-appb-000025
Figure PCTCN2021080597-appb-000025
实施例22至实施例28Example 22 to Example 28
实施例22至实施例28：与实施例1的差异在于，正极材料中Ni元素的摩尔含量不同。在制备正极材料过程中，通过调配镍盐、钴盐和锰盐的比例，得到具有不同的Ni元素摩尔百分比的正极材料。Example 22 to Example 28: The difference from Example 1 is that the molar content of Ni element in the positive electrode material is different. In the process of preparing the positive electrode material, by adjusting the ratios of nickel salt, cobalt salt and manganese salt, positive electrode materials with different molar percentages of Ni elements are obtained.
实施例22：与实施例1的差异在于，Ni:Co:Mn摩尔比＝50:20:30；Example 22: The difference from Example 1 is that Ni:Co:Mn molar ratio=50:20:30;
实施例23：与实施例1的差异在于，Ni:Co:Mn摩尔比＝60:20:20；Example 23: The difference from Example 1 is that Ni:Co:Mn molar ratio=60:20:20;
实施例24：与实施例1的差异在于，Ni:Co:Mn摩尔比＝70:10:20；Example 24: The difference from Example 1 is that Ni:Co:Mn molar ratio=70:10:20;
实施例25：与实施例1的差异在于，Ni:Co:Mn摩尔比＝83:12:5；Example 25: The difference from Example 1 is that the molar ratio of Ni:Co:Mn=83:12:5;
实施例26：与实施例1的差异在于，Ni:Co:Mn摩尔比＝88:7:5；Example 26: The difference from Example 1 is that the molar ratio of Ni:Co:Mn=88:7:5;
实施例27：与实施例1的差异在于，Ni:Co:Mn摩尔比＝90:5:5；Example 27: The difference from Example 1 is that Ni:Co:Mn molar ratio=90:5:5;
实施例28：与实施例1的差异在于，Ni:Co:Mn摩尔比＝100:0:0；Example 28: The difference from Example 1 is that Ni:Co:Mn molar ratio=100:0:0;
表3table 3
Figure PCTCN2021080597-appb-000026
Figure PCTCN2021080597-appb-000026
Figure PCTCN2021080597-appb-000027
Figure PCTCN2021080597-appb-000027
从表3的数据中可以看出，不同的Ni元素对于电池的放电比容量、首次效率和循环性能会有一定的影响，随着Ni元素含量的提高，对电池的放电比容量不断提高，而对电池的首次效率则不断的降低。因此，适宜的Ni元素含量能够使电池的放电比容量、首次效率和循环性能均得到一定程度的改善。It can be seen from the data in Table 3 that different Ni elements will have a certain impact on the discharge specific capacity, initial efficiency and cycle performance of the battery. The first efficiency of the battery is continuously reduced. Therefore, a suitable Ni content can improve the discharge specific capacity, initial efficiency and cycle performance of the battery to a certain extent.
实施例29至实施例34Example 29 to Example 34
实施例29至实施例34与实施例1的差异在于，正极材料的平均粒径不同。在制备正极材料过程中，通过控制α相前驱体反应时间，得到具有不同的平均粒径的正极材料。Examples 29 to 34 differ from Example 1 in that the average particle size of the positive electrode material is different. In the process of preparing the positive electrode material, by controlling the reaction time of the α-phase precursor, positive electrode materials with different average particle sizes are obtained.
实施例29：与实施例1的差异在于，当反应浆料中的粒度数值达到0.8μm，停釜，提浓，搅拌，在大颗粒达到1μm时停止搅拌；Example 29: The difference from Example 1 is that when the particle size value in the reaction slurry reaches 0.8 μm, the kettle is stopped, concentrated, and stirred, and the stirring is stopped when the large particles reach 1 μm;
实施例30：与实施例1的差异在于，当反应浆料中的粒度数值达到2.4μm，停釜，提浓，搅拌，在大颗粒达到3μm时停止搅拌；Example 30: The difference from Example 1 is that when the particle size value in the reaction slurry reaches 2.4 μm, the kettle is stopped, concentrated, and stirred, and the stirring is stopped when the large particles reach 3 μm;
实施例31：与实施例1的差异在于，当反应浆料中的粒度数值达到4μm，停釜，提浓，搅拌，在大颗粒达到5μm时停止搅拌；Example 31: The difference from Example 1 is that when the particle size value in the reaction slurry reaches 4 μm, stop the kettle, concentrate, stir, and stop stirring when the large particles reach 5 μm;
实施例32：与实施例1的差异在于，当反应浆料中的粒度数值达到9.6μm，停釜，提浓，搅拌，在大颗粒达到12μm时停止搅拌；Example 32: The difference from Example 1 is that when the particle size value in the reaction slurry reaches 9.6 μm, the kettle is stopped, concentrated, and stirred, and the stirring is stopped when the large particles reach 12 μm;
实施例33：与实施例1的差异在于，当反应浆料中的粒度数值达到16μm，停釜，提浓，搅拌，在大颗粒达到20μm时停止搅拌；Example 33: The difference from Example 1 is that when the particle size value in the reaction slurry reaches 16 μm, the kettle is stopped, concentrated, and stirred, and the stirring is stopped when the large particles reach 20 μm;
实施例34：与实施例1的差异在于，当反应浆料中的粒度数值达到24μm，停釜，提浓，搅拌，在大颗粒达到30μm时停止搅拌；Example 34: The difference from Example 1 is that when the particle size value in the reaction slurry reaches 24 μm, the kettle is stopped, concentrated, and stirred, and the stirring is stopped when the large particles reach 30 μm;
表4示出了实施例29至实施例34中的正极材料的相关性能参数以及所对应的电池的性能。Table 4 shows the relevant performance parameters of the positive electrode materials in Examples 29 to 34 and the performance of the corresponding batteries.
表4Table 4
Figure PCTCN2021080597-appb-000028
Figure PCTCN2021080597-appb-000028
Figure PCTCN2021080597-appb-000029
Figure PCTCN2021080597-appb-000029
从表4的数据中可以看出，不同的二次颗粒平均粒径对于电池的放电比容量、首次效率和循环性能会有一定的影响，随着二次颗粒平均粒径的提高，对电池的放电比容量不断降低，而对电池的首次效率和循环性能则不断的提高。因此，适宜的二次颗粒平均粒径能够使电池的放电比容量、首次效率和循环性能均得到一定程度的改善。It can be seen from the data in Table 4 that different average particle sizes of secondary particles will have a certain impact on the discharge specific capacity, primary efficiency and cycle performance of the battery. The discharge specific capacity is continuously reduced, while the first efficiency and cycle performance of the battery are continuously improved. Therefore, a suitable average particle size of secondary particles can improve the discharge specific capacity, initial efficiency and cycle performance of the battery to a certain extent.
此外，图1示出了本申请实施例1提供的正极材料的Li与O的层间距的示意图；图2示出了本申请对比例1提供的正极材料的Li与O的层间距的示意图。结合图1和图2可以看出，本申请实施例1的正极材料的Li与O的层间距远大于对比例1的正极材料的Li与O的层间距。In addition, FIG. 1 shows a schematic diagram of the interlayer distance between Li and O of the positive electrode material provided in Example 1 of the present application; FIG. 2 shows a schematic diagram of the interlayer distance between Li and O of the positive electrode material provided in Comparative Example 1 of the present application. 1 and 2, it can be seen that the interlayer distance between Li and O of the positive electrode material of Example 1 of the present application is much larger than the interlayer distance of Li and O of the positive electrode material of Comparative Example 1.
图3示出了本申请实施例提供的正极材料Li/Ni互占位的示意图。图4示出了本申请实施例1提供的正极材料的X射线衍射谱图(XRD图)。其中，Li/Ni阳离子混排，晶胞参数c/晶胞参数a的比值越大，锂镍混排越低。FIG. 3 shows a schematic diagram of the mutual occupancy of the cathode material Li/Ni provided in the embodiment of the present application. FIG. 4 shows the X-ray diffraction pattern (XRD pattern) of the cathode material provided in Example 1 of the present application. Among them, Li/Ni cations are mixed, and the larger the ratio of the unit cell parameter c/unit cell parameter a, the lower the lithium-nickel mixing.
