CN116247161A - Battery cell - Google Patents

Battery cell Download PDF

Info

Publication number
CN116247161A
CN116247161A CN202310493382.5A CN202310493382A CN116247161A CN 116247161 A CN116247161 A CN 116247161A CN 202310493382 A CN202310493382 A CN 202310493382A CN 116247161 A CN116247161 A CN 116247161A
Authority
CN
China
Prior art keywords
battery
positive electrode
ternary
electrode material
ternary positive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202310493382.5A
Other languages
Chinese (zh)
Other versions
CN116247161B (en
Inventor
王哲
张潇阳
李奎
李康
单旭意
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Innovation Aviation Technology Group Co ltd
Original Assignee
China Innovation Aviation Technology Group Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Innovation Aviation Technology Group Co ltd filed Critical China Innovation Aviation Technology Group Co ltd
Priority to CN202310493382.5A priority Critical patent/CN116247161B/en
Publication of CN116247161A publication Critical patent/CN116247161A/en
Application granted granted Critical
Publication of CN116247161B publication Critical patent/CN116247161B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

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

Abstract

The invention provides a battery, which comprises a positive plate, wherein a positive active material layer is arranged on the positive plate, and the positive active material layer comprises a ternary positive material; the ternary positive electrode material is doped with at least one metal element M, wherein the highest valence of the metal element M is more than 3; in the ternary positive electrode material, calculated according to the mole ratio, li: ni: co: mn: m=0.95 to 1.1: x: y: and z: a, wherein 0.7 < x < 1,0 < y < 1,0 < z < 1, x+y+z+a=1; in the 100% SOC state of the battery, the ternary positive electrode material meets the requirement of Ni 4+ The mole number of (C) is inThe proportion of the total mole number of Ni element is not less than 65%. The ternary positive electrode material has good structural stability and improves the cycle performance of the battery.

