CN108682795B - Surface pickling coating TiO of ternary anode material of lithium ion battery2Method (2) - Google Patents
Surface pickling coating TiO of ternary anode material of lithium ion battery2Method (2) Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 20
- 239000010405 anode material Substances 0.000 title claims abstract description 15
- 239000011248 coating agent Substances 0.000 title claims abstract description 15
- 238000005554 pickling Methods 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 49
- 239000000725 suspension Substances 0.000 claims abstract description 28
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims abstract description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000010406 cathode material Substances 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 22
- 239000007774 positive electrode material Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002244 precipitate Substances 0.000 claims abstract description 11
- 238000001291 vacuum drying Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000000967 suction filtration Methods 0.000 claims abstract description 4
- DQTJHJVUOOYAMD-UHFFFAOYSA-N oxotitanium(2+) dinitrate Chemical compound [O-][N+](=O)O[Ti](=O)O[N+]([O-])=O DQTJHJVUOