CN115000391A - Positive electrode material and preparation method and application thereof - Google Patents

Positive electrode material and preparation method and application thereof Download PDF

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CN115000391A
CN115000391A CN202210849141.5A CN202210849141A CN115000391A CN 115000391 A CN115000391 A CN 115000391A CN 202210849141 A CN202210849141 A CN 202210849141A CN 115000391 A CN115000391 A CN 115000391A
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lithium
equal
doped
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王涛
李超
王严杰
刘治猛
林葆雯
陈奕林
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Dongguan University of Technology
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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
    • H01M4/362—Composites
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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
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    • 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
    • H01M4/52—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
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    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to the technical field of secondary batteries, in particular to a positive electrode material and a preparation method and application thereof 1+α A x B y C z CoO 2 Wherein x is more than or equal to 0 and less than or equal to 0.05, y is more than or equal to 0 and less than or equal to 0.05, z is more than or equal to 0 and less than or equal to 0.05, alpha is more than or equal to-0.05 and less than or equal to 0.08, and x/y is 2-4, A, B and C are doping elements, and the trace and ordered doping is realized by compounding a lithium cobaltate matrix and the stripped nano transition metal oxide layer, so that the electrochemical performance of the material is effectively improved; the preparation method provided by the application realizes multielement by orderly and accurately introducing trace amounts of doping elementsThe doping method has universality, is simple to implement and can be used for large-scale production.

Description

Positive electrode material and preparation method and application thereof
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a positive electrode material and a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high power density and energy density, small volume, long service life and the like, and is widely applied to the fields of consumer electronics, mobile terminals, communication energy storage, electric automobiles and the like. In recent two years, due to rapid development of '5G' and mobile terminals (such as smart phones, unmanned planes, household robots and the like), the demand of people on endurance is higher and higher, and therefore, as a power core of the mobile terminals, the lithium ion batteries with high energy density become a core appeal for consumers and equipment manufacturers. Lithium cobaltate is currently used due to its excellent electrical properties and extremely high tap density (5.1 g/cm) 3 ) Still is not the second choice for the positive electrode material of the high-energy density battery.
Increasing lithium cobaltate (LiCoO) 2 ) Is one of the strategies employed in the industry to increase energy density. However, the increase in charging voltage may result in LiCoO 2 The positive electrode material undergoes crystal form transformation, the structure collapses and loses electrochemical activity; on the other hand, at a high potential, the side reaction of cobalt in a high valence state with the electrolyte is intensified, and the electrolyte is decomposed more intensely. The high-temperature storage, safety performance and cycle stability of the battery are remarkably reduced, and the actual requirements are difficult to meet.
Doping and cladding are effective means for improving the structural stability of the material and reducing the interface side reaction at present. For example by coating of surface metal oxides, coating of surface polymers, coating of fast-ionic conductors, doping of elements and surface treatment (plasma, SO) 2 Acid treatment, etc.) to inhibit and improve the bottlenecks described above. For example, patent CN 104409700B discloses a positive electrode material of nickel-based lithium ion battery and a preparation method thereof, which comprisesThe core, the doping layer and the cladding layer; the chemical formula of the core is LiNi x Co y M z O 2 (ii) a The doped layer is a core containing M '(M' is one or the combination of more than two of Mg, Fe, Zn, Cu, Mn, Sr, Al, Ga, In, Ge, Zr and Cr); the coating layer at least contains M' and oxygen; the cathode material has a core-shell structure and comprises a core, a doping layer and a coating layer from inside to outside in sequence. The material has less lithium and nickel mixed discharge and obviously improved cycling stability.
Chinese patent CN106654237B discloses a core-shell material, which utilizes doped core materials such as cerium oxide, lanthanum oxide, and zirconium oxide to reduce oxygen release, and utilizes strong bonding ability of elements such as cerium, lanthanum, zirconium, and aluminum in the shell material to oxygen atoms to inhibit oxygen release, thereby enhancing structural stability of the material under high temperature and high pressure conditions. The doping elements often need to enter the material lattice site precisely to avoid the formation of new phases.
Therefore, the realization of the accurate doping and the uniform and controllable coating of multiple elements is one of the difficulties and the keys of the surface modification of the high-voltage lithium cobalt oxide material.
Disclosure of Invention
In order to solve the problems, the invention provides a positive electrode material and a preparation method and application thereof, and the positive electrode material has good cycle performance and high capacity under high voltage and can buffer or release stress caused by lattice constant change in the charge and discharge process.
The technical scheme adopted by the invention is as follows:
the positive electrode material is characterized by comprising a doped lithium cobaltate matrix and a coating layer coated on the surface of the doped lithium cobaltate matrix; the general formula of the material is Li 1+α Co 1-x-y-z A x B y C z O 2 (ii) a Wherein x is more than or equal to 0 and less than or equal to 0.05, y is more than or equal to 0 and less than or equal to 0.05, z is more than or equal to 0 and less than or equal to 0.05, alpha is more than or equal to 0.05 and less than or equal to 0.08, and x/y is 2-4; the A is a doped divalent element, the B is a doped trivalent element, and the C is a doped tetravalent or pentavalent or hexavalent element;
specifically, the doping element a is used to replace cobalt sites or lithium sites in the lithium cobaltate structure, wherein the doping elements a and B comprise one or more of Al, Mg, Ti, Sn, V, Cu, Zn, Zr, Cr, Mn, Ni, Co, Fe, Ga, Mo, Sb, W, Y, and Nb.
In the invention, the working voltage range of the high-voltage lithium cobaltate anode material is 3.0V-4.8V.
The lithium cobaltate has a primary particle having a median particle diameter of 1.0 to 50.0 μm and a compacted density of 2.2 to 4.4g/cm 3 (ii) a The secondary particles have a median particle diameter of 5.0 to 50.0 μm and a compacted density of 2.2 to 4.4g/cm 3 。
Wherein the material constituting the doped lithium cobaltate matrix has a general formula of Li 1+α Co 1-x-y-z A x B y C z O 2 (ii) a X is more than or equal to 0 and less than or equal to 0.01, y is more than or equal to 0 and less than or equal to 0.01, z is more than or equal to 0 and less than or equal to 0.01, alpha is more than or equal to 0.05 and less than or equal to 0.08, and x/y is 2-4; the A is a doped divalent element, the B is a doped trivalent element, and the C is a doped tetravalent or pentavalent or hexavalent element;
wherein the coating material has a general formula of Li γ1 Mc γ2 O γ3 The Mc is at least two of A, B and C, and γ 1, γ 2, and γ 3 are arbitrary positive numbers satisfying the formula γ 1+ Mc γ 2 ═ γ 3.
The A element is a divalent element Mg 2+ ，Ca 2+ ，Ba 2+ ，Mn 2+ ，Ni 2+ ，Cu 2+ ，Zn 2+ ，Cd 2+ At least one of;
the B element is trivalent element Al 3+ ，Ga 3+ ，In 3+ ，Sc 3+ ，V 3+ ，Cr 3+ ，Mn 3+ ，Y 3+ ，Bi 3+ At least one of;
the element C is Ti 4+ ，Zr 4+ ，Sn 4+ ,Hf 4+ ，V 5+ ,W 6+ At least one of (1).
The mass of the coating layer accounts for 0.1-5% of the total mass of the high-voltage lithium cobalt oxide positive electrode material.
The thickness of the coating layer is 0.1nm-50 nm.
Based on the same inventive concept, the invention also provides a preparation method of the anode material, which comprises the following steps:
s1, preparing layered double hydroxides with orderly arranged elements to be doped;
s2, stripping the obtained layered double hydroxide by adopting a formamide stripping method or an intercalation auxiliary stripping method to obtain a single-layer or less than 20-layer layered double hydroxide;
and S3, coating the obtained single-layer or few-layer layered double metal hydroxide on the surface of lithium cobaltate to obtain the element-accurate co-doped high-voltage lithium cobaltate cathode material.
Specifically, soluble salt of a doping element is taken to prepare 0.2-4mol/L solution, and the molar ratio of divalent metal ions to trivalent metal ions is 2-5: L; adding an alkaline solution under high-speed stirring to obtain a layered double metal hydroxide (LDH) material, inserting the obtained LDH into an organic macromolecule, and carrying out mechanical auxiliary stripping to obtain a stripped LDH nanosheet solution. The A/B ions designed in advance on the nano-chip are arranged according to a specific sequence and have a determined proportion.
And adding lithium cobaltate into the peeled LDH nanosheet solution, and performing mechanical stirring or ultrasonic treatment and spray drying to obtain the LDH and lithium cobaltate composite.
The LDH preparation method comprises the following steps: coprecipitation, ion exchange, hydrothermal, urea decomposition, sol-gel method.
Sintering the composite at 800-1100 ℃ for 6-24 hours to obtain a crude product, and crushing the crude product to obtain the high-voltage lithium cobaltate cathode material.
In the sintering process, the temperature is increased to 800-1100 ℃ at the heating rate of 0.2-10 ℃/min.
And after the crushing treatment is finished, further preparing a coating layer on the surface of the lithium cobaltate, wherein the material of the coating layer comprises one or a mixture of more of oxides, hydroxides, carbonates, nitrates, oxalates, acetates, phosphates and silicates containing Li, Al, Mg, Co, Ti, Zr, Hf, La, Nb, In, W, Ta, Ba, Te, Y, Sb, V, O, P, Si, S, F, As, Sb, I and/or N.
The coating layer is prepared by adopting one or more methods of a mechanical stirring method, a high-energy ball milling method, a mechanical fusion method, an in-situ growth method, an epitaxial growth method, an atomic layer deposition method, a vapor deposition method, a magnetron sputtering method, a liquid phase reaction method, a sol-gel method, a solvothermal method, a vacuum thermal deposition method, a plasma sputtering method, a microwave reaction method and a high-temperature sintering method.
The sintering temperature for preparing the coating layer by adopting a high-temperature sintering method is 300-1000 ℃, and the sintering time is 3-48 h.
The invention has the following beneficial effects:
1. the cathode material comprises a doped lithium cobaltate matrix and a coating layer coated on the surface of the doped lithium cobaltate matrix, and the general formula of the cathode material is Li 1+α A x B y C z CoO 2 Wherein x, z and y are more than 0 and less than or equal to 0.05, alpha is more than or equal to 0.05 and less than or equal to 0.08, and the A, B and C respectively represent bivalent, trivalent and high-valent (tetravalent or pentavalent or hexavalent) doping elements; on the basis of keeping the capacity and the dynamic characteristic of lithium cobaltate, the method skillfully utilizes the characteristics of ordered arrangement of metal elements, adjustable element types and element proportions and easy stripping of the metal elements on the layered double-metal hydroxide laminate, realizes trace and ordered doping by composite coating of the lithium cobaltate and the stripped nano layer, and effectively improves the electrical property of the material;
2. according to the preparation method provided by the application, through an accurate trace and one-step doping coating method, trace doping coating is realized on the surface of lithium cobaltate, the high doping efficiency is ensured, the introduction of a new phase is avoided, multi-element doping can be realized, the proportion of doping elements can be accurate to the atomic scale, and the doping elements are doped into a lithium cobaltate structure.
Drawings
FIG. 1 is a schematic diagram of the Layered Double Hydroxide (LDH) structure of the present application, wherein 1a is an octahedral structural unit, 1b is an anion, 2a is a divalent metal, and 2b is a trivalent metal;
FIG. 2 is a schematic structural diagram of the ordered arrangement of elements on a single layer magnesium aluminum double hydroxide (MgAl-LDH) laminate of the present application;
FIG. 3 is a schematic process flow diagram of the present application of doping coated lithium cobaltate with magnesium aluminum double metal hydroxide (MgAl-LDH);
FIG. 4 is a scanning electron micrograph of a sample prepared in example 5 of the present application;
figure 5 is an XRD pattern of the sample prepared in example 5 of the present application;
fig. 6 is charging and discharging curves (room temperature condition, 0.1C/0.1C, v.s. metallic lithium) of samples prepared in examples 1 and 5, comparative example 1 and comparative example 2 of the present application, wherein a is the charging curve in example 1, b is the discharging curve in example 1, C is the charging curve in example 5, d is the discharging curve in example 5, e is the charging curve in comparative example 1, f is the charging curve in comparative example 1, g is the charging curve in comparative example 2, and h is the discharging curve in comparative example 2.
Detailed Description
The invention will be further described with reference to the accompanying drawings and preferred embodiments.
The preparation method of the LDH-doped lithium cobaltate-coated positive electrode material provided by the application comprises the following steps:
s1, preparing and designing a doped element double metal hydroxide (LDH)
Determination of M based on the structural requirements of the LDH precursor for the sheet metal cations, preferably the nitrate, sulfate or chloride salt of a suitable divalent or trivalent doping element, the solution is prepared 2+ /M 3+ The ratio of (A) to (B) is within a certain range. Adding an alkali metal salt or basic salt containing carbonate, ammonium or hydroxyl. The layered double-metal oxide of divalent and trivalent doping elements with a certain proportion is prepared by coprecipitation, hydrothermal method and the like.
Specifically, preparing a soluble metal salt mixed solution; the mixed solution of the soluble metal salt contains at least three metal ionsThe metal ion is A 2+ 、B 3+ (ii) a Wherein A is 2+ ：B 3+ The molar ratio is 2-4: 1, A represents a divalent metal ion, A 2+ Is Mg 2 + 、Zn 2+ 、Co 2+ 、Fe 2+ 、Mn 2+ 、Cu 2+ Nitrate or chloride; b is 3+ Represents Al 3+ 、Fe 3+ 、Ga 3+ 、Mn 3+ 、Cr 3+ 、Ce 3 + 、V 3+ 、Rh 3+ 、Ir 3+ 、In 3+ 、Ti 3+ At least one of nitrate or chloride, C is variable valence metal ion, and the variable valence metal ion is Fe 3+ 、Ga 3+ 、Mn 3+ 、Cr 3+ 、Ce 3+ 、Ti 4+ One of (1);
adding the soluble metal salt mixed solution and a precipitator in the step A into a reaction kettle at the same time, and quickly stirring, wherein the adding amount of the precipitator is such that the pH value of the mixed solution is 9-11; crystallizing at 45-200 ℃ for 6-48 h, naturally cooling to room temperature, filtering out precipitates, washing until the pH of a supernatant solution is 7-8, and drying at 40-80 ℃ for 6-18 h to obtain a hydrotalcite LDH precursor;
the precipitant is urea, NaOH, KOH, ammonia water, Na 2 CO 3 Or NaHCO 3 The concentration of one of the aqueous solutions of (1) to (10) mol/L;
s2.LDH exfoliation
The LDH material in S1 is stripped by formamide stripping method or intercalation auxiliary stripping method, organic anions are inserted between LDHs layers, the layer plate spacing is enlarged, the interaction between a main layer plate and an object molecule is weakened, then the LDHs is stripped under the action of external force (ultrasonic and stirring), a single-layer or few-layer (less than 20 layers) LDH solution is obtained, the solution has obvious Tyndall phenomenon, wherein the stripped organic anions are short-chain alcohol, formamide, toluene, carbon tetrachloride or water.
S3. doping coating of LCO
Adding uncoated LCO particles into an LDH solution for stripping a single layer or a few layers, stirring for a certain time, filtering or spray drying to obtain the LDH-coated LCO, and then carrying out air atmosphere heat treatment to obtain the ordered doped and coated lithium ion battery anode material.
The following are specific preparation examples of the positive electrode material provided in the present application.
Example 1 magnesium aluminum LDH coated LCO
In this example, a high voltage lithium cobaltate cathode material for a lithium ion battery, which is coated with ordered Mg-Al (molar ratio 4: 1), is provided and assembled into a secondary battery.
Preparation of Mg-Al-LDHs
Adding 0.0020mol of Mg (NO) 3 ) 2 ·6H 2 O (0.5134g), 0.0005mol of Al (NO) 3 ) 3 ·9H 2 O (0.1870g), 25% aqueous ammonia 0.75mL (0.01mol) was dissolved in 50mL of distilled water so that [ Mg 2+ ]/[Al 3+ ]/[urea]The molar ratio of the mixed solution is 4/1/10, the mixed solution is stirred until the mixed solution is clear and transparent, and then the mixed solution is transferred into a high-pressure reaction kettle for 24 hours at the temperature of 150 ℃. Cooling to room temperature, washing the obtained precipitate with distilled water and anhydrous ethanol repeatedly for 3 times, and drying at 60 deg.C for 12 hr to obtain white powder.
Preparation of Mg-Al-LDHs stripping solution
0.0503g of Mg-Al-LDHs are weighed, evenly dispersed in 40mL of formamide and kept stand for 2 days. Centrifugation was carried out at 10,000rpm for 5min to give a clear colloidal solution.
LCO doping coating Mg-Al
Mixing cobaltosic oxide, lithium hydroxide and the transparent colloidal solution, or adding a certain amount of ethanol solvent into lithium cobaltate and the transparent colloidal solution to prepare a solution, carrying out spray pyrolysis, wherein the inlet temperature is 200 ℃, the outlet temperature is 120 ℃, the feeding rate is 4L/min, and collecting a sample. The product was then subjected to a heat treatment at 600-1000 ℃ in an air atmosphere for a treatment time of 24 hours. And naturally cooling to obtain the final doped and coated Mg-Al @ LCO with different proportions.
Method for manufacturing secondary battery
Mixing the Mg-Al @ LCO material prepared in the embodiment, the conductive agent Super P and the binder polyvinylidene fluoride (PVDF) according to a mass ratio of 96: 0.2: 0.2 is dispersed in N-methyl pyrrolidone (NMP) solvent, evenly stirred to obtain electrode slurry, the electrode slurry is coated on the surface of an aluminum foil, vacuum baking is carried out for 12 hours at 120 ℃, rolling and cutting are carried out, and the positive electrode plate is obtained. The graphite negative electrode is matched, 1mol/L LiPF6/(EC + DEC) electrolyte (the volume ratio is 1: 1) and a PP/PE/PP three-layer diaphragm are used for manufacturing a soft package battery of about 4000mAh for battery test and use.
Example 2 magnesium-aluminum LDH coated LCO
In this example, a high voltage lithium cobaltate cathode material for a lithium ion battery, which is coated with ordered Mg-Al (molar ratio 2: 1), is provided and assembled into a secondary battery.
Preparation of Mg-Al-LDHs
0.0010mol of Mg (NO) 3 ) 2 ·6H 2 O (0.2567g), 0.0005mol of Al (NO) 3 ) 3 ·9H 2 O (0.1870g), 0.0050mol of urea (0.3009g) was dissolved in 50mL of distilled water so that [ Mg 2+ ]/[Al 3+ ]/[urea]The molar ratio of the mixed solution is 2/1/10, the mixed solution is stirred until the mixed solution is clear and transparent, and then the mixed solution is transferred into a high-pressure reaction kettle for 24 hours at the temperature of 150 ℃. Cooling to room temperature, washing the obtained precipitate with distilled water and anhydrous ethanol repeatedly for 3 times, and drying at 60 deg.C for 12 hr to obtain white powder.
Preparation of Mg-Al-LDHs stripping solution
0.0503g of Mg-Al-LDHs are weighed, evenly dispersed in 40mL of formamide and kept stand for 2 days. Centrifugation was carried out at 10,000rpm for 5min to give a clear colloidal solution.
LCO doping coating Mg-Al
Mixing cobaltosic oxide, lithium hydroxide and the transparent colloidal solution, or adding a certain amount of ethanol solvent into lithium cobaltate and the transparent colloidal solution to prepare a solution, carrying out spray pyrolysis, wherein the inlet temperature is 200 ℃, the outlet temperature is 120 ℃, the feeding rate is 4L/min, and collecting a sample. Then the product is subjected to 600-1000 ℃ heat treatment in air or oxygen atmosphere for 12 hours. Naturally cooling to obtain the final doped and coated Mg-Al @ LCO
Method for manufacturing secondary battery
Mixing the Mg-Al @ LCO material prepared in the embodiment, the conductive agent Super P and the binder polyvinylidene fluoride (PVDF) according to a mass ratio of 96: 0.2: 0.2, dispersing in N-methyl pyrrolidone (NMP) solvent, uniformly stirring to obtain electrode slurry, coating the electrode slurry on the surface of an aluminum foil, baking for 12 hours at 120 ℃, rolling and cutting to obtain the positive electrode plate. The graphite negative electrode is matched, 1mol/L LiPF6/(EC + DEC) electrolyte (the volume ratio is 1: 1) and a PP/PE/PP three-layer diaphragm are used for manufacturing a soft package battery of about 4000mAh for battery test and use.
Example 3Ni-Al-LDH coated LCO
In this embodiment, a high-voltage lithium cobaltate cathode material for a Ni-Al ordered doped coated lithium ion battery is provided and assembled into a secondary battery.
Preparation of Mg-Al-LDHs
0.0010mol of Ni (NO) 3 ) 2 ·6H 2 O (0.2908g), 0.0005mol Al (NO) 3 ) 3 ·9H 2 O (0.1870g), 0.0050mol of urea (0.3009g) was dissolved in 50mL of distilled water so that [ Ni 2+ ]/[Al 3+ ]/[urea]Is 2/1/10. Stirring the mixed solution until the mixed solution is clear and transparent, and then transferring the mixed solution into a high-pressure reaction kettle for 24 hours at the temperature of 150 ℃. Cooling to room temperature, repeatedly washing the obtained precipitate with distilled water and anhydrous ethanol for 3 times, and drying at 60 deg.C for 12 hr to obtain green powder.
Preparation of Mg-Al-LDHs stripping solution
0.0503g of Ni-Al-LDHs are weighed and evenly dispersed in 40Ml of 0.2M lithium acetate, ultrasonic treatment is carried out for 2 hours at the frequency of 40Hz, and then stirring is carried out for 2 days at the rotating speed of 1000rpm, thus obtaining transparent colloidal solution.
LCO doping cladding Ni-Al
Mixing cobaltosic oxide, lithium hydroxide and the transparent colloidal solution, adding a certain amount of ethanol solvent to prepare a solution, carrying out spray pyrolysis, wherein the inlet temperature is 200 ℃, the outlet temperature is 120 ℃, and the feeding rate is 4L/min. The product was then heat treated at 900 ℃ in an air atmosphere for 12 hours. Naturally cooling to obtain the final doped and coated Ni-Al @ LCO
Method for manufacturing secondary battery
Mixing the material Ni-Al @ LCO prepared in the embodiment, the conductive agent Super P and the binder polyvinylidene fluoride (PVDF) according to a mass ratio of 96: 0.2: 0.2, dispersing in N-methyl pyrrolidone (NMP) solvent, uniformly stirring to obtain electrode slurry, coating the electrode slurry on the surface of an aluminum foil, baking for 12 hours at 120 ℃, rolling and cutting to obtain the positive electrode plate. The graphite negative electrode is matched, 1mol/L LiPF6/(EC + DEC) electrolyte (the volume ratio is 1: 1) and a PP/PE/PP three-layer diaphragm are used for manufacturing a soft package battery of about 4000mAh for battery test and use.
Example 4 Mg/Ga-Ce LDH-coated LCO
In this embodiment, a high-voltage lithium cobaltate cathode material for a Mg/Ga-Ce LDH-doped and coated lithium ion battery is provided and assembled into a secondary battery.
Preparation of Mg/Ga-Ce LDHs
0.0010mol of Mg (NO) 3 ) 2 ·6H 2 O (0.2567g), 0.0005mol of Ga (NO) 3 ) 3 (0.1279g), 0.0001mol of Ge (NO) 3 ) 3 ·6H 2 O (0.0434g) and 0.0050mol of urea (0.3009g) were dissolved in 50mL of distilled water so that [ Mg 2+ ]/[Ga 3+ ]/[Ce 3+ ]/[urea]The molar ratio of (A) to (B) is: 2: 1: 0.1: 10. the mixed solution is stirred until the mixed solution is clear and transparent, and then the mixed solution is transferred into a high-pressure reaction kettle for 24 hours at the temperature of 150 ℃. Cooling to room temperature, washing the obtained precipitate with distilled water and anhydrous ethanol repeatedly for 3 times, and drying at 60 deg.C for 12 hr to obtain white powder.
Preparation of Mg/Ga-Ce LDH stripping solution
0.0503g of Mg/Ga-Ce LDH is weighed, evenly dispersed in 40mL of formamide and kept stand for 2 days. Centrifugation was carried out at 10,000rpm for 5min to give a clear colloidal solution.
LCO doping coating Mg-Al
Mixing cobaltosic oxide, lithium hydroxide and the transparent colloidal solution, or adding a certain amount of ethanol solvent into lithium cobaltate and the transparent colloidal solution to prepare a solution, carrying out spray pyrolysis, wherein the inlet temperature is 200 ℃, the outlet temperature is 120 ℃, the feeding rate is 4L/min, and collecting a sample. Then the product is subjected to 600-1000 ℃ heat treatment in air or oxygen atmosphere for 36 hours. Naturally cooling to obtain the final doped and coated Mg-Al @ LCO
Preparation of secondary battery
Mixing the Mg-Al @ LCO material prepared in the embodiment, the conductive agent Super P and the binder polyvinylidene fluoride (PVDF) according to a mass ratio of 96: 0.2: 0.2 is dispersed in N-methyl pyrrolidone (NMP) solvent, evenly stirred to obtain electrode slurry, the electrode slurry is coated on the surface of an aluminum foil, vacuum baking is carried out for 12 hours at 120 ℃, rolling and cutting are carried out, and the positive electrode plate is obtained. The graphite negative electrode is matched, 1mol/L LiPF6/(EC + DEC) electrolyte (the volume ratio is 1: 1) and a PP/PE/PP three-layer diaphragm are used for manufacturing a soft package battery of about 4000mAh for battery test and use.
Example 5 Mg/Al/Ti LDH-coated LCO
In this embodiment, a Mg/Al-Ti multi-element ordered doped coated high-voltage lithium cobalt oxide positive electrode material for a lithium ion battery is provided and assembled into a secondary battery.
Preparation of Mg/Al/Ti-LDHs
0.0010mol of Mg (NO) 3 ) 2 ·6H 2 O (0.2567g), 0.0010mol of Al (NO) 3 ) 3 ·9H 2 O (0.3740g), 0.0010mol of TiCl4(0.1897g) was dissolved in 100ml of deionized water. Labeled as solution a. 100ml of 2M NaOH and 0.5M Na 2 CO 3 The mixed solution of (1) is labeled as solution B, and solution A and solution B are added together to 100ml of 0.01M Na 2 CO 3 In the solution, the pH was adjusted to 10, and then the mixed solution was stirred in a water bath at 70 ℃ for 24 hours. Obtaining the nano Mg/Al/Ti LDH.
Preparation of Mg/Al/Ti-LDHs stripping solution
0.0503g of Mg/Al/Ti-LDHs are weighed, evenly dispersed in 40mL of formamide and kept stand for 2 days. Centrifugation was carried out at 10,000rpm for 5min to give a clear colloidal solution.
LCO doping coating Mg/Al/Ti
Mixing cobaltosic oxide, lithium hydroxide and the transparent colloidal solution, or adding a certain amount of ethanol solvent into lithium cobaltate and the transparent colloidal solution to prepare a solution, carrying out spray pyrolysis, wherein the inlet temperature is 200 ℃, the outlet temperature is 120 ℃, the feed rate is 4L/min, and collecting a sample. Then the product is subjected to heat treatment at 600-1000 ℃ in an air or oxygen atmosphere for 12 hours. Naturally cooling to obtain the final doped and coated Mg/Al/Ti @ LCO
Preparation of secondary battery
Mixing the Mg/Al/Ti @ LCO material prepared in the embodiment, the Super P conductive agent and the polyvinylidene fluoride (PVDF) binder according to a mass ratio of 96: 0.2: 0.2 is dispersed in N-methyl pyrrolidone (NMP) solvent, evenly stirred to obtain electrode slurry, the electrode slurry is coated on the surface of an aluminum foil, vacuum baking is carried out for 12 hours at 120 ℃, rolling and cutting are carried out, and the positive electrode plate is obtained. The graphite negative electrode is matched, 1mol/L LiPF6/(EC + DEC) electrolyte (the volume ratio is 1: 1) and a PP/PE/PP three-layer diaphragm are used for manufacturing a soft package battery of about 4000mAh for battery test and use.
Example 6(Mg/Cu/Zn/Ru) - (In/Sc/Y/Rh) -LDH coated LCO
The present embodiment provides a method for assembling a secondary battery by using a high-voltage lithium cobalt oxide positive electrode material of a multi-element ordered doped and coated lithium ion battery.
Preparation of a Multi-LDH
0.0010mol of Mg (NO) 3 ) 2 ·6H 2 O(0.2567g)、0.0010mol Cu(NO 3 ) 2 ·6H 2 O(0.1876g)、0.0010mol Zn(NO 3 ) 2 ·6H 2 O(0.2975g)、0.0001mol RuCl 3 (0.0207g) and 0.0010mol of In (NO) 3 ) 3 ·6H 2 O (0.3008g), Sc (NO) (0.2309g) 0.0010mol, Y (NO) 0.0010mol 3 ) 2 ·6H 2 O (0.3830g) and 0.0001mol Rh (NO) 3 ) 3 (0.0289g) was dissolved in 100ml of deionized water. 100ml of 2M NaOH and 0.5M Na were added 2 CO 3 The pH of the mixed solution of (1) was adjusted to 10 with aqueous ammonia, and then the mixed solution was stirred in a water bath at 70 ℃ for 24 hours. Obtaining the nano-poly LDH.
Preparation of LDHs stripping solution
0.0503g of the above polybasic LDHs are weighed, evenly dispersed in 40mL of formamide, and kept stand for 2 days. Centrifugation was carried out at 10,000rpm for 5min to give a clear colloidal solution.
LCO doping cladding
Mixing cobaltosic oxide, lithium hydroxide and the transparent colloidal solution, or adding a certain amount of ethanol solvent into lithium cobaltate and the transparent colloidal solution to prepare a solution, carrying out spray pyrolysis, wherein the inlet temperature is 200 ℃, the outlet temperature is 120 ℃, the feeding rate is 4L/min, and collecting a sample. Then the product is subjected to 600-1000 ℃ heat treatment in air or oxygen atmosphere for 24 hours. Naturally cooling to obtain final doped coating (Mg/Cu/Zn/Ru) - (In/Sc/Y/Rh) @ LCO
Preparation of secondary battery
Mixing the material (Mg/Cu/Zn/Ru) - (In/Sc/Y/Rh) @ LCO prepared In the embodiment, the conductive agent Super P and the binder polyvinylidene fluoride (PVDF) according to the mass ratio of 96: 0.2: 0.2 is dispersed in N-methyl pyrrolidone (NMP) solvent, evenly stirred to obtain electrode slurry, the electrode slurry is coated on the surface of an aluminum foil, vacuum baking is carried out for 12 hours at 120 ℃, rolling and cutting are carried out, and the positive electrode plate is obtained. The graphite negative electrode is matched, 1mol/L LiPF6/(EC + DEC) electrolyte (the volume ratio is 1: 1) and a PP/PE/PP three-layer diaphragm are used for manufacturing a soft package battery of about 4000mAh for battery test and use.
Comparative example 1 magnesium aluminum oxide coated LCO
In this comparative example, a magnesium-aluminum doped coated lithium cobaltate positive electrode material was provided and assembled into a secondary battery.
Adding 0.0010mol of MgO and 0.0005mol of Al 2 O 3 (0.1870g), cobaltosic oxide and lithium hydroxide are mixed by ball milling according to a proper stoichiometric ratio, a certain amount of ethanol solvent is added to prepare a solution, spray pyrolysis is carried out, the inlet temperature is 200 ℃, the outlet temperature is 120 ℃, the feeding rate is 4L/min, and samples are collected. The product was then subjected to a heat treatment at 900 ℃ in an air atmosphere for 12 hours. Naturally cooling to obtain the final doped and coated Mg-Al @ LCO
Mixing the Mg-Al @ LCO material prepared in the comparative example, the conductive agent Super P and the binder polyvinylidene fluoride (PVDF) according to a mass ratio of 96: 0.2: 0.2 dispersing in N-methyl pyrrolidone (NMP) solvent, stirring to obtain electrode slurry, coating the electrode slurry on the surface of aluminum foil, and vacuum-coating at 120 deg.CBaking for 12h, rolling and cutting to obtain the positive electrode plate. A graphite negative electrode was used in combination with 1mol/L LiPF 6 And (2) preparing an (EC + DEC) electrolyte (volume ratio is 1: 1) and a PP/PE/PP three-layer diaphragm into a soft package battery of about 4000mAh for battery test and use.
Comparative example 2 magnesium aluminum oxide coated LCO
In the comparative example, a conventional magnesium, aluminum and titanium doped and coated lithium cobaltate positive electrode material is provided and assembled into a secondary battery.
Adding 0.0010mol of MgO and 0.0005mol of Al 2 O 3 、0.0010mol TiO 2 And the cobaltosic oxide and the lithium hydroxide are ball-milled and mixed according to a proper stoichiometric ratio, a certain amount of ethanol solvent is added to prepare a solution, spray pyrolysis is carried out, the inlet temperature is 200 ℃, the outlet temperature is 120 ℃, the feeding rate is 4L/min, and samples are collected. The product was then heat treated at 950 ℃ in an air atmosphere for 12 hours. Naturally cooling to obtain the final doped and coated Mg-Al @ LCO
Mixing the Mg-Al-Ti @ LCO material prepared in the comparative example, the Super P conductive agent and the polyvinylidene fluoride (PVDF) binder according to a mass ratio of 96: 0.2: 0.2, dispersing in N-methyl pyrrolidone (NMP) solvent, uniformly stirring to obtain electrode slurry, coating the electrode slurry on the surface of an aluminum foil, baking for 12 hours at 120 ℃, rolling and cutting to obtain the positive electrode plate. A graphite negative electrode was used in combination with 1mol/L LiPF 6 And (2) preparing an (EC + DEC) electrolyte (volume ratio is 1: 1) and a PP/PE/PP three-layer diaphragm into a soft package battery of about 4000mAh for battery test and use.
COMPARATIVE EXAMPLE 3 Multi-element doped clad LCO
The comparative example provides a lithium cobaltate positive electrode material doped and coated by multiple elements of magnesium, copper, zinc, ruthenium, indium, scandium, yttrium and rhodium, and a secondary battery is assembled.
0.0010mol of MgO, CuO, ZnO and In 2 O 3 、Sc 2 O 3 、Y 2 O 3 And 0.0001mol of RuO and Rh 2 O 3 And Co with 3 O 4 Ball-milling and mixing the mixture with lithium hydroxide according to a proper stoichiometric ratio (doping element: cobaltosic oxide: LiOH ═ 1: 30: 100), and adding mono-cobaltQuantifying ethanol solvent, preparing into solution, performing spray pyrolysis, collecting sample at inlet temperature of 200 deg.C and outlet temperature of 120 deg.C and feeding rate of 4L/min, and naturally cooling to obtain final doped coated multielement @ LCO
The material multielement @ LCO prepared by the comparative example, the conductive agent Super P and the binder polyvinylidene fluoride (PVDF) are mixed according to the mass ratio of 96: 0.2: 0.2 is dispersed in N-methyl pyrrolidone (NMP) solvent, evenly stirred to obtain electrode slurry, the electrode slurry is coated on the surface of an aluminum foil, vacuum baking is carried out for 12 hours at 120 ℃, rolling and cutting are carried out, and the positive electrode plate is obtained. A graphite negative electrode was used in combination with 1mol/L LiPF 6 And (2) preparing an electrolyte (the volume ratio of EC and DEC) is 1: 1, and preparing a PP/PE/PP three-layer diaphragm into a soft package battery with the thickness of about 4000mAh for battery test and use.
The batteries manufactured in examples 1 to 6 and comparative examples 1 to 3 were subjected to an electrochemical performance test, which is a normal temperature cycle test, and a voltage range: 3.0-4.5V, the discharge is 1.0C constant current discharge in the test, the charge is 0.5C constant current constant voltage charge, the cut-off current is 0.05C, and the test results are shown in Table 1:
TABLE 1 electrochemical Properties (3.0-4.5V) of examples 1-6 and comparative examples 1-3
Figure BDA0003754182720000151
Figure BDA0003754182720000161
Table 1 shows that the capacity retention rates of the lithium ion batteries prepared by using the materials in examples 1 to 6 after 500 cycles are all in the range of 70.5 to 85.4%, compared with the comparative examples, the battery samples prepared by using the embodiments of the present invention all show excellent performance in terms of the first discharge efficiency of the positive electrode material, the gram capacity exertion of the positive electrode and the cycle performance of the battery, because the embodiment of the present invention designs the nano-layered double metal hydroxide (LDH) with the orderly arranged doping elements in advance, and obtains the doping element nano-layer with the designed proportion by the stripping means, and the nano-layer is orderly doped in the lithium cobaltate structure in the heat treatment process, so that the nano-layer has more uniform element distribution, and simultaneously realizes the trace amount of high-efficiency coating. The lithium-ion battery has more balanced charge distribution in a high lithium-ion removal state, effectively relieves expansion and shrinkage of unit cells and cobalt dissolution, stabilizes a material structure, and improves specific capacity and cycle performance; and the elements of the nano layer are orderly coated, so that the rapid transmission of lithium ions in the material is facilitated, and the reaction kinetics and the rate capability of the material are improved. In addition, the existence of the coating layer can avoid the contact of the lithium cobaltate matrix and the electrolyte in a high delithiation state, relieve the side reaction of the lithium cobaltate matrix material and the electrolyte and the dissolution of cobalt in the high delithiation state, and improve the structural stability and the cycling stability of the lithium cobaltate matrix material.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. The positive electrode material is characterized by comprising a doped lithium cobaltate matrix and a coating layer coated on the surface of the doped lithium cobaltate matrix;
wherein the material constituting the doped lithium cobaltate matrix has a general formula of Li 1+α Co 1-x-y-z A x B y C z O 2 (ii) a X is more than or equal to 0 and less than or equal to 0.05, y is more than or equal to 0 and less than or equal to 0.05, z is more than or equal to 0 and less than or equal to 0.05, alpha is more than or equal to 0.05 and less than or equal to 0.08, and x/y is 2-4; the A is a doped divalent element, the B is a doped trivalent element, and the C is a doped tetravalent or pentavalent or hexavalent element;
wherein the coating material has a general formula of Li γ1 M γ2 O γ3 M is at least two of A, B and C, and γ 1, γ 2, and γ 3 are arbitrary positive numbers satisfying the formula γ 1+ Mc γ 2-2 γ 3.
2. The positive electrode material as claimed in claim 1, wherein the element A is Mg 2+ ，Ca 2+ ，Ba 2+ ，Mn 2+ ，Ni 2+ ，Cu 2+ ，Zn 2+ ，Cd 2+ At least one of;
the B element is Al 3+ ，Ga 3+ ，In 3+ ，Sc 3+ ，V 3+ ，Cr 3+ ，Mn 3+ ，Y 3+ ，Bi 3+ At least one of (a);
the C element is Ti 4+ ，Zr 4+ ，Sn 4+ ,Hf 4+ ，V 5+ ,W 6+ At least one of (a).
3. The positive electrode material according to claim 1, wherein the mass of the coating layer accounts for 0.01-5% of the total mass of the high-voltage lithium cobalt oxide positive electrode material; the thickness of the coating layer is 0.1nm-50 nm.
4. A method for producing a positive electrode material according to any one of claims 1 to 3, comprising the steps of:
s1, reacting doping elements with a precipitator to synthesize layered double hydroxides with the doping elements arranged in order;
s2, stripping the obtained layered double hydroxide by adopting a formamide stripping method or an intercalation auxiliary stripping method to obtain a single-layer or less than 20-layer layered double hydroxide;
and S3, compounding the obtained single-layer or few-layer laminated double metal hydroxide with a lithium cobaltate matrix to obtain the element-accurate co-doped high-voltage lithium cobaltate cathode material.
5. The method for preparing the positive electrode material according to claim 4, wherein the specific steps of preparing the layered double hydroxide with the elements to be doped arranged in order in S1 are as follows:
preparing a solution with the concentration of 0.2-4mol/L by taking soluble salt of a doping element, wherein the molar ratio of divalent metal ions to trivalent metal ions is 2-4: l; adding the mixture and a precipitant into a reaction kettle at the same time and quickly stirring to obtain the layered double hydroxide.
6. The method for preparing the positive electrode material according to claim 5, wherein the precipitant is urea, NaOH, KOH, ammonia water, or Na having a concentration of 1 to 10mol/L 2 CO 3 Or NaHCO 3 Any of the aqueous solutions of (a).
7. The method for preparing the cathode material according to claim 5, wherein the solution is an aqueous solution containing the bimetallic element to be doped prepared by using a soluble salt containing an element Ma and a soluble salt containing an element Mb;
wherein the soluble salt containing the element Ma is at least one of nitrate, oxalate, acetate, fluoride, chloride and sulfate containing the Ma;
wherein the soluble salt containing the element Mb is at least one of oxide, hydroxide, carbonate, nitrate, oxalate and acetate containing the element Mb.
8. The preparation method of the cathode material according to claim 4, wherein the step of coating the obtained single-layer or few-layer layered double metal hydroxide on the surface of the lithium cobaltate comprises the following specific steps:
and mixing the obtained single-layer or few-layer layered double metal hydroxide with an oxide precursor of cobalt and a lithium source, and sintering at 700-1100 ℃ for 8-48 hours to obtain the element-accurately co-doped high-voltage lithium cobaltate cathode material.
9. The method according to claim 8, wherein the lithium source is at least one of lithium hydroxide, lithium nitrate, lithium carbonate, lithium oxalate, lithium acetate, lithium oxide, and lithium citrate.
10. Use of the positive electrode material according to any one of claims 1 to 3 or the positive electrode material produced by the production method according to any one of claims 4 to 9 in a lithium ion secondary battery.
CN202210849141.5A 2022-07-19 2022-07-19 Positive electrode material and preparation method and application thereof Pending CN115000391A (en)

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