Description

Battery cell
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a battery.
Background
Lithium Ion Batteries (LIBs) have advantages of high energy density, high reversible capacity, environmental friendliness, and the like, and are widely used in portable electronic devices and Electric Vehicles (EVs). Nickel-cobalt-manganese ternary positive electrode material LiNi x Co y Mn z O 2 （NCM，x+y+z=1）LiCoO 2 、LiNiO 2 And LiMnO 2 The positive electrode material has the advantages of being widely applied and researched in recent years, and is one of the positive electrode materials of the lithium battery with the most development prospect at present. In the nickel-cobalt-manganese ternary cathode material, the high cost and the relative scarcity of Co are high, and the requirement on the battery energy density in practical application is continuously increased, so that the content of Ni is required to be continuously increased in order to improve the specific capacity, and the high-nickel ternary cathode material becomes the key point of researches of a plurality of scholars and enterprises at present.
The high-nickel ternary nickel-cobalt-manganese material has a hexagonal layered structure, and the structure is similar to NaFeO 2 The space point group is R-3m. Li (Li) ＋ And transition metal ions occupy the 3a and 3b positions, O 2- Occupy position 6c, O 2- Is hexagonal close packed, transition metal ions and Li ＋ Respectively occupy the octahedral gaps alternately and are arranged in a layered manner. The atomic arrangement structure ensures that NCM has superior electrochemical performance, but high-nickel NCM anode materials also have some electrochemical characteristics which are insufficient: (1) due to Ni 2+ With Li ＋ Is similar in ionic radius, and therefore Li during discharge ＋ Is largely separated from Ni 2+ Occupying Li ＋ Causing lithium nickel mixed discharge; while too much Ni makes Ni 3+ Is easy to be reduced into Ni 2+ The cation mixing degree is aggravated, and the circulation stability of the anode material is reduced; (2) because of the anisotropy of particles in the material crystal, microcrack is easy to generate in the charge and discharge process, so that the electrolyte reacts with the anode material, active substances are further reduced, and irreversible loss of capacity is caused; (3) ni (Ni) 3+ /Ni 4+ And the oxygen atoms are overlapped with the energy bands, so that in the high-delithiation state, the oxygen atoms in the crystal lattice are oxidized into oxygen to be released, and the cycle stability is reduced.
Disclosure of Invention
In order to solve the problems and the defects existing in the prior art, the invention provides a battery, wherein the positive electrode active material in the positive electrode plate of the battery is a ternary positive electrode material doped with high-valence metal elements, and Ni is oxidized by controlling the ternary positive electrode material 4+ The mole content of ions relative to Ni element is more than 65%, the bonding strength of doped metal and oxygen atoms is stabilized, and Ni is reduced 2+ The component content of ions ensures that the ternary positive electrode material has a relatively stable lattice structure, reduces the lithium-nickel mixed arrangement degree in the ternary positive electrode material, keeps relatively high energy exertion of the positive electrode material, and improves the long-term cycling stability of the battery.
The invention provides a battery, which comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein a positive active material layer is arranged on the positive plate, and the positive active material layer comprises a ternary positive material; the ternary positive electrode material is doped with at least one metal element M, wherein the valence of the metal element M is more than 3; in the ternary positive electrode material, calculated according to the mole ratio, li: ni: co: mn: m=0.95 to 1.1: x: y: and z: a, wherein 0.7 < x < 1,0 < y < 1,0 < z < 1, x+y+z+a=1; in the 100% soc state of the battery, the ternary positive electrode material satisfies: ni (Ni) 4+ The ratio of the number of moles of (C) in the total number of moles of Ni element is not less than 65%.
In the battery, the ternary positive electrode material has good structural stability, so that the cycle performance of the battery is improved. Wherein, ni is controlled at 100% SOC after oxidation by controlling the ternary positive electrode material of nickel, cobalt and manganese 4+ The molar content of (2) is not less than 65% in Ni element, ni can be reduced 2+ The proportion of the ionic components reduces the mixing degree of lithium and nickel, improves the lattice stability of the ternary cathode material, and further improves the cycle performance of the battery; and Ni is controlled when 100% of SOC of the nickel-cobalt-manganese ternary cathode material 4+ The molar content of the (B) is not less than 65% in Ni element, the bonding bond energy of the doped metal element M and oxygen atoms can be improved, the release of lattice oxygen is inhibited, the structural stability of the ternary positive electrode material is further enhanced, and the (B) has a better effect on inhibiting the release of lattice oxygen of the high-nickel ternary material, thereby improving the capacity attenuation, gas generation and thermal effect of the batteryAnd the like.
The metal element M with the valence state more than 3 is doped into the crystal lattice of the ternary positive electrode material, and Ni can be reduced through a charge compensation mechanism 2+ The content of Ni in 100% SOC state can be controlled by the doping means together with other preparation processes 4+ The molar content of the lithium-nickel composite material is not less than 65% of the molar content of the nickel composite material in Ni element, so that the lithium-nickel mixed discharge degree is reduced, the migration barrier of lithium ions is reduced, and the stability of the ternary positive electrode material is improved.
Detailed Description
The invention provides a battery, which comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein a positive active material layer is arranged on the positive plate, and the positive active material layer comprises a ternary positive material; the ternary positive electrode material is doped with at least one metal element M, wherein the valence of the metal element M is more than 3; in the ternary positive electrode material, calculated according to the mole ratio, li: ni: co: mn: m=0.95 to 1.1: x: y: and z: a, wherein 0.7 < x < 1,0 < y < 1,0 < z < 1, x+y+z+a=1; in the 100% soc state of the battery, the ternary positive electrode material satisfies: ni (Ni) 4+ The ratio of the number of moles of (C) in the total number of moles of Ni element is not less than 65%.
In the battery, the ternary positive electrode material has good structural stability, so that the cycle performance of the battery is improved. Wherein, ni is controlled at 100% SOC after oxidation by controlling the ternary positive electrode material of nickel, cobalt and manganese 4+ The molar content of (2) is not less than 65% in Ni element, ni can be reduced 2+ The proportion of the ionic components reduces the mixing degree of lithium and nickel, improves the lattice stability of the ternary cathode material, and further improves the cycle performance of the battery; and Ni is controlled when 100% of SOC of the nickel-cobalt-manganese ternary cathode material 4+ The molar content of the (B) is not less than 65% in Ni element, the bonding bond energy of the doped metal element M and oxygen atoms can be improved, the release of lattice oxygen is inhibited, the structural stability of the ternary positive electrode material is further enhanced, and the (B) has a good effect on inhibiting the release of lattice oxygen of the high-nickel ternary material, and further the problems of capacity attenuation, gas generation, thermal effect and the like of a battery are improved.
And a metal element M with a valence greater than 3 is doped into the ternary positive electrode materialIn the crystal lattice, ni can be reduced by a charge compensation mechanism 2+ The content of Ni in 100% SOC state can be controlled by the doping means together with other preparation processes 4+ The molar content of the lithium-nickel composite material is not less than 65% of the molar content of the nickel composite material in Ni element, so that the lithium-nickel mixed discharge degree is reduced, the migration barrier of lithium ions is reduced, and the stability of the ternary positive electrode material is improved.
Preferably, the ternary positive electrode material satisfies, at a battery 100% soc state: ni (Ni) 4+ The ratio of the number of moles of (C) in the total number of moles of Ni element is not less than 80%.
Preferably, the metal element M includes at least one of Nb, ti, mo, ta, W. The metal elements M have higher highest valence state, can be combined with a part of charges, and improve Ni in the ternary positive electrode active material 4+ Is favorable for ensuring Ni content 4+ The ratio of the number of moles of (C) to the total number of moles of Ni element is not less than 65%, ni is reduced 2+ The content of cations is reduced; and the metal elements M can have stronger bonding energy with oxygen atoms, so that the stability of lattice oxygen is improved, and the stability of the lattice structure of the ternary positive electrode active material is further improved.
Preferably, the metal element M includes at least one of Mo and Ta.
Preferably, the metal element M is Ta.
Preferably, a=0.001 to 0.01. Because of the transition metal ion (Ni 2+ ) Form inactive sites after occupying one lithium site, and the Ni is bypassed when other lithium ions diffuse 2+ Therefore, the diffusion path of lithium ions becomes relatively long, resulting in a slow diffusion rate of lithium ions. Therefore, the effect of lithium nickel back-fill defects on the lithium ion diffusion rate depends on the dominance of both the activation energy reduction (thrust) and the diffusion path lengthening (resistance). Therefore, the amount of doped metal elements is ensured to be within a certain range, when a proper amount of mixed lithium and nickel are present in crystal lattices, the activation energy of lithium ions can be obviously reduced without causing a relatively longer diffusion path, at the moment, the diffusion rate and the multiplying power performance of lithium ions in the material are optimal, the improvement effect is weakened when the lithium ions are lower than the range, and the lithium nickel is aggravated when the lithium ions are higher than the rangeMixing, and damaging the structural stability of the material.
Preferably, a=0.003 to 0.007. The doping amount of the metal element M is in the range, and the ternary positive electrode material has proper lithium nickel mixed arrangement degree, so that the ternary positive electrode material has better lattice stability and long-term cycle stability.
Preferably, the D50 of the ternary positive electrode material is 1.5-6.0 μm. The D50 is in accordance with the ternary positive electrode material in the range, so that the ternary positive electrode active particles are not easy to agglomerate, and the integral strength of the ternary positive electrode active material layer is ensured.
Preferably, the D50 of the ternary positive electrode material is 3.0-5 μm.
Preferably, the ternary positive electrode material has a BET of 0.1m 2 /g~2m 2 And/g. The ternary positive electrode material is ensured to have proper specific surface area, the problem that the specific surface area is too small, and particles are usually large in size, so that the diffusion distance of lithium ions is increased, the activity of the ternary positive electrode material is reduced, and the charge and discharge performance is deteriorated is avoided; meanwhile, the phenomenon that the capacity of the battery is exerted and the primary efficiency is reduced due to the fact that the interfacial side reaction between the active material and the electrolyte is increased due to the fact that the specific surface area is too large is avoided.
Preferably, the ternary positive electrode material has a BET of 0.5m 2 /g~1.3m 2 /g。
Preferably, the ternary positive electrode material comprises at least one of single crystal NCM, polycrystalline NCA. Wherein NCM represents a nickel cobalt manganese material, NCA represents a nickel cobalt aluminum material, and NCMA represents a nickel cobalt manganese aluminum material. Under the doping of the metal element M, the ternary positive electrode material reduces the lithium nickel mixed discharge degree and improves the lattice stability to different degrees.
Preferably, the ternary positive electrode material is single crystal NCM. The monocrystalline NCM can form a more stable lattice structure with the doped metal element M in the invention, is suitable for a higher voltage system, and has better long-term cycling stability under the high voltage system.
Preferably, preparing the ternary cathode material comprises the steps of: s1, preparing a soluble salt solution by using nickel salt, cobalt salt and manganese salt; s2, preparing a spherical precursor by utilizing a soluble salt solution and part of a material containing metal elements M, wherein the metal elements M are homogeneously doped in the spherical precursor; s3, mixing the spherical precursor with an alkaline material and calcining to obtain a primary sintering material; s4, mixing the primary sintering material with lithium salt and calcining to obtain a secondary sintering material; s5, continuously calcining the secondary sintering material to obtain a tertiary sintering material; s6, mixing the three-time sintering material, the rest material containing the metal element M and the alkaline lithium compound, and calcining to obtain the ternary positive electrode material.
In the method for preparing the ternary cathode material, the material containing the metal element M is added in batches, which is beneficial to the metal element M to be more uniformly doped in the ternary cathode material, so that the metal element M can fully exert the charge compensation function of the metal element M to reduce Ni 2+ Content of Ni is increased 4+ The content is as follows. And the material is subjected to several times of calcination in the whole preparation process, so that volatile substances and moisture in the raw materials can be fully removed, the density and strength of the material are improved, the crystal structure of the material is improved, the stability of the material is improved, the higher stability of the material in the subsequent charge-discharge cycle is ensured, and the cycle life of the material is prolonged.
Preferably, the battery further comprises a negative electrode plate, wherein a negative electrode active material layer is arranged on the negative electrode plate, and the negative electrode active material layer comprises at least one of graphite, a graphite/silicon composite material and a graphite/silicon composite material.
In order that those skilled in the art will better understand the present invention, a technical solution of the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments.
Example 1
(1) Preparation of ternary cathode material
The preparation of the ternary positive electrode material adopts the combination of an ion exchange method and a high-temperature solid phase reaction method, and comprises the following specific steps:
s1, nickel salt (NiSO 4 ·6H 2 O), cobalt salts (CoSO 4 ·7H 2 O), manganese salt (MnSO 4 ·H 2 O) dissolving in deionized water, and uniformly mixing to obtain a soluble salt solution; wherein, according to Ni: co: mn ofThe molar ratio is 92:5:3, calculating the feeding amount of nickel salt, cobalt salt and manganese salt;
s2, dissolving the soluble salt solution, naOH solution and NH 3 ·H 2 The O complexing agent solution is co-current and directed to Ta therein 2 O 5 Solution (calculated as Ta in terms of a molar ratio of Ta (Ni+Co+Mn) of 0.001:0.999) 2 O 5 Transferring into a continuous stirred tank reactor, introducing oxygen with the purity of 99.5%, starting a stirring device of the continuous stirred tank reactor, controlling the temperature of the continuous stirred tank reactor at 50 ℃, continuously monitoring the pH value of a reaction system in the reaction process, regulating the pH value of the reaction system to be 12.1, and performing coprecipitation reaction to obtain a spherical precursor, wherein the spherical precursor is Ta/[ N ] 92 Co 5 Mn 3 ](OH 2 ) Wherein Ta is homogeneously doped at [ N 92 Co 5 Mn 3 ](OH 2 ) In (a) and (b);
s3, mixing the spherical precursor prepared in the step S2 with NaOH, and using Na: [ Ni+Mn+Co ]]The molar ratio of NaOH is 1.1:1, the temperature of the mixture obtained is raised to 650 ℃ at the temperature rising rate of 4 ℃/min, and the mixture is calcined for 24 hours in the atmosphere of 100% volume of oxygen to obtain a primary sintering material, wherein the primary sintering material is Ta/NaNi 0.92 Co 0.05 Mn 0.03 O 2 Wherein Ta is homogeneously doped with NaNi 0.92 Co 0.05 Mn 0.03 O 2 In (a) and (b);
s4, sintering the primary sintering material prepared in S3, lithium chloride (LiCl) and lithium nitrate (LiNO) 3 ) Mixing at a molar ratio of 10:12:88, heating the mixture to 300 ℃ at a heating rate of 4 ℃/min, and calcining for 8 hours in air to obtain a secondary sintering material, wherein the secondary sintering material is Ta/LiNi 0.92 Co 0.05 Mn 0.03 O 2 Wherein Ta is homogeneously doped in LiNi 0.92 Co 0.05 Mn 0.03 O 2 In (a) and (b); flushing the secondary sintering material for 5 times by distilled water and ethanol to remove redundant lithium salt and exchanged sodium salt, and then drying at 60 ℃ for 24 hours;
s5, heating the powder dried in the step S4 to 800 ℃ at a heating rate of 4 ℃/min, performing heat treatment in a tube furnace for 3 hours under an oxygen atmosphere, cooling to room temperature along with the furnace, and crushing and screening to obtain a three-time sintered material;
s6, sintering the materials and Ta for three times in the step S5 2 O 5 Simultaneously adding LiOH into a mixer to mix, wherein the mixing is carried out according to the following steps: ta: the molar ratio of Li is 0.996:0.04:0.05, and the three times of sintering material and Ta are calculated 2 O 5 The addition amount of LiOH is sintered according to the following procedures: under the atmosphere of 100% oxygen by volume, firstly heating to 400 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 4 hours, then heating to 830 ℃ at the heating rate of 4 ℃/min, keeping the temperature for 12 hours to obtain a four-time sintered material, crushing and screening the four-time sintered material to obtain the Ta-doped ternary anode material, wherein the Ta-doped ternary anode material is a single crystal material, D50=3.50 mu m and BET is 0.85m 2 /g。
(2) Preparation of a Battery
(1) Preparation of positive plate
Mixing the prepared ternary positive electrode material, a conductive agent acetylene black and a binder PVDF (polyvinylidene fluoride) according to a mass ratio of 96:2:2, adding a solvent NMP (N-methylpyrrolidone), and stirring in a vacuum stirrer until the system is uniform to obtain positive electrode slurry; and uniformly coating the positive electrode slurry on two surfaces of a positive electrode current collector aluminum foil, airing at room temperature, transferring to an oven, continuously drying, and then carrying out cold pressing and cutting to obtain the positive electrode plate.
(2) Preparation of negative electrode sheet
Mixing graphite as a negative electrode active material or a mixture of graphite and other active materials according to different mass ratios, acetylene black as a conductive agent, CMC (sodium carboxymethyl cellulose) as a thickening agent and SBR (styrene butadiene rubber) as a binder according to a mass ratio of 96.4:1:1.2:1.4, adding deionized water as a solvent, and stirring in a vacuum stirrer until the system is uniform to obtain negative electrode slurry; and uniformly coating the negative electrode slurry on two surfaces of a negative electrode current collector copper foil, airing at room temperature, transferring to an oven for continuous drying, and then carrying out cold pressing and slitting to obtain a negative electrode plate.
(3) Preparation of electrolyte
Mixing EC (ethylene carbonate), EMC (methyl ethyl carbonate) and diethyl carbonate) DEC according to a volume ratio of 1:1:1 to obtainTo a mixed organic solvent, followed by a sufficiently dry lithium salt LiPF 6 Dissolving in a mixed organic solvent to prepare the electrolyte with the concentration of 1 mol/L.
(4) Preparation of a separator film
Selected from polyethylene films as barrier films.
(5) Preparation of a Battery
Sequentially stacking the positive plate, the isolating film and the negative plate, enabling the isolating film to be positioned between the positive plate and the negative plate to play a role of isolation, and then winding to obtain a bare cell; the bare cell is placed in an outer packaging shell, electrolyte is injected after drying, and the battery is obtained through the procedures of vacuum packaging, standing, formation, shaping and the like; the specific process of the formation comprises the following steps: charging the vacuum packed and left standing battery to 3.8V with a charging current of 0.04C and to 4.15V with a charging current of 0.02C; then the battery is discharged to 3.75V with a current of 0.02C, and then the battery is charged and discharged 3 times between 3.75 and 4.15V with a current of 0.04C.
Example 2
(1) Preparation of ternary cathode material the preparation of ternary cathode material in this example was identical to example 1; the ternary positive electrode material obtained in this example was also a Ta-doped ternary positive electrode material, and it was a single crystal material with d50=3.52 μm and BET of 0.88 m 2 /g。
(2) Preparation of a Battery
In the preparation of the battery of the embodiment, the steps (1) - (4) are consistent with the embodiment 1; the battery formation step in step (5) was different from that in example 1, and the remainder was the same as that in example 1; the specific formation procedure is as follows:
the vacuum packed and standing battery is charged to 3.8V with a charging current of 0.04C, then charged for 10 minutes at constant voltage, charged to 4.15V with 0.02C, then discharged to 3.75V with a current of 0.02C, and then charged and discharged 3 times with a current of 0.04C between 3.75 and 4.15V.
Example 3
(1) Preparation of ternary cathode material
The preparation of the ternary positive electrode material in this example was identical to example 1; the ternary positive electrode material obtained in the final embodiment is also Ta doped ternary positive electrodeThe material is a single crystal material, d50=3.48 μm, BET 0.86m 2 /g。
(2) Preparation of a Battery
In the preparation of the battery of the embodiment, the steps (1) - (4) are consistent with the embodiment 1; the battery formation step in step (5) was different from that in example 1, and the remainder was the same as that in example 1; the specific formation procedure is as follows:
the prepared battery is charged to 3.85V with a charging current of 0.04C, then charged for 20 minutes at a constant voltage, charged to 4.25V with 0.02C, then discharged to 3.85V with a current of 0.02C, and then charged and discharged 3 times with a current of 0.04C between 3.75 and 4.25V.
Example 4
(1) Preparation of ternary cathode material
The preparation of the ternary positive electrode material in this example was identical to example 1 of example 1; the ternary positive electrode material of the final embodiment is also a Ta doped ternary positive electrode material, and it is a single crystal material with d50=3.54 μm and BET of 0.89 m 2 /g。
(2) Preparation of a Battery
In the preparation of the battery of the embodiment, the steps (1) - (4) are consistent with the embodiment 1; the battery formation step in step (5) was different from that in example 1, and the remainder was the same as that in example 1; the specific formation procedure is as follows:
the prepared battery was charged to 3.85V at a charging current of 0.04C and to 4.25V at 0.02C.
Example 5
(1) Preparation of ternary cathode material
The ternary cathode material of this example was prepared differently from example 1 in that the doped metallic element Ta was replaced with Mo, i.e. Ta in example 1 2 O 5 Replaced by MoO 3 The remainder were identical to example 1; the ternary positive electrode material obtained in the final example was a Mo-doped ternary positive electrode material and was a single crystal material with d50=3.59 μm and BET of 0.90m 2 /g。
(2) Preparation of a Battery
In the preparation of the battery of the embodiment, the steps (1) - (4) are consistent with the embodiment 1; the battery formation step in step (5) was different from that in example 1, and the remainder was the same as that in example 1; the specific formation procedure is as follows:
the vacuum packed and standing battery is charged to 3.8V with a charging current of 0.04C, then charged for 10 minutes at constant voltage, charged to 4.15V with 0.02C, then discharged to 3.75V with a current of 0.02C, and then charged and discharged 3 times with a current of 0.04C between 3.75 and 4.15V.
Example 6
(1) Preparation of ternary cathode material
The ternary cathode material of this example was prepared differently from example 1 in that the doped metallic element Ta was replaced with Mo, i.e. Ta in example 1 2 O 5 Is replaced by WO 3 The remainder were identical to example 1; the ternary positive electrode material obtained in this example was a W-doped ternary positive electrode material, and it was a single crystal material with d50=3.70 μm and BET of 0.95m 2 /g。
(2) Preparation of a Battery
In the preparation of the battery of the embodiment, the steps (1) - (4) are consistent with the embodiment 1; the battery formation step in step (5) was different from that in example 1, and the remainder was the same as that in example 1; the specific formation procedure is as follows:
the vacuum packed and standing battery is charged to 3.8V with a charging current of 0.04C, then charged for 10 minutes at constant voltage, charged to 4.15V with 0.02C, then discharged to 3.75V with a current of 0.02C, and then charged and discharged 3 times with a current of 0.04C between 3.75 and 4.15V.
Example 7
(1) Preparation of ternary cathode material
The preparation of the ternary positive electrode material in the embodiment adopts a liquid phase/high temperature solid phase reaction method, and comprises the following specific steps:
s1, firstly, ta is added 2 O 5 Dissolving in absolute ethanol, stirring at 60deg.C for 2 hr to dissolve completely, adding LiOH, stirring for 30min, and adding ternary positive electrode material precursor [ N 92 Co 5 Mn 3 ](OH 2 ) Adding and stirring for 4h, wherein the molar ratio of Li to Ta (Ni+Co+Mn) is 0.85:0.001:0.999, and finally obtainingPlacing the mixed solution in a blast drying oven at 120 ℃ for drying for 24 hours to obtain powder;
s2, heating the powder prepared in the step S1 to 800 ℃ at a heating rate of 4 ℃/min, performing heat treatment in a tube furnace under 100% oxygen by volume for 3 hours, cooling to room temperature along with the furnace, and crushing and screening to obtain primary sintered materials;
s3, adding the primary sintering material in the S2 and LiOH into a mixer for mixing, wherein the addition amount of the LiOH and the primary sintering material is calculated according to the mole ratio of Li (Ni+Co+Mn) of 0.2:0.1, and then sintering according to the following procedures: under the oxygen atmosphere, firstly heating to 400 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 4 hours, then heating to 830 ℃ at the heating rate of 4 ℃/min, keeping the temperature for 12 hours to obtain a secondary sintering material, crushing and screening the secondary sintering material to obtain the Ta doped ternary anode material, wherein the Ta doped ternary anode material is a single crystal material, D50=2μm and BET is 0.3m 2 /g。
(2) Preparation of a Battery
In the preparation of the battery of the embodiment, the steps (1) - (4) are consistent with the embodiment 1; the battery formation step in step (5) was different from that in example 1, and the remainder was the same as that in example 1; the specific formation procedure is as follows:
the vacuum packed and standing battery is charged to 3.8V with a charging current of 0.04C, then charged for 10 minutes at constant voltage, charged to 4.15V with 0.02C, then discharged to 3.75V with a current of 0.02C, and then charged and discharged 3 times with a current of 0.04C between 3.75 and 4.15V.
Example 8
(1) Preparation of ternary cathode material
The preparation of the ternary cathode material in this embodiment is different from that of embodiment 1 in that the sintering process of S5 is different, and the specific operation is as follows: heating the powder dried in the step S4 to 750 ℃ at a heating rate of 4 ℃/min, performing heat treatment in a tube furnace for 3 hours under an oxygen atmosphere, cooling to room temperature along with the furnace, and crushing and screening to obtain a three-time sintered material; in S6 (ni+co+mn): ta: the molar ratio of Li varies, specifically (ni+co+mn): ta: li=0.998:0.02:0.05; the remainder was the same as in example 1; the ternary positive electrode material obtained in the final embodiment is also Ta doped ternary positive electrode materialThe material, and which is a single crystal material, d50=4.5 μm, BET 1.1 m 2 /g。
(2) Preparation of a Battery
In the preparation of the battery of the embodiment, the steps (1) - (4) are consistent with the embodiment 1; the battery formation step in step (5) was different from that in example 1, and the remainder was the same as that in example 1; the specific formation procedure is as follows:
the vacuum packed and standing battery is charged to 3.8V with a charging current of 0.04C, then charged for 10 minutes at constant voltage, charged to 4.15V with 0.02C, then discharged to 3.75V with a current of 0.02C, and then charged and discharged 3 times with a current of 0.04C between 3.75 and 4.15V.
Example 9
(1) Preparation of ternary cathode material
The preparation of the ternary cathode material in this embodiment is different from that of embodiment 1 in that the sintering process of S5 is different, and the specific operation is as follows: heating the powder dried in the step S4 to 820 ℃ at a heating rate of 4 ℃/min, performing heat treatment in a tube furnace for 12 hours under an oxygen atmosphere, cooling to room temperature along with the furnace, and crushing and screening to obtain a three-time sintered material; in S6 (ni+co+mn): ta: the molar ratio of Li varies, specifically (ni+co+mn): ta: li=0.994:0.06:0.05; the remainder was identical to example 1; the ternary positive electrode material obtained in this example was also a Ta-doped ternary positive electrode material, and it was a single crystal material with d50=3.49 μm and BET of 0.84m 2 /g。
(2) Preparation of a Battery
In the preparation of the battery of the embodiment, the steps (1) - (4) are consistent with the embodiment 1; the battery formation step in step (5) was different from that in example 1, and the remainder was the same as that in example 1; the specific formation procedure is as follows:
the vacuum packed and standing battery is charged to 3.8V with a charging current of 0.04C, then charged for 10 minutes at constant voltage, charged to 4.15V with 0.02C, then discharged to 3.75V with a current of 0.02C, and then charged and discharged 3 times with a current of 0.04C between 3.75 and 4.15V.
Example 10
(1) Preparation of ternary cathode material
The preparation of the ternary cathode material in this embodiment is different from that of embodiment 1 in that the sintering process of S5 is different, and the specific operation is as follows: heating the powder dried in the step S4 to 730 ℃ at a heating rate of 4 ℃/min, performing heat treatment in a tube furnace for 2 hours under an oxygen atmosphere, cooling to room temperature along with the furnace, and crushing and screening to obtain a three-time sintered material; in S6 (ni+co+mn): ta: the molar ratio of Li varies, specifically (ni+co+mn): ta: li=0.991:0.09:0.05; the remainder was identical to example 1; the ternary positive electrode material obtained in this example was also a Ta-doped ternary positive electrode material, and it was a single crystal material with d50=5.0 μm and BET of 1.3m 2 /g。
(2) Preparation of a Battery
In the preparation of the battery of the embodiment, the steps (1) - (4) are consistent with the embodiment 1; the battery formation step in step (5) was different from that in example 1, and the remainder was the same as that in example 1; the specific formation procedure is as follows:
the vacuum packed and standing battery is charged to 3.8V with a charging current of 0.04C, then charged for 10 minutes at constant voltage, charged to 4.15V with 0.02C, then discharged to 3.75V with a current of 0.02C, and then charged and discharged 3 times with a current of 0.04C between 3.75 and 4.15V.
Example 11
(1) Preparation of ternary cathode material
The ternary cathode material in this example was prepared differently from example 1 in that Ta in S2: the molar ratio of (Ni+Co+Mn) is different, specifically Ta: (ni+co+mn) =0.0005:0.9995; the sintering process of S5 is different, and the specific operation is as follows: heating the powder dried in the step S4 to 830 ℃ at a heating rate of 4 ℃/min, performing heat treatment in a tube furnace for 18 hours under an oxygen atmosphere, cooling to room temperature along with the furnace, and crushing and screening to obtain a third-time sintered material; in S6 (ni+co+mn): ta: the molar ratio of Li varies, specifically (ni+co+mn): ta: li=0.9995:0.0005:0.05; the remainder was identical to example 1; the ternary positive electrode material obtained in this example was also a Ta-doped ternary positive electrode material, and it was a single crystal material with d50=1.5 μm and BET of 0.1m 2 /g。
(2) Preparation of a Battery
In the preparation of the battery of the embodiment, the steps (1) - (4) are consistent with the embodiment 1; the battery formation step in step (5) was different from that in example 1, and the remainder was the same as that in example 1; the specific formation procedure is as follows:
the vacuum packed and standing battery is charged to 3.8V with a charging current of 0.04C, then charged for 10 minutes at constant voltage, charged to 4.15V with 0.02C, then discharged to 3.75V with a current of 0.02C, and then charged and discharged 3 times with a current of 0.04C between 3.75 and 4.15V.
Example 12
(1) Preparation of ternary cathode material
The preparation of the ternary cathode material in this embodiment is different from that of embodiment 1 in that the sintering process of S5 is different, and the specific operation is as follows: heating the powder dried in the step S4 to 700 ℃ at a heating rate of 4 ℃/min, performing heat treatment in a tube furnace for 2 hours under the oxygen atmosphere, cooling to room temperature along with the furnace, and crushing and screening to obtain a three-time sintered material; in S6 (ni+co+mn): ta: the molar ratio of Li varies, specifically (ni+co+mn): ta: li=0.986:0.014:0.05; the remainder was identical to example 1; the ternary positive electrode material obtained in this example was also a Ta-doped ternary positive electrode material, and it was a single crystal material with d50=6μm and BET of 1.8 m 2 /g。
(2) Preparation of a Battery
In the preparation of the battery of the embodiment, the steps (1) - (4) are consistent with the embodiment 1; the battery formation step in step (5) was different from that in example 1, and the remainder was the same as that in example 1; the specific formation procedure is as follows:
the vacuum packed and standing battery is charged to 3.8V with a charging current of 0.04C, then charged for 10 minutes at constant voltage, charged to 4.15V with 0.02C, then discharged to 3.75V with a current of 0.02C, and then charged and discharged 3 times with a current of 0.04C between 3.75 and 4.15V.
Comparative example 1
(1) Preparation of ternary cathode material
The ternary cathode material of this comparative example was prepared differently from example 1 in that the sintering process of S4 hadThe specific operation is as follows: the primary sinter prepared in S3, lithium chloride (LiCl) and lithium nitrate (LiNO) 3 ) Mixing at a molar ratio of 10:12:88, heating the mixture to 300 ℃ at a heating rate of 4 ℃/min, and calcining in oxygen for 6 hours to obtain a secondary sintering material, wherein the secondary sintering material is Ta/LiNi 0.92 Co 0.05 Mn 0.03 O 2 Wherein Ta is homogeneously doped in LiNi 0.92 Co 0.05 Mn 0.03 O 2 In (a) and (b); flushing the secondary sintering material for 5 times by distilled water and ethanol to remove redundant lithium salt and exchanged sodium salt, and then drying at 60 ℃ for 24 hours; the sintering process of S5 is different, and the specific operation is as follows: heating the powder dried in the step S4 to 650 ℃ at a heating rate of 4 ℃/min, performing heat treatment in a tube furnace for 3 hours under an oxygen atmosphere, cooling to room temperature along with the furnace, and crushing and screening to obtain a three-time sintered material; the remainder was identical to example 1; the ternary positive electrode material obtained in the final comparative example was also a Ta-doped ternary positive electrode material, and it was a single crystal material, d50=3.51 μm, and BET was 0.89 m 2 /g。
(2) Preparation of a Battery
In the preparation of the comparative example battery, the steps (1) - (4) are consistent with example 1; the battery formation step in step (5) was different from that in example 1, and the remainder was the same as that in example 1; the specific formation procedure is as follows:
the prepared battery was charged to 3.8V at a charging current of 0.04C and charged to 4.15V at 0.02C.
Comparative example 2
(1) Preparation of ternary cathode material
The ternary cathode material of this comparative example was prepared differently from example 1 in that the doped metallic element Ta was replaced with Mo, i.e., ta in example 1 2 O 5 Replaced by MO 3 The method comprises the steps of carrying out a first treatment on the surface of the The sintering process of S4 is different, and the specific operation is as follows: the primary sinter prepared in S3, lithium chloride (LiCl) and lithium nitrate (LiNO) 3 ) Mixing at a molar ratio of 10:12:88, heating the mixture to 300 ℃ at a heating rate of 4 ℃/min, and calcining in oxygen for 6 hours to obtain a secondary sintering material, wherein the secondary sintering material is preparedThe binder is Mo/LiNi 0.92 Co 0.05 Mn 0.03 O 2 Wherein Mo is homogeneously doped in LiNi 0.92 Co 0.05 Mn 0.03 O 2 In (a) and (b); flushing the secondary sintering material for 5 times by distilled water and ethanol to remove redundant lithium salt and exchanged sodium salt, and then drying at 60 ℃ for 24 hours; the sintering process of S5 is different, and the specific operation is as follows: heating the powder dried in the step S4 to 700 ℃ at a heating rate of 4 ℃/min, performing heat treatment in a tube furnace for 3 hours under an oxygen atmosphere, cooling to room temperature along with the furnace, and crushing and screening to obtain a three-time sintered material; the remainder was identical to example 1; the ternary positive electrode material obtained in the final comparative example was a Mo-doped ternary positive electrode material, and it was a single crystal material, d50=3.52 μm, BET 0.86m 2 /g。
(2) Preparation of a Battery
In the preparation of the comparative example battery, the steps (1) - (4) are consistent with example 1; the battery formation step in step (5) was different from that in example 1, and the remainder was the same as that in example 1; the specific formation procedure is as follows:
the vacuum-packed and left-standing battery was charged to 3.8V at a charging current of 0.04C and to 4.15V at 0.02C.
Comparative example 3
(1) Preparation of ternary cathode material
The ternary cathode material of this comparative example was prepared differently from example 1 in that the doped metallic element Ta was replaced with Mo, i.e., ta in example 1 2 O 5 MgO is substituted, the remainder being the same as in example 1; the ternary positive electrode material obtained in the final comparative example was a Mg-doped ternary positive electrode material, and it was a single crystal material with d50=3.53 μm and BET of 0.87m 2 /g 。
(2) Preparation of a Battery
In the preparation of the comparative example battery, the steps (1) - (4) are consistent with example 1; the battery formation step in step (5) was different from that in example 1, and the remainder was the same as that in example 1; the specific formation procedure is as follows:
the vacuum-packed and left-standing battery was charged to 3.85V at a charging current of 0.04C and to 4.25V at 0.02C.
Test case
Experimental construction method the batteries of examples 1 to 12 and comparative examples 1 to 3 were tested for capacity performance and cycle performance, and the ternary cathode materials of examples 1 to 12 and comparative examples 1 to 3 were subjected to Ni before and after cycle 4+ And (5) testing the content.
The test method of each performance is as follows:
(1) Capacity performance test: and setting the voltage range to be 2.75-4.3V at 25 ℃, charging and discharging the prepared battery at 0.33C multiplying power, recording the first-circle charge and discharge capacity, and calculating the gram capacity according to the weight of the pole piece.
(2) And (3) testing the cycle performance: the voltage range is set to be 2.75-4.3V at 45 ℃, the prepared battery is charged and discharged at 0.33C multiplying power within the range of 2.75-4.3V, and when the battery circulates for 400 circles, the capacity retention rate is recorded.
（3）Ni 4+ The retention test method is as follows:
charging the battery to 100% SOC, disassembling the battery to obtain a positive plate, collecting surface signals of the positive plate by XPS, performing peak-by-peak fitting on Ni by peak-by-peak software, and determining Ni valence distribution to obtain Ni 4+ Ion to Ni element ratio.
Experimental results the batteries of examples 1 to 12 and comparative examples 1 to 3 were subjected to capacity performance and cycle performance, and the ternary cathode materials Ni of examples 1 to 12 and comparative examples 1 to 3 were subjected to 4+ The results of the content test are shown in Table 1.
TABLE 1 Capacity Performance and cycle Performance of batteries in examples 1-12, comparative examples 1-3, ni before and after cycling of ternary cathode materials 4+ Test results of content
Figure SMS_1
As can be seen from the test results of Table 1, by doping the ternary positive electrode active material with the metal element M having the highest valence state of not less than 3 and applying appropriate formation conditions, ni at 100% SOC can be controlled 4+ Molar content of (2) in Ni elementLess than 65%, so as to reduce the lithium-nickel mixed discharge degree of the ternary positive electrode active material, improve the lattice stability of the ternary positive electrode active material, and further improve the cycle performance of the battery, and referring to examples 1-12, the reference battery in these examples is Ni under 100% SOC 4+ The molar content of (2) is not less than 65% in the Ni element, so that the reference batteries have higher gram capacity and higher high-temperature cycle capacity retention rate. In the reference cells of comparative examples 1-2, the formation conditions applied were not suitable, resulting in a cell at 100% SOC, ni 4+ The molar content of (2) is lower than 65% in Ni element, so that the lithium nickel mixed discharge degree in the ternary positive electrode active material is higher, and the gram capacity and the high-temperature cycle retention rate of the battery are correspondingly reduced, namely the cycle performance of the battery is poorer. In comparative example 3, when preparing a ternary positive electrode active material, the doped metal element M is Mg, the highest valence state is +2, and Ni cannot be reduced well by a charge compensation mechanism 2+ The content of lithium and nickel in the ternary positive electrode active material is high, so that the gram capacity and the high-temperature cycle retention rate of the battery are correspondingly reduced.
Further, as can be seen from comparative examples 1 to 12, ni when the battery is controlled at 100% SOC 4+ When the molar content of the (B) is not less than 80% in the Ni element, the battery has higher gram capacity and high-temperature cycle capacity retention rate, which means that the battery has better cycle performance.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention, but these modifications or substitutions are all within the scope of the present invention.

Claims (10)

1. A battery, includes positive plate, its characterized in that:
the positive plate is provided with a positive electrode active material layer, and the positive electrode active material layer comprises a ternary positive electrode material;
the ternary positive electrode material is doped with at least one metal element M, wherein the highest valence of the metal element M is more than 3;
in the ternary cathode material, calculated according to the mole ratio, li: ni: co: mn: m=0.95 to 1.1: x: y: and z: a, wherein 0.7 < x < 1,0 < y < 1,0 < z < 1, x+y+z+a=1;
at a battery 100% soc state, the ternary positive electrode material satisfies: ni (Ni) 4+ The ratio of the number of moles of (C) in the total number of moles of Ni element is not less than 65%.
2. The battery of claim 1, wherein the ternary positive electrode material satisfies, at 100% soc of the battery: ni (Ni) 4+ The ratio of the number of moles of (C) in the total number of moles of Ni element is not less than 80%.
3. The battery of claim 1, wherein: the metal element M includes at least one of Nb, ti, mo, ta, W.
4. A battery as claimed in claim 3, wherein: the metal element M comprises at least one of Mo and Ta.
5. The battery of claim 4, wherein: the metal element M is Ta.
6. The battery of claim 1, wherein: a=0.001 to 0.01.
7. The battery of claim 6, wherein: a=0.003 to 0.007.
8. The battery of claim 1, wherein: the D50 of the ternary positive electrode material is 1.5-6.0 mu m.
9. The battery of claim 8, wherein: the BET of the ternary positive electrode material is 0.1m 2 /g~2m 2 /g。
10. The battery of claim 1, wherein preparing the ternary positive electrode material comprises the steps of:
s1, preparing a soluble salt solution by using nickel salt, cobalt salt and manganese salt;
s2, preparing a spherical precursor by utilizing the soluble salt solution and part of the material containing the metal element M, wherein the metal element M is homogeneously doped in the spherical precursor;
s3, mixing the spherical precursor with an alkaline material and calcining to obtain a primary sintered material;
s4, mixing the primary sintering material with lithium salt and calcining to obtain a secondary sintering material;
s5, continuously calcining the secondary sintering material to obtain a tertiary sintering material;
s6, mixing the three-time sintering material, the rest material containing the metal element M and the alkaline lithium compound, and calcining to obtain the ternary positive electrode material.
CN202310493382.5A 2023-05-05 2023-05-05 Battery cell Active CN116247161B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310493382.5A CN116247161B (en) 2023-05-05 2023-05-05 Battery cell