尽管已经演示和描述了说明性实施例，本领域技术人员应该理解上述实施例不能被解释为对本申请的限制，并且可以在不脱离本申请的精神、原理及范围的情况下对实施例进行改变，替代和修改。Although illustrative embodiments have been shown and described, it should be understood by those skilled in the art that the above-described embodiments are not to be construed as limitations of the application, and changes may be made in the embodiments without departing from the spirit, principles and scope of the application , alternatives and modifications.

Claims (10)

  1. 一种正极材料，其特征在于，所述正极材料具有属于空间群Cmc2 1的晶体结构。 A positive electrode material, characterized in that the positive electrode material has a crystal structure belonging to the space group Cmc2 1 .
  2. 根据权利要求1所述的正极材料，其特征在于，在所述正极材料的X射线衍射谱图中，003晶面衍射峰位于12°至18.5°范围内。The positive electrode material according to claim 1, wherein in the X-ray diffraction spectrum of the positive electrode material, the 003 crystal plane diffraction peak is located in the range of 12° to 18.5°.
  3. 根据权利要求1所述的正极材料，其特征在于，在所述正极材料的X射线衍射谱图中，003晶面衍射峰与104晶面衍射峰的强度比I (003)/I (104)满足：I (003)/I (104)≥1.8。 The positive electrode material according to claim 1, wherein, in the X-ray diffraction spectrum of the positive electrode material, the intensity ratio of the 003 crystal plane diffraction peak and the 104 crystal plane diffraction peak is I (003) /I (104) Satisfaction: I (003) /I (104) ≥ 1.8.
  4. 根据权利要求1所述的正极材料，其特征在于，所述正极材料满足以下条件a)至c)中的至少一者：The positive electrode material according to claim 1, wherein the positive electrode material satisfies at least one of the following conditions a) to c):
    a)晶胞参数
    Figure PCTCN2021080597-appb-100001
    a) Unit cell parameters
    Figure PCTCN2021080597-appb-100001
    b)晶胞参数
    Figure PCTCN2021080597-appb-100002
    b) Unit cell parameters
    Figure PCTCN2021080597-appb-100002
    c)晶胞参数c/晶胞参数a≥4.95。c) Unit cell parameter c/unit cell parameter a ≥ 4.95.
  5. 根据权利要求1所述的正极材料，其特征在于，所述正极材料包括锂过渡金属氧化物，其中Li与O的层间距范围为
    Figure PCTCN2021080597-appb-100003
    至
    Figure PCTCN2021080597-appb-100004
    The positive electrode material according to claim 1, wherein the positive electrode material comprises a lithium transition metal oxide, wherein the interlayer distance between Li and O ranges from
    Figure PCTCN2021080597-appb-100003
    to
    Figure PCTCN2021080597-appb-100004
  6. 根据权利要求1所述的正极材料，其特征在于，所述正极材料包括锂过渡金属氧化物，所述锂过渡金属氧化物中含有过渡金属元素Me，所述过渡金属元素Me包括Ni元素，基于所述过渡金属元素Me的摩尔量，所述Ni元素的摩尔百分比≥50％。The positive electrode material according to claim 1, wherein the positive electrode material comprises a lithium transition metal oxide, the lithium transition metal oxide contains a transition metal element Me, and the transition metal element Me comprises Ni element, based on The molar amount of the transition metal element Me and the molar percentage of the Ni element are ≥50%.
  7. 根据权利要求1所述的正极材料，其特征在于，所述正极材料包括由一次颗粒组成的二次颗粒，所述一次颗粒的平均粒径为0.1μm至1.5μm，所述二次颗粒的平均粒径为1μm至30μm。The positive electrode material according to claim 1, wherein the positive electrode material comprises secondary particles composed of primary particles, the average particle diameter of the primary particles is 0.1 μm to 1.5 μm, and the average particle diameter of the secondary particles is 0.1 μm to 1.5 μm. The particle size is 1 μm to 30 μm.
  8. 根据权利要求1至7中任一项所述的正极材料，其特征在于，所述正极材料包括Li xNi yCo zMn kZ qO b-aT a，其中，Z包括B、Mg、Al、Si、P、S、Ti、Cr、Fe、Cu、Zn、Ga、Y、Zr、Mo、Ag、W、In、Sn、Pb、Sb、Sr和Ce中的至少一种，T为卤素，并且x、y、z、k、q、a和b分别满足：0.2＜x≤1.2、0＜y≤1、0≤z≤1、0≤k≤1、0≤q≤1、1≤b≤2以及0≤a≤1；优选地，0.6≤x≤1.2、0.5≤y≤1、0≤z≤0.5、0≤k≤0.5、0≤q≤0.5、1.5≤b≤2以及0≤a≤0.5。 The positive electrode material according to any one of claims 1 to 7, wherein the positive electrode material comprises Li x Ni y Co z Mn k Z q O ba Ta , wherein Z comprises B, Mg, Al, At least one of Si, P, S, Ti, Cr, Fe, Cu, Zn, Ga, Y, Zr, Mo, Ag, W, In, Sn, Pb, Sb, Sr, and Ce, T is a halogen, and x, y, z, k, q, a and b satisfy: 0.2<x≤1.2, 0<y≤1, 0≤z≤1, 0≤k≤1, 0≤q≤1, 1≤b≤ 2 and 0≤a≤1; preferably, 0.6≤x≤1.2, 0.5≤y≤1, 0≤z≤0.5, 0≤k≤0.5, 0≤q≤0.5, 1.5≤b≤2, and 0≤a ≤0.5.
  9. 一种电化学装置，其特征在于，所述电化学装置包括如权利要求1 至8中任一项所述的正极材料。An electrochemical device, characterized in that, the electrochemical device comprises the positive electrode material according to any one of claims 1 to 8 .
  10. 一种电子设备，其特征在于，所述电子设备包括如权利要求9中所述的电化学装置。An electronic device, characterized in that the electronic device comprises the electrochemical device as claimed in claim 9 .
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1665053A (en) * 2004-03-03 2005-09-07 王岩 A positive electrode active material of Li-ion battery and its preparing process
CN1773753A (en) * 2004-11-08 2006-05-17 深圳市比克电池有限公司 Lithium ion battery anode material and producing method thereof
CN109671924A (en) * 2018-11-29 2019-04-23 兰州金通储能动力新材料有限公司 A kind of preparation method of nickel-cobalt-manganternary ternary anode material
JP2020035693A (en) * 2018-08-31 2020-03-05 住友金属鉱山株式会社 Transition metal composite hydroxide, manufacturing method thereof, lithium transition metal composite oxide active material, and lithium ion secondary battery
CN111354943A (en) * 2018-12-20 2020-06-30 中国科学院深圳先进技术研究院 Use of fluorinated oxalate materials and products comprising fluorinated oxalate materials, methods of making and uses thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1665053A (en) * 2004-03-03 2005-09-07 王岩 A positive electrode active material of Li-ion battery and its preparing process
CN1773753A (en) * 2004-11-08 2006-05-17 深圳市比克电池有限公司 Lithium ion battery anode material and producing method thereof
JP2020035693A (en) * 2018-08-31 2020-03-05 住友金属鉱山株式会社 Transition metal composite hydroxide, manufacturing method thereof, lithium transition metal composite oxide active material, and lithium ion secondary battery
CN109671924A (en) * 2018-11-29 2019-04-23 兰州金通储能动力新材料有限公司 A kind of preparation method of nickel-cobalt-manganternary ternary anode material
CN111354943A (en) * 2018-12-20 2020-06-30 中国科学院深圳先进技术研究院 Use of fluorinated oxalate materials and products comprising fluorinated oxalate materials, methods of making and uses thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
GAO JIANHUA, SHA XUNSHAN, LIU XI, SONG LIMEI, ZHAO PAN: "Preparation, structure and properties of Na 2 Mn 3 (SO 4 ) 4 : a new potential candidate with high voltage for Na-ion batteries", JOURNAL OF MATERIALS CHEMISTRY A, ROYAL SOCIETY OF CHEMISTRY, GB, vol. 4, no. 30, 1 January 2016 (2016-01-01), GB , pages 11870 - 11877, XP055964949, ISSN: 2050-7488, DOI: 10.1039/C6TA02629J *

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