CN110299535B - Ternary material precursor, preparation method thereof, ternary material and battery - Google Patents
Ternary material precursor, preparation method thereof, ternary material and battery Download PDFInfo
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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
- 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
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/46—Alloys based on magnesium or aluminium
- H01M4/463—Aluminium based
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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
- H01M4/50—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- 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
Abstract
Ternary material precursor, preparation method thereof, ternary material and battery, wherein the ternary material precursor comprises Ni x Co y (OH) z Ni formed by primary particle agglomeration x Co y (OH) z Secondary particles and uniformly dispersed in Ni x Co y (OH) z Alumina particles in the primary particle gaps, based on the total mole number of nickel element and cobalt element in the ternary material precursor, wherein the Ni is x Co y (OH) z The aluminum content of the surface of the secondary particles is less than 0.1%; the precursor of the ternary material of nickel, cobalt and aluminum prepared by the method has extremely low content of alumina on the surface of the precursor, and can greatly reduce the surface inertia alpha-Al of the ternary material in the later high-temperature lithiation process 2 O 3 Forming of (3).
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a precursor of a positive electrode active material of a lithium ion battery, a preparation method of the precursor, a positive electrode material and a battery.
Background
In the prior art, a coprecipitation method is generally adopted for preparing a nickel-cobalt-aluminum ternary material, three elements of nickel, cobalt and aluminum are prepared into a mixed salt solution, the mixed salt solution, a complexing agent and a precipitating agent are simultaneously pumped into a reaction kettle according to a certain speed, and a spherical nickel-cobalt-aluminum ternary material precursor is prepared by stirring at a certain temperature 3 Has a much lower solubility product than Ni (OH) 2 And Co (OH) 2 Therefore, Al (OH) 3 Will precipitate preferentially, the three elements are difficult to achieve the blending of atomic level, the precursor with uniform internal element distribution is difficult to form, in addition, Al (OH) 3 The precipitate is flocculent precipitate, which easily damages the spherical growth of the precursor and leads to difficult formation of uniform secondary spheres; in the scheme, a new complexing agent is added in the mixing process to reduce the precipitation speed of Al and realize the coprecipitation of Al, Ni and Co, but the complexing agent can complex Ni and Co simultaneously, so that the precipitation of Ni and Co is influenced, and the spherical shape of the synthesized precursor is poor. In order to solve the problems, a binary precursor of nickel and cobalt is prepared firstly, and then an Al source and a Li source are supplemented for heat treatment.
Disclosure of Invention
The invention provides a precursor of positive active material, which aims at the technical problem, and comprises Ni x Co y (OH) z Ni formed by primary particle agglomeration x Co y (OH) z The secondary particles and the nano alumina particles uniformly dispersed in the gaps of the primary particles, wherein the content of aluminum on the surface of the ternary material precursor is lower than 0.1 percent based on the weight of the ternary material precursor.
The inventor of the application finds that in the nickel, cobalt and aluminum ternary material precursor prepared by the prior art, alumina can be enriched on the surface of the precursor, and the partially enriched alumina can be used as inert alpha-Al in the process of high-temperature lithiation of the precursor 2 O 3 The form (b) exists, which seriously affects the lithium conducting performance of the positive active material; the precursor of the nickel, cobalt and aluminum ternary material prepared by the method has extremely low content of alumina on the surface of the precursor, and can greatly reduce the surface inertia alpha-Al of the ternary material in the later high-temperature lithiation process 2 O 3 Is performed.
The invention also provides a preparation method of the ternary material precursor, which is characterized by comprising the following steps:
(1) mixing nickel salt and cobalt salt according to a ratio to form a mixed solution;
(2) dispersing nano alumina powder in water solution to form suspension;
(3) and mixing the mixed solution, the suspension and the aqueous solution of the complexing agent at the same speed, and performing spray drying after reaction to prepare the ternary material precursor.
The preparation method of the ternary material precursor comprises the steps of dispersing nano-alumina in an aqueous solution by utilizing ultrasound to prepare a suspension with uniformly dispersed nano-alumina, mixing the suspension with nickel salt and cobalt salt easily and mixing a complexing agent at the same speed to prepare the ternary material precursor, wherein the alumina is not enriched on the surface of secondary particles but uniformly dispersed in gaps of primary particles forming the secondary particles, the aluminum content of the surface of the secondary particles is extremely low, the formation of inert alumina on the surface of the ternary material in the later-stage precursor and lithium salt mixing and high-temperature sintering process is reduced, and the lithium conductivity of the anode is improved.
The invention further provides a ternary material precursor, which is prepared by the preparation method of the ternary material precursor.
The invention further provides a preparation method of the ternary material, which comprises the step of mixing and sintering the ternary material precursor and a lithium source in an oxygen-containing atmosphere.
The invention further provides a ternary material prepared by the preparation method of the ternary material.
The invention further provides a positive electrode which comprises the ternary material.
The invention also provides a battery comprising the positive electrode.
Detailed Description
In order to make the technical problems, technical solutions and beneficial effects solved by the present invention more clear, the present invention is further described in detail below with reference to specific embodiments; it should be understood that the detailed description and specific examples, while indicating the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
The invention provides a nickel, cobalt and aluminum ternary material precursor which is characterized by comprising Ni x Co y (OH) z Ni formed by primary particle agglomeration x Co y (OH) z The secondary particles and the nano alumina particles uniformly dispersed in the gaps of the primary particles, wherein the content of aluminum on the surface of the ternary material precursor is lower than 0.1 percent by taking the weight of the ternary material precursor as a reference; the content of aluminum on the surface of the ternary material precursor refers to the ratio of aluminum element in the aluminum oxide on the surface of the precursor particles to the weight of the whole precursor based on the weight of the precursor; the smaller the ratio of aluminum element in the aluminum oxide on the surface of the precursor particle to the weight of the whole precursor is, the lower the content of the aluminum oxide on the surface of the precursor particle is; the inert substances converted from the alumina on the surface are converted in the process of further preparing the ternary material by adopting the ternary material precursorThe smaller the amount of alpha-Al 2O3, the better the lithium conducting performance of the prepared ternary material.
According to the ternary material precursor provided by the invention, preferably, the nano alumina particles are uniformly dispersed in Ni x Co y (OH) z Inside the secondary spherical particles.
Nano alumina particles are uniformly dispersed in Ni x Co y (OH) z The interior of the secondary spherical particles is in a 'dragon fruit' type model, namely the surface of the precursor does not contain alumina, and the formation of inert alpha-Al 2O3 on the surface of the ternary material is avoided after the ternary material precursor is prepared into the ternary material.
According to the ternary material precursor provided by the invention, preferably, the nano aluminum oxide is subjected to surface amination treatment.
According to the ternary material precursor provided by the invention, preferably, the nano aluminum oxide is subjected to surface amination treatment and surface hydroxylation treatment.
By carrying out surface amination treatment on the nano-alumina in advance or carrying out surface amination treatment and surface hydroxylation treatment on the nano-alumina colleagues, on one hand, the nano-alumina can be subjected to Ni treatment x Co y (OH) z The secondary spherical particles are uniformly distributed inside, so that the ternary material with uniform aluminum distribution and high tap density can be obtained conveniently, the formation of inert alpha-Al 2O3 on the surface of the ternary material can be reduced, and the ionic conductivity of the ternary material is improved.
According to the ternary material precursor provided by the invention, preferably, the average particle size of the nano alumina particles is 20nm-100 nm.
The grain size of the nano alumina is controlled in the range, which is more beneficial to forming a ternary material precursor with low aluminum content on the surface.
According to the ternary material precursor provided by the invention, preferably, the content of aluminum in the ternary material precursor is 1-2% by weight of the ternary material precursor.
The invention also provides a preparation method of the ternary material precursor, which comprises the following steps:
(1) mixing a nickel source and a cobalt source according to a ratio to form a mixed solution;
(2) dispersing nano alumina powder in an aqueous solution to form a suspension;
(3) and mixing the mixed solution, the suspension and the aqueous solution of the complexing agent at the same speed, and drying after reaction to prepare the ternary material precursor.
Wherein the nickel source and the cobalt source are various nickel salts and cobalt salts which are conventionally used in the field, and the ratio of the nickel source to the cobalt source is 3:1-10: 1.
According to the preparation method of the ternary material precursor, provided by the invention, the complexing agent is selected from one or more of ammonia, tartaric acid, heptonate, sodium gluconate, sodium alginate, salicylic acid, boric acid, ethylene diamine tetraacetic acid or disodium ethylene diamine tetraacetate; in the water solution of the complexing agent, the concentration of the complexing agent is 0.1 to 10 percent
According to the preparation method of the ternary material precursor, provided by the invention, the average grain diameter of the nano-alumina is 20nm-100 nm.
According to the preparation method of the ternary material precursor provided by the invention, the dispersion method in the step (2) is not particularly limited as long as the nano alumina can form a uniformly dispersed suspension, and ultrasonic dispersion, emulsifying dispersion or grinding dispersion can be adopted, and ultrasonic dispersion is preferably adopted.
According to the preparation method of the ternary material precursor, provided by the invention, in the step (3), the reaction is carried out in a reaction kettle, the mixed solution, the suspension and the aqueous solution of the complexing agent can be pumped into the reaction kettle at the same speed, the stirring speed of the reaction kettle is 200r/min-800r/min, and the pumping speed of the mixed solution, the suspension and the aqueous solution of the complexing agent into the reaction kettle is 1ml/min-10 ml/min; the drying method in step (3) may be spray drying.
According to the preparation method of the ternary material precursor, provided by the invention, the reaction temperature is 25-60 ℃, the reaction time is 8-60h, and the pH value of a reaction system is 10-13; preferably, the reaction temperature is 30-50 ℃, the reaction time is 10-12h, and the pH value of the reaction system is 10-12, wherein sodium hydroxide solution and the like can be added into the reaction kettle to adjust the pH value of the whole reaction.
According to the preparation method of the ternary material precursor, provided by the invention, the nano aluminum oxide is subjected to surface amination treatment.
According to the preparation method of the ternary material precursor, provided by the invention, the surface amination treatment comprises the steps of immersing nano aluminum oxide into an organic solvent of an amination reagent for heat treatment and then washing.
The preparation method of the ternary material precursor provided by the invention is characterized in that the heat treatment temperature is 40-100 ℃, and the heat treatment time is 0.5-10 h.
According to the preparation method of the ternary material precursor, provided by the invention, the concentration of the organic solution of the amination reagent is 0.1% -10%; the organic solvent may be a conventional organic solvent, and for example, absolute ethanol may be used.
According to the preparation method of the ternary material precursor, provided by the invention, the amination treatment further comprises a step of aging after heat treatment, the aging time is 2-48h, and the temperature during aging can be 40-100 ℃.
According to the preparation method of the ternary material precursor, provided by the invention, the nano aluminum oxide further comprises a surface hydroxylation treatment step after the surface amination treatment.
According to the preparation method of the ternary material precursor, provided by the invention, the surface hydroxylation treatment comprises the step of immersing the nano-alumina subjected to the surface amination treatment into hydrogen peroxide for treatment; wherein the concentration of the hydrogen peroxide is 0.01-30 wt%, preferably 1-15 wt%.
The preparation method of the ternary material precursor is characterized in that the amination reagent is selected from one or more of polyethyleneimine, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane and polyglycidyl methacrylate.
According to the preparation method of the ternary material precursor, provided by the invention, the complexing agent is selected from one or more of ammonia, tartaric acid, heptonate, sodium gluconate, sodium alginate, salicylic acid, boric acid, ethylenediamine tetraacetic acid or disodium ethylenediamine tetraacetic acid.
The invention also provides a ternary material precursor, which is prepared by the method.
The invention also provides a preparation method of the ternary material, which comprises the step of mixing and sintering the ternary material precursor and a lithium source in an oxygen-containing atmosphere.
According to the preparation method of the ternary material provided by the invention, preferably, the temperature of the mixed sintering is 600-1100 ℃, and the sintering time is 8-20 h; the lithium source is one or more selected from lithium carbonate, lithium hydroxide monohydrate, lithium acetate and lithium nitrate.
According to the preparation method of the ternary material provided by the invention, preferably, the molar ratio of the positive electrode active material precursor to the lithium source is 1: 1.0-1.1.
The invention also provides a ternary material prepared by the method.
The above method for sintering the ternary material precursor and the lithium source in an oxygen-containing atmosphere is well known in the art, and includes mixing the ternary material precursor and the lithium source, and then sintering the mixture in an oxygen-containing atmosphere, wherein the sintering method is as follows: sintering at 600-1100 deg.c for 8-20 hr and cooling to room temperature. The lithium source is well known in the art, and may be selected from one or more of lithium hydroxide, lithium carbonate, lithium nitrate, and organic lithium salts. When mixed, the molar ratio of the ternary material precursor to the lithium source, based on the moles of the nuclear metal and the lithium, is 1: 1.0-1.1.
The invention also provides a positive electrode which comprises the ternary material.
The invention discloses a lithium ion battery, wherein a positive electrode comprises a positive active material, a positive binder and a positive conductive agent, wherein the positive active material is a ternary material disclosed by the invention; the cathode binder can adopt cathode binders known in the art, for example, one or more of polyvinylidene fluoride, polytetrafluoroethylene or styrene butadiene rubber; the content of the positive electrode binder is 0.1-15wt% of the positive electrode material, preferably 1-7 wt%; the positive electrode conductive agent can adopt any conductive agent known in the field, for example, one or more of graphite, acetylene black, carbon fiber, carbon black, metal powder and fiber can be adopted; the content of the positive electrode conductive agent is 0.1-20wt% of the positive electrode material, and preferably 2-10 wt%. The preparation method of the positive electrode can adopt various methods commonly used in the field, for example, a positive electrode active material, a positive electrode binder and a positive electrode conductive agent are prepared into positive electrode slurry by using a solvent, the adding amount of the solvent is well known to a person skilled in the art, and the solvent can be flexibly adjusted according to the viscosity and operability requirements of slurry coating of the prepared positive electrode slurry. And coating the prepared anode slurry on an anode current collector, drying and tabletting, and cutting into pieces to obtain the anode. The drying temperature is generally 120 ℃ and the drying time is generally 5 hours. The solvent used in the positive electrode slurry may be any of various solvents known in the art, such as one or more selected from N-methylpyrrolidone (NMP), Dimethylformamide (DMF), Diethylformamide (DEF), Dimethylsulfoxide (DMSO), Tetrahydrofuran (THF), and water and alcohols. The solvent is used in an amount such that the slurry can be applied to the conductive substrate. Generally, the solvent is used in an amount such that the content of the positive electrode material in the slurry is 40 to 90 wt%, preferably 50 to 85 wt%.
The invention also discloses a lithium battery which comprises the anode provided by the invention.
The structure and the preparation method of the lithium ion battery disclosed by the invention are known by technicians in the field, and the lithium ion battery comprises a shell, pole cores positioned in the shell, a cover plate for sealing the shell and electrolyte positioned in the shell and between the pole cores; the pole core comprises a positive pole piece, a negative pole piece and a diaphragm positioned between the positive pole piece and the negative pole piece; the positive plate comprises a positive current collector and a positive material coated on the positive current collector; the negative plate comprises a negative current collector and a negative material coated on the negative current collector; the positive electrode material comprises a positive electrode active material, a positive electrode binder and a positive electrode conductive agent, and the positive electrode active material is the positive electrode material disclosed by the invention.
The preparation method of the lithium ion battery is well known to those skilled in the art, and for example, the positive/negative electrode active material, the positive/negative electrode conductive agent and the positive/negative electrode binder are dissolved in a solvent according to a certain ratio to be mixed into a positive/negative electrode slurry, and the slurry is coated on a wide conductive substrate, and then dried, rolled and slit to obtain a positive/negative electrode sheet. The conditions for drying and rolling are well known to those skilled in the art, for example, the temperature for drying the negative electrode sheet is generally 60 to 120 c, preferably 80 to 110 c, and the drying time is 0.5 to 5 hours. The pole core structure of the battery provided by the invention is a pole core structure commonly used in the field, and generally, the pole core can be manufactured by winding or stacking a positive plate, a separator and a negative plate, and the winding or stacking manner is well known to those skilled in the art. The separator of the battery of the present invention has electrical insulation properties and liquid retention properties. The separator may be selected from various separators used in lithium ion secondary batteries well known to those skilled in the art, such as polyolefin microporous films, polyethylene mats, glass fiber mats, or ultra fine glass fiber papers.
The negative electrode forming the lithium ion battery of the present invention may be a negative electrode conventionally used in the art; for example, the negative electrode includes a current collector and a negative electrode material coated and/or filled on the current collector, the negative electrode material including a negative electrode active material and a negative electrode binder; the negative active material is not particularly limited, and a negative active material capable of intercalating and releasing lithium, which is conventional in the art, may be used, such as one or more of natural graphite, artificial graphite, petroleum coke, organic pyrolysis carbon, mesocarbon microbeads, carbon fibers, tin alloys, and silicon alloys, preferably artificial graphite. The negative electrode material may further include a negative electrode conductive agent, which is not particularly limited and may be one or more of negative electrode conductive agents conventional in the art, such as ketjen black carbon, acetylene black, furnace black, carbon fibers VGCF, conductive carbon black, and conductive graphite; the content of the negative electrode conductive agent is 1 to 15wt%, preferably 2 to 10wt%, based on the weight of the negative electrode material. The kind and content of the negative electrode binder are well known to those skilled in the art, and may be, for example, one or more selected from fluorine-containing resin and polyolefin compound such as polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR); generally, the content of the negative electrode binder is 0.01 to 8 wt%, preferably 0.02 to 5wt%, based on the weight of the negative electrode material, depending on the kind of the binder used; preferably, the negative electrode binder is a mixture of a cellulose-based polymer and a rubber latex, such as a mixture of a cellulose-based polymer and Styrene Butadiene Rubber (SBR). The amount of the cellulose-based polymer and styrene-butadiene rubber is well known to those skilled in the art; the negative electrode current collector may be a conventional negative electrode current collector in a lithium ion battery, such as a stamped metal, a metal foil, a net metal, a foamed metal, and a copper foil is used as the negative electrode current collector in the embodiment of the present invention.
The electrolyte of the battery of the invention is a nonaqueous electrolyte. The nonaqueous electrolytic solution is a solution of an electrolytic lithium salt in a nonaqueous solvent, and a conventional nonaqueous electrolytic solution known to those skilled in the art can be used. For example, the electrolyte lithium salt may be selected from lithium hexafluorophosphate (LiPF) 6 ) Lithium perchlorate (LiClO) 4 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium hexafluoroarsenate (LiAsF) 6 ) Lithium hexafluorosilicate (LiSiF) 6 ) Lithium tetraphenylborate (LiB (C) 6 H 5 ) 4 ) Lithium chloride (LiCl), lithium bromide (LiBr), lithium chloroaluminate (LiAlCl) 4 ) And fluoro-carbon lithium fluorosulfonate (LiC (SO) 2 CF 3 ) 3 ）、LiCH 3 SO 3 、LiN(SO 2 CF 3 ) 2 One or more of them. The non-aqueous solvent can be selected from a chain acid ester and cyclic acid ester mixed solution, wherein the chain acid ester can be one or more of dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), Methyl Propyl Carbonate (MPC), dipropyl carbonate (DPC) and other chain organic esters containing fluorine, sulfur or unsaturated bonds. The cyclic acid ester can be one or more of Ethylene Carbonate (EC), Propylene Carbonate (PC), Vinylene Carbonate (VC), gamma-butyrolactone (gamma-BL), sultone and other cyclic organic esters containing fluorine, sulfur or unsaturated bonds. Concentration of electrolyte lithium salt in nonaqueous electrolyteThe degree is generally from 0.1 to 2mol/l, preferably from 0.8 to 1.2 mol/l.
The method for manufacturing the battery of the present invention is well known to those skilled in the art, and generally, the method for manufacturing the battery includes placing a core into a battery case, adding an electrolyte, and then sealing to obtain the battery. The sealing method and the amount of the electrolyte are known to those skilled in the art.
The present invention will be further described with reference to the following specific examples.
Example 1
(1) Preparing a ternary material precursor: dissolving nickel sulfate and cobalt sulfate in an aqueous solution according to a molar ratio of 80:15 to prepare a mixed metal salt solution with the concentration of 2 mol/L; taking nano alumina (the average particle size is 150nm), ultrasonically dispersing the nano alumina in an aqueous solution to prepare a suspension, wherein the molar ratio of the nano alumina to nickel sulfate to cobalt sulfate meets the following requirements: nickel sulfate: the preparation method comprises the following steps of (1) mixing a metal salt solution, a suspension of nano alumina and 1mol/L ammonia water into a reaction kettle at a rotation speed of 600r/min under the condition of continuous stirring, wherein the cobalt sulfate ratio is =2.5:15:80, the mixed metal salt solution, the suspension of the nano alumina and the 1mol/L ammonia water are simultaneously pumped into the reaction kettle at an equivalent speed, the pumping speed is 3ml/min, sodium hydroxide is adopted in the reaction kettle to adjust the pH value, the PH value in the reaction kettle is controlled to be 11, the temperature in the reaction kettle is controlled to be 60 ℃, and after 24 hours of continuous reaction, spray drying is carried out, so that ternary precursor powder A1 is prepared;
(2) preparing a ternary material: taking 0.04kg of lithium carbonate and 0.915 kg of precursor A1 powder, and adopting a high-speed mixer according to the molar ratio of a lithium source to a ternary material precursor of 1.08: 1, introducing air into a muffle furnace, heating to 950 ℃, sintering at constant temperature for 12 hours, and cooling to room temperature to obtain a ternary material C1;
(3) preparing a battery: the positive electrode active material, acetylene black and PVDF are mixed in a weight ratio of 100: 4: 5 dissolving in N-methyl pyrrolidone, stirring, coating on aluminum foil, baking at 100 + -5 deg.C, rolling to a certain thickness with a tablet machine, and rolling to obtain positive plate; graphite, acetylene black and PVDF are mixed in a weight ratio of 100: 3: dissolving 6 in N-methyl pyrrolidone, stirringUniformly mixing, coating on a copper foil, baking at the temperature of 100 +/-5 ℃, rolling to a certain thickness by using a tablet press, and rolling and cutting into a negative plate; winding the positive and negative electrode plates and a polypropylene diaphragm with the thickness of 20 mu m into a square lithium ion battery core, collecting the lithium ion battery core in a battery case, welding the lithium ion battery core, and then injecting 1.0mol/L LiPF 6 And (EC + EMC + DMC) (wherein the mass ratio of EC, EMC and DMC is 1: 1: 1) electrolyte, sealing and preparing the lithium battery S1.
Example 2
The ternary precursor, the ternary material and the lithium ion battery of the lithium ion battery are prepared by the same method as the embodiment 1, except that the average particle size of the nano alumina particles adopted in the step (1) is 20nm, and the prepared ternary precursor, ternary material and lithium ion battery are respectively A2, C2 and S2.
Example 3
The ternary precursor, the ternary material and the lithium ion battery of the lithium ion battery are prepared by the same method as the embodiment 1, except that the average particle size of the nano alumina particles adopted in the step (1) is 50nm, and the prepared ternary precursor, ternary material and lithium ion battery are respectively A3, C3 and S3.
Example 4
The ternary precursor, the ternary material and the lithium ion battery of the lithium ion battery are prepared by the same method as the embodiment 1, except that the average particle size of the nano alumina particles adopted in the step (1) is 100nm, and the prepared ternary precursor, ternary material and lithium ion battery are respectively A4, C4 and S4.
Example 5
Preparing a ternary precursor, a ternary material and a lithium ion battery of the lithium ion battery by using the same method as that of the embodiment 1, wherein the difference is that the nano alumina adopted in the step (1) is the nano alumina subjected to surface amination treatment, and the prepared ternary precursor, ternary material and lithium ion battery are A5, C5 and S5 respectively;
the surface amination treatment method of the nano aluminum oxide comprises the following steps: soaking nano-alumina into an absolute ethyl alcohol solution of polyethyleneimine, keeping the temperature at 60 ℃, treating for 4 hours, then aging for 24 hours, and then washing with absolute ethyl alcohol; wherein the solution of ethylene imine in absolute ethyl alcohol is 5 percent.
Example 6
The ternary precursor, the ternary material and the lithium ion battery of the lithium ion battery are prepared by the same method as the embodiment 1, except that the nano alumina adopted in the step (1) is the alumina subjected to surface amination and surface hydroxylation treatment, and the prepared ternary precursor, ternary material and lithium ion battery are respectively A6, C6 and S6;
the surface amination and surface hydroxylation treatment method of the nano-alumina comprises the following steps: soaking nano aluminum oxide into an absolute ethyl alcohol solution of polyethyleneimine, wherein the absolute ethyl alcohol solution of polyethyleneimine is 5%, keeping the temperature at 60 ℃, treating for 4 hours, then aging for 24 hours, and then washing with absolute ethyl alcohol; the treated nano alumina particles were immersed in hydrogen peroxide at a concentration of 8 wt%.
Comparative example 1
The method comprises the following steps of (1) preparing a ternary material precursor by adopting a coprecipitation method, specifically dissolving nickel sulfate, cobalt sulfate and aluminum sulfate in an aqueous solution according to a molar ratio of 80:15:5 to prepare a mixed metal salt solution with the concentration of 2mol/L, pumping the mixed metal salt solution into a reaction kettle at a stirring speed of 600r/min, pumping 1mol/L ammonia water solution into the reaction kettle, adjusting the pH value of the reaction kettle by using sodium hydroxide as a precipitator, controlling the pH value to be stable at 11 at 60 ℃, continuously reacting for 24 hours, and then carrying out spray drying to prepare a ternary material precursor DA1, a ternary material DC1 and a lithium ion battery DS 1.
Performance testing
(1) Content measurement of aluminum on the surface of precursor
The specific test method and steps are as follows: performing surface element analysis on energy dispersive X-ray spectroscopy (EDS) on JSM-7600F type field emission scanning electron microscope (JEOL corporation); the test results are shown in Table 1.
TABLE 1
(2) Energy density test
The specific test method comprises the following steps: 5g of the ternary material in the embodiment and the comparative example are respectively mixed with the positive electrode conductive agent and the positive electrode binder and placed in a mold with the diameter of 2cm, the powder is pressed to the highest height h capable of being compressed under the pressure of 10Mpa, and then the compaction density of the powder is as follows:
meanwhile, the energy density value of the positive electrode active material was calculated by measuring the energy density = charge average voltage × compacted density of the powder, and the test results are shown in table 2.
TABLE 2
(3) Battery rate capability test
The specific test method comprises the following steps: taking the batteries of the examples and the comparative examples, charging the batteries from 2.8V to 4.3V at 0.2C, and keeping the 4.3V constant voltage for charging for 5 min; then, the discharge was carried out at 5C to 2.5V, and the first charge capacity and the first discharge capacity were recorded, respectively, and the discharge rate = first discharge capacity/first charge capacity, and the test results are shown in table 3.
TABLE 3
As can be seen from Table 1, the aluminum content of the surface of the ternary material precursor prepared by the method is lower than 0.02%; as can be seen from table 2, the energy density of the nickel cobalt lithium manganate composite material prepared by mixing and sintering the precursor with a lithium source as the positive electrode active material of the lithium ion battery is greater than that of the positive electrode active material prepared in the comparative example; as can be seen from table 3, when the cathode active material prepared by the present invention is used in a lithium ion battery, the rate capability of the battery is greatly improved.