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310493382.5A CN116247161B (en) 2023-05-05 2023-05-05 Battery cell

Publications (2)

Publication Number Publication Date
CN116247161A true CN116247161A (en) 2023-06-09
CN116247161B CN116247161B (en) 2023-08-25

Family

ID=86635275

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310493382.5A Active CN116247161B (en) 2023-05-05 2023-05-05 Battery cell

Country Status (1)

Country Link
CN (1) CN116247161B (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108123115A (en) * 2017-07-12 2018-06-05 北京大学 O2 configuration anode material of lithium battery and preparation method thereof
CN108545785A (en) * 2018-03-07 2018-09-18 格林美（无锡）能源材料有限公司 A kind of large single crystal nickel cobalt manganese anode material and preparation method thereof
CN110993903A (en) * 2019-11-13 2020-04-10 北京理工大学 Tantalum modified high-nickel cathode material and preparation method and application thereof
CN111837265A (en) * 2018-03-07 2020-10-27 日立金属株式会社 Positive electrode active material for lithium ion secondary battery and lithium ion secondary battery
CN112186138A (en) * 2019-07-02 2021-01-05 湖南杉杉新能源有限公司 W-containing high-nickel ternary positive electrode material and preparation method thereof
CN112786876A (en) * 2021-03-02 2021-05-11 昆明理工大学 Preparation method of lithium-rich lithium battery cathode material with single crystal structure

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108123115A (en) * 2017-07-12 2018-06-05 北京大学 O2 configuration anode material of lithium battery and preparation method thereof
CN108545785A (en) * 2018-03-07 2018-09-18 格林美（无锡）能源材料有限公司 A kind of large single crystal nickel cobalt manganese anode material and preparation method thereof
CN111837265A (en) * 2018-03-07 2020-10-27 日立金属株式会社 Positive electrode active material for lithium ion secondary battery and lithium ion secondary battery
CN112186138A (en) * 2019-07-02 2021-01-05 湖南杉杉新能源有限公司 W-containing high-nickel ternary positive electrode material and preparation method thereof
CN110993903A (en) * 2019-11-13 2020-04-10 北京理工大学 Tantalum modified high-nickel cathode material and preparation method and application thereof
CN112786876A (en) * 2021-03-02 2021-05-11 昆明理工大学 Preparation method of lithium-rich lithium battery cathode material with single crystal structure

Also Published As

Publication number Publication date
CN116247161B (en) 2023-08-25

Similar Documents

Publication Publication Date Title
CN112750999B (en) Cathode material, preparation method thereof and lithium ion battery
CN109721109A (en) A kind of lithium battery nickel-cobalt-manganternary ternary anode material presoma and preparation method thereof and the positive electrode being prepared
US20230335713A1 (en) Positive electrode material, preparation method therefor and lithium ion battery
CN110931797A (en) High-nickel positive electrode material with composite coating layer and preparation method thereof
CN106910887B (en) Lithium-rich manganese-based positive electrode material, preparation method thereof and lithium ion battery containing positive electrode material
CN111081994B (en) Surface-modified lithium-rich layered transition metal oxide and preparation method and application thereof
CN110233250A (en) A kind of preparation method of single crystal grain tertiary cathode material
CN110459764B (en) Lithium ion battery positive electrode material and preparation method and application thereof
CN106025208A (en) Preparation method for carbon-coated ternary positive electrode material
CN112510200A (en) Preparation method of lithium-rich manganese-based material coated by double conductive layers
JP2011249293A (en) Lithium transition metal compound and its manufacturing method, and lithium ion battery
CN112701276A (en) Quaternary polycrystalline positive electrode material and preparation method and application thereof
CN102832381A (en) Preparation method of high-voltage cathode material Lil+xMn3/2-yNil/2-zMy+zO4 of lithium ion battery with long service life
CN112421009A (en) Positive electrode material, method for producing same, and secondary battery
CN116014104A (en) Lithium-rich nickel positive electrode material, preparation method thereof, positive electrode sheet and secondary battery
CN105826568A (en) Lithium-rich positive electrode material with hypoxic metallic oxide coating layer structure, preparation method and application
CN103413935A (en) Mo-doped lithium-rich positive electrode material and preparation method thereof
CN102544473A (en) Lithium ion battery anode material layered lithium manganese oxide and manufacturing method thereof
CN113582253A (en) Quaternary positive electrode material and preparation method and application thereof
CN107834054B (en) Preparation method of lithium nickel manganese oxide-graphene composite material for lithium ion battery
CN113745514B (en) Fluorine-doped and lithium silicate-coated lithium-rich manganese-based positive electrode material and preparation method and application thereof
CN115148970A (en) Olivine NaMPO 4 High-nickel-coated ternary or lithium-rich manganese-based positive electrode material and preparation method thereof
CN115133018A (en) Preparation method and application of positive electrode lithium supplement additive
CN116247161B (en) Battery cell
CN113745478A (en) Electrode material and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant