CN110492061B - Coating method for assisting interface growth of boron-aluminum oxide thin layer of cathode material by water-soluble additive - Google Patents
Coating method for assisting interface growth of boron-aluminum oxide thin layer of cathode material by water-soluble additive Download PDFInfo
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- 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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- 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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Abstract
The invention discloses a coating method for growing a boron-aluminum oxide thin layer on an interface of a cathode material by using a water-soluble additive, which comprises the following steps: weighing three solid coating raw materials, namely a boron raw material, an aluminum raw material, an organic additive, an inorganic additive and an anode material according to the mass ratio of (0.001-1: 0-1: 0.0001-1: 1-50) to obtain the boron raw material, the aluminum raw material, the organic additive and the inorganic additive, mixing the weighed solid coating raw materials with a liquid dispersing agent, completely dissolving, adding the anode material to prepare slurry, stirring, filtering (or centrifuging) and drying to obtain a coated precursor, and annealing in a treatment atmosphere to obtain the anode material with good boron aluminide coating property. The invention can effectively carry out uniform surface coating on the anode material, improves the cycling stability of the anode material, has stable product performance and simple and convenient operation process, and is easy to realize industrial production.
Description
Technical Field
The invention belongs to the field of lithium ion battery anode materials, and particularly relates to a method for coating a boron-aluminum oxide thin layer on an interface of a water-soluble additive auxiliary anode material.
Background
The popularization of power automobiles and the portable development of 3C electronic products make the demands for high-energy, high-power and long-life lithium ion batteries increasingly urgent. And a positive electrode having a layered structure (e.g., LiCoO) 2 Ternary material LiNi x Co y Mn z O 2 、LiNi x Co y Al z O 2 Lithium-rich materialxLi 2 MnO 3 ·(1-x)LiMO 2 Etc.), spinel type positive electrode (LiMn) 2 O 4 、LiNi x Mn 2-x O 4 ) And olivine type positive electrode (LiFePO) 4 ) Along with the rise of voltage, multiplying power and working temperature, irreversible side reactions are more likely to occur on the interface, so that the performance is attenuated.
In the technical invention for improving the interface stability of the anode material, one idea is to dope the bulk phase boron element into the anode material. For example, in the patent CN103296249A, when the ternary material is synthesized, B is added as the raw material 2 O 3 Firing at 900 ℃ to obtain a boron-doped ternary material; when the patent CN103413931B is used for synthesizing a lithium-rich material, a boron-containing oxide is added to the raw material, and the boron-doped lithium-rich material is obtained by firing at 800-900 ℃. Bulk boron doping has advantages and disadvantages on the influence of the positive electrode material on the battery performance, is mostly discovered in academic exploration and is not used for actual production. Another new idea for improving the interface performance of the cathode material is to coat the subsequent interface of the cathode material with boron-containing oxide. For example, in LiOH. H, the literature (electrochim. Acta, 2015,174,1225) 2 O and H 3 BO 3 Adding LiNi into the mixed aqueous solution of (1: 2) .05 Co .02 Mn .03 O 2 The product is dried by distillation at 80 ℃ and then calcined at 500 ℃ to obtain Li 2 O·2B 2 O 3 Coated LiNi .05 Co .02 Mn .03 O 2 A material; the literature (J. Power Sources, 2017, 362, 131) refers to LiCoO 2 The boric acid aqueous solution is dried by distillation at 90 ℃ and then burnt at 500 ℃ to obtain B 2 O 3 Coated LiCoO 2 . In the two reports, the thicknesses of the coating layers are not uniform, the interface phase change caused by the fact that the anode material is heated in a water phase for a long time is caused, and the high-voltage performance of the material is not optimal. CN101359736 directly adds LiOH and H 3 BO 3 Ball-milling with ternary material, and calcining at 600 ℃ and 1000 ℃ to obtain mLi 2 O·nB 2 O 3 A coated product. The material suffers from both cladding layer non-uniformity and bulk boron doping. The patent CN103236521A mixes and ultrasonically treats the boron-containing neutral organic solution and the ternary material, then subsequently adds an organic dispersant, evaporates the organic solvent to dryness at 70 ℃, and finally calcines in air at 600-850 ℃ to obtain the Li-B-O coated ternary material. In the method, the additive is helpful for improving the uniformity of the coating layer, but the selection of the type of the additive and the feeding time are not optimal, particularly, the coating operation is completed by long-time heating in a neutral organic solvent, the phase change of an interface is easy to occur, the process cost is high, and the practical value is not high.
Around the problems, the invention realizes the controllable growth thickness, uniform coating and adjustable doping component of the interface of the anode material by the water phase on the basis of not damaging the interface structure of the anode material and the performance of the battery through the coating method of the water-soluble additive auxiliary anode material interface boron-aluminum oxide thin layer.
Disclosure of Invention
Aiming at the aim, the corresponding technical scheme of the invention is a coating method for growing a boron-aluminum oxide thin layer on an interface of a water-soluble additive auxiliary anode material, which is characterized by comprising the following steps:
weighing four solid coating raw materials, namely a boron raw material, an aluminum raw material, an organic additive and a positive electrode material according to the mass ratio of the boron raw material to the aluminum raw material to the inorganic additive to the positive electrode material (0.001-1: 0-1: 0.0001-1: 1-50), mixing the weighed solid coating raw materials with a liquid dispersing agent according to the solid-liquid ratio of (0.00001-1) g/mL, and completely dissolving to obtain a solution A, wherein the temperature of the solution A is constant at 0-80 ℃;
weighing the positive electrode material according to the mass ratio in the step I, adding the positive electrode material into the solution A, stirring at a constant temperature (0-80 ℃) for 0.5-12 hours, and performing suction filtration (or centrifugation) and drying at 50-180 ℃ (vacuum drying or forced air drying) to obtain a coated precursor; and calcining the coated precursor at 300-900 ℃ for 1-10 h in a heat treatment atmosphere to obtain the ultrathin boron oxide coated cathode material.
The method for coating the boron-aluminum oxide thin layer on the interface of the water-soluble additive auxiliary anode material is characterized by comprising the following steps of: in the step I, the boron raw material is one or a mixture of boric acid, metaboric acid, diboron trioxide and sodium borate.
The method for coating the boron-aluminum oxide thin layer on the interface of the water-soluble additive auxiliary anode material is characterized by comprising the following steps of: in the step (I), the aluminum raw material is one or a mixture of aluminum nitrate, aluminum chloride, aluminum sulfate and aluminum acetate.
The method for coating the boron-aluminum oxide thin layer on the interface of the water-soluble additive auxiliary anode material is characterized by comprising the following steps of: the organic additive in the step (i) is one or a mixture of glucose, cassava native starch, soluble starch, wheat native starch, corn native starch, carboxymethyl starch, polyvinyl alcohol, citric acid, fructose, Cetyl Trimethyl Ammonium Bromide (CTAB), Polyacrylamide (PAM), polyvinylpyrrolidone (PVP), Sodium Dodecyl Sulfate (SDS), stearic acid and Sodium Dodecyl Benzene Sulfonate (SDBS).
The method for coating the boron-aluminum oxide thin layer on the interface of the water-soluble additive auxiliary anode material is characterized by comprising the following steps of: in the step I, the inorganic additive is one or a mixture of more of copper chloride, copper sulfate, zinc nitrate, lanthanum chloride, lanthanum sulfate, cerium chloride, cerium nitrate, yttrium nitrate, ammonium metavanadate, lithium hydroxide, lithium carbonate, lithium chloride, lithium nitrate, sodium chloride, sodium sulfate, potassium chloride, potassium sulfate, sodium acetate and potassium acetate.
The method for coating the boron-aluminum oxide thin layer on the interface of the water-soluble additive auxiliary anode material is characterized by comprising the following steps of: the dispersant in the step (i) is a mixture of pure water and one or more of ethanol, methanol, glycol, isopropanol and glycerol (the volume ratio of the pure water in the dispersant is not less than 50%).
The method for coating the boron-aluminum oxide thin layer on the interface of the water-soluble additive auxiliary anode material is characterized by comprising the following steps of: in the step I, the positive electrode material is LiCoO 2 、LiNi x Co 1-x-y Mn y O 2 (0﹤x﹤1、0﹤y﹤1) 、LiNi x Co y Al 1-x-y O 2 (0.7﹤x﹤1、0﹤y﹤0.3)、xLi 2 MnO 3 ·(1-x)LiMO 2 、LiMn 2 O 4 (0﹤x﹤1、M=Ni、Co、Mn)。
The method for coating the boron-aluminum oxide thin layer on the interface of the water-soluble additive auxiliary anode material is characterized by comprising the following steps of: and secondly, in the step, the heat treatment atmosphere is one or a mixture of air, oxygen (99.6-99.9%) and high-purity oxygen (99.99%).
Drawings
FIG. 1 is a schematic representation of an ultra-thin boron oxide coated LiNi prepared in accordance with one embodiment of the present invention 0.5 Co 0.2 Mn 0.3 O 2 XRD pattern of the material.
FIG. 2 is a second preparation of example II of the present inventionThe ultrathin boron-aluminum oxide coated LiNi 0.5 Co 0.2 Mn 0.3 O 2 XRD pattern of the material;
FIG. 3 is an ultra-thin boron oxide coated LiNi prepared in accordance with one embodiment of the present invention 0.5 Co 0.2 Mn 0.3 O 2 Scanning electron microscope macroscopic view of the material:
FIG. 4 is an ultra-thin boron oxide coated LiNi prepared in accordance with one embodiment of the present invention 0.5 Co 0.2 Mn 0.3 O 2 Scanning electron microscope high magnification of the material:
FIG. 5 is an ultra-thin boron aluminum oxide coated LiNi prepared in example two of the present invention 0.5 Co 0.2 Mn 0.3 O 2 Scanning electron microscope macroscopic view of the material:
FIG. 6 shows LiNi coated with ultra-thin boron-aluminum oxide prepared in the second embodiment of the present invention 0.5 Co 0.2 Mn 0.3 O 2 Scanning electron microscope high magnification image of material:
FIG. 7 is an ultra-thin boron oxide coated LiNi prepared in accordance with one embodiment of the present invention 0.5 Co 0.2 Mn 0.3 O 2 A multiplying power performance diagram of the button cell battery made of the material under 0.1C, 0.5C, 1C, 5C, 10C and 0.1C;
FIG. 8 is an ultra-thin boron oxide coated LiNi prepared in accordance with one embodiment of the present invention 0.5 Co 0.2 Mn 0.3 O 2 Cycle life plot at 1C for button cell of material;
FIG. 9 is an ultra-thin boron aluminum oxide coated LiNi prepared in example four of the present invention 0.5 Co 0.2 Mn 0.3 O 2 A multiplying power performance diagram of the button cell battery made of the material under 0.1C, 0.5C, 1C, 5C, 10C and 0.1C;
FIG. 10 is an ultra-thin boron aluminum oxide coated LiNi prepared in example two of the present invention 0.5 Co 0.2 Mn 0.3 O 2 Button cell life of material at 1C.
Detailed Description
Example 1
According to the water-soluble additive for assisting the interface coating of the cathode material with the aluminum boride to oxidizeA method for laminating a substrate, comprising the steps of: 0.9275g of boric acid and 1g of polyvinylpyrrolidone (PVP) are weighed, the weighed solid coating raw materials are mixed with 100mL of pure water and completely dissolved to obtain a solution A, and the temperature of the solution A is kept at 0 ℃; then weighing 10g of LiNi 0.5 Co 0.2 Mn 0.3 O 2 Adding the solution A, then keeping the temperature at 0 ℃, stirring for 2h, performing suction filtration, and performing vacuum drying at 120 ℃ to obtain a coated precursor; and uniformly placing the coated precursor in a magnetic boat, and calcining for 2 hours at the temperature of 500 ℃ in oxygen to obtain the ultrathin boron oxide coated cathode material.
Example 2
The method for coating the boron-aluminum oxide thin layer on the interface of the water-soluble additive auxiliary anode material is characterized by comprising the following steps of: 0.9275g of boric acid, 0.0759g of aluminum nitrate nonahydrate and 1g of polyvinylpyrrolidone (PVP) are weighed, the weighed solid coating raw materials are mixed with 100mL of ethanol, and the mixture is completely dissolved to obtain a solution A, wherein the temperature of the solution A is kept at 25 ℃; then weighing 10g of LiNi 0.5 Co 0.2 Mn 0.3 O 2 Adding the solution A, then keeping the temperature at 0 ℃, stirring for 2h, performing suction filtration, and performing vacuum drying at 120 ℃ to obtain a coated precursor; and uniformly placing the coated precursor in a magnetic boat, and calcining for 2h at the temperature of 500 ℃ in oxygen to obtain the ultrathin boron-aluminum oxide coated cathode material.
Example 3
The method for coating the boron-aluminum oxide thin layer on the interface of the water-soluble additive auxiliary anode material is characterized by comprising the following steps of: 0.9275g of boric acid, 0.0918g of aluminum nitrate nonahydrate, 1g of soluble starch and 0.1g of lanthanum chloride are weighed, the weighed solid coating raw materials are mixed with 100mL of ethanol and completely dissolved to obtain a solution A, and the temperature of the solution A is kept at 0 ℃; then weighing 10g of LiNi 0.6 Co 0.2 Mn 0.2 O 2 After the solution A is added, the solution A is stirred for 2 hours at the constant temperature of 0 ℃, and then a coated precursor is obtained through suction filtration and vacuum drying at 120 ℃; and uniformly placing the coated precursor in a magnetic boat, and calcining for 2 hours at the temperature of 700 ℃ in oxygen to obtain the ultrathin boron aluminum oxide coated cathode material.
Example 4
According to one kind ofThe method for coating the boron-aluminum oxide thin layer on the interface of the water-soluble additive auxiliary anode material is characterized by comprising the following steps of: 0.9275g of boric acid, 0.0759g of aluminum nitrate nonahydrate, 1g of glucose and 0.1g of yttrium nitrate are weighed, the weighed solid coating raw materials are mixed with 100mL of pure water and completely dissolved to obtain a solution A, and the temperature of the solution A is kept at 25 ℃; then weighing 10g of LiNi 0.8 Co 0.1 Mn 0.1 O 2 Adding the solution A, then stirring for 2h at the constant temperature of 25 ℃, and then carrying out suction filtration and vacuum drying at 120 ℃ to obtain a coated precursor; and uniformly placing the coated precursor in a magnetic boat, and calcining for 2 hours at the temperature of 500 ℃ in oxygen to obtain the ultrathin boron aluminum oxide coated cathode material.
Example 5
The method for coating the boron-aluminum oxide thin layer on the interface of the water-soluble additive auxiliary anode material is characterized by comprising the following steps of: 0.9275g of boric acid, 0.8g of carboxymethyl starch and 0.08g of sodium acetate are weighed, the weighed solid coated raw materials are mixed with 100mL of pure water and are completely dissolved to obtain a solution A, and the temperature of the solution A is kept at 25 ℃; then weighing 10g of LiNi 0.8 Co 0.1 Mn 0.1 O 2 Adding the solution A, then stirring for 2h at the constant temperature of 25 ℃, and then carrying out suction filtration and vacuum drying at 120 ℃ to obtain a coated precursor; and uniformly placing the coated precursor in a magnetic boat, and calcining for 2h at 800 ℃ under oxygen to obtain the ultrathin boron oxide coated anode material.
Example 6
The method for coating the boron-aluminum oxide thin layer on the interface of the water-soluble additive auxiliary anode material is characterized by comprising the following steps of: 0.9275g of boric acid, 0.0607g of aluminum nitrate nonahydrate, 1g of cassava native starch and 0.1g of lanthanum sulfate are weighed, the weighed solid coating raw materials are mixed with 100mL of pure water and completely dissolved to obtain a solution A, and the temperature of the solution A is constant at 0 ℃; then weighing 10g of LiNi 0.8 Co 0.15 Al 0.05 O 2 Adding the solution A, then keeping the temperature at 0 ℃, stirring for 2h, performing suction filtration, and performing vacuum drying at 120 ℃ to obtain a coated precursor; and uniformly placing the coated precursor in a magnetic boat, and calcining for 2h at the temperature of 450 ℃ by using oxygen to obtain the ultrathin boron-aluminum oxide coated cathode material.
Example 7
The method for coating the boron-aluminum oxide thin layer on the interface of the water-soluble additive auxiliary anode material is characterized by comprising the following steps of: 0.9275g of boric acid, 0.0380g of aluminum nitrate nonahydrate, 1g of fructose and 0.1g of ammonium metavanadate are weighed, the weighed solid coating raw materials are mixed with 100mL of ethanol, and a solution A is obtained by complete dissolution, wherein the temperature of the solution A is constant at 0 ℃; then weighing 10g of LiNi 0.8 Co 0.15 Al 0.05 O 2 Adding the solution A, then keeping the temperature at 0 ℃, stirring for 2h, performing suction filtration, and performing vacuum drying at 120 ℃ to obtain a coated precursor; and uniformly placing the coated precursor in a magnetic boat, and calcining for 2h at the temperature of 500 ℃ in oxygen to obtain the ultrathin boron-aluminum oxide coated cathode material.