Claims (22)
1. The ternary material precursor is characterized by comprising Ni x Co y (OH) z Ni formed by agglomeration of primary particles x Co y (OH) z Secondary particles and uniformly dispersed in Ni x Co y (OH) z The nano alumina particles in the primary particle gaps are based on the weight of a ternary material precursor, and the content of aluminum on the surface of the ternary material precursor is lower than 0.1%;
the nano aluminum oxide is subjected to surface amination treatment.
2. The ternary material precursor of claim 1, wherein the nano alumina particles are uniformly dispersed in Ni x Co y (OH) z Inside the secondary particles.
3. The ternary material precursor according to claim 2, wherein the nano-alumina is subjected to a surface amination treatment and then a surface hydroxylation treatment.
4. The ternary material precursor according to claim 1, wherein the nano alumina particles have an average particle size of 20nm to 100 nm.
5. The ternary material precursor according to claim 1, wherein the content of aluminum in the ternary material precursor is 1% to 2% based on the weight of the ternary material precursor.
6. A method of preparing a ternary material precursor, the method comprising:
(1) mixing a nickel source and a cobalt source according to a ratio to form a mixed solution;
(2) dispersing nano alumina powder in water solution to form suspension;
(3) mixing the mixed solution, the suspension and the aqueous solution of the complexing agent at the same speed, and drying after reaction to prepare a ternary material precursor;
the nano aluminum oxide is subjected to surface amination treatment.
7. The method for preparing a ternary material precursor according to claim 6, wherein the nano alumina has an average particle diameter of 20nm to 100 nm.
8. The method for preparing the ternary material precursor according to claim 7, wherein the surface amination treatment comprises immersing nano alumina in an organic solvent of an amination reagent to perform heat treatment, and then washing.
9. The method for preparing the ternary material precursor according to claim 8, wherein the heat treatment temperature is 40-100 ℃ and the heat treatment time is 0.5-10 h.
10. The method for preparing a ternary material precursor according to claim 9, wherein said amination step further comprises a step of aging after the heat treatment, and the aging time is 2 to 48 hours.
11. The method for preparing the ternary material precursor according to claim 7, wherein the nano alumina further comprises a surface hydroxylation treatment step after the surface amination treatment.
12. The method for preparing the ternary material precursor according to claim 11, wherein the surface hydroxylation treatment comprises a treatment of immersing the nano-alumina subjected to the surface amination treatment in hydrogen peroxide.
13. The method for preparing the ternary material precursor according to claim 8, wherein the amination reagent is selected from one or more of polyethyleneimine, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane and polyglycidyl methacrylate.
14. The method for preparing the ternary material precursor of claim 6, wherein the complexing agent is selected from one or more of ammonia, tartaric acid, heptonate, sodium gluconate, sodium alginate, salicylic acid, boric acid, ethylenediaminetetraacetic acid or disodium ethylenediaminetetraacetate.
15. The method for preparing the ternary material precursor according to claim 6, wherein the reaction temperature is 25-60 ℃, the reaction time is 8-60h, and the pH value of the reaction system is 10-13.
16. A ternary material precursor, characterized in that it is prepared by a method according to any one of claims 6 to 15.
17. A method for preparing a ternary material, comprising mixing and sintering the ternary material precursor as claimed in any one of claims 1 to 5 and 16 with a lithium source in an oxygen-containing atmosphere.
18. The method for preparing the ternary material according to claim 17, wherein the temperature of the mixed sintering is 600 ℃ to 1100 ℃, and the sintering time is 8 to 20 hours; the lithium source is selected from one or more of lithium carbonate, lithium hydroxide monohydrate, lithium acetate, lithium nitrate, lithium oxalate and lithium oxide.
19. The method of claim 18, wherein the molar ratio of the ternary material precursor to the lithium source is 1: 1.0-1.1.
20. A ternary material, characterised by being produced by the method of any one of claims 17 to 19.
21. A positive electrode, characterized in that it comprises the ternary material according to claim 20.
22. A battery comprising the positive electrode of claim 21.
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