Example 8
The method for coating the boron-aluminum oxide thin layer on the interface of the water-soluble additive auxiliary anode material is characterized by comprising the following steps of: 0.9275g of boric acid, 0.0759g of aluminum nitrate nonahydrate, 1g of glucose and 0.1g of yttrium nitrate are weighed, the weighed solid coating raw materials are mixed with 100mL of pure water, and a solution A is obtained by complete dissolution, wherein the temperature of the solution A is constant at 0 ℃; further, 10g of 0.5Li was weighed 2 MnO 3 ·0.5Li 0.44 Co 0.25 Mn 0.31 O 2 Adding the solution A, then keeping the temperature at 0 ℃, stirring for 2h, performing suction filtration, and performing vacuum drying at 120 ℃ to obtain a coated precursor; and uniformly placing the coated precursor in a magnetic boat, and calcining for 2 hours at the temperature of 500 ℃ in oxygen to obtain the ultrathin boron aluminum oxide coated cathode material.
The invention reduces the side reaction on the surface of the anode material by preparing the ultrathin and uniform coating layer for the first time, improves the chemical stability of the material in the charging and discharging process, and further improves the cycling stability under the high voltage of 4.5V. The method is simple to operate, has an excellent coating effect, is non-toxic and environment-friendly, and is easy to realize industrial production.
Claims (3)
1. A coating method for growing a boron-aluminum oxide thin layer on an interface of a water-soluble additive auxiliary anode material is characterized by comprising the following steps:
(1) and according to the boron raw material: aluminum raw material: organic additives: inorganic additives: the mass ratio of the positive electrode material is 0.001-1: 0-1: 0.0001 to 1: 0.0001 to 1: 1-50 weighing four solid coating raw materials, namely a boron raw material, an aluminum raw material, an organic additive and an inorganic additive, mixing the weighed solid coating raw materials with a liquid dispersant according to a solid-liquid ratio of 0.00001-1 g/mL, and completely dissolving to obtain a solution A, wherein the temperature of the solution A is constant at 0-25 ℃;
(2) weighing the positive electrode material according to the mass ratio in the step (1), adding the positive electrode material into the solution A, stirring at a constant temperature for 0.5-2 h at the temperature of 0-25 ℃, performing suction filtration or centrifugation, and drying at 50-180 ℃, wherein vacuum drying or forced air drying is adopted for drying to obtain a coated precursor; calcining the coated precursor for 1-10 h at 300-900 ℃ in a heat treatment atmosphere, wherein the heat treatment atmosphere is oxygen, and thus obtaining the ultrathin boron oxide coated anode material;
the organic additive in the step (1) is one or a mixture of glucose, cassava native starch, soluble starch, wheat native starch, corn native starch, carboxymethyl starch, polyvinyl alcohol, citric acid, fructose, cetyl trimethyl ammonium bromide, polyvinylpyrrolidone, sodium dodecyl sulfate, stearic acid and sodium dodecyl benzene sulfonate;
the inorganic additive in the step (1) is one or a mixture of more of copper chloride, copper sulfate, zinc nitrate, lanthanum chloride, lanthanum sulfate, cerium chloride, cerium nitrate, yttrium nitrate, ammonium metavanadate, sodium chloride, sodium sulfate, potassium chloride, potassium sulfate, sodium acetate and potassium acetate.
2. The coating method for assisting the interface growth of the boron-aluminum oxide thin layer of the cathode material by the water-soluble additive according to claim 1, wherein the boron raw material in the step (1) is one or a mixture of boric acid, metaboric acid, diboron trioxide and sodium borate.
3. The coating method for the interface growth of the boron-aluminum oxide thin layer of the cathode material assisted by the water-soluble additive according to claim 1, wherein the aluminum raw material in the step (1) is one or a mixture of aluminum nitrate, aluminum chloride, aluminum sulfate and aluminum acetate.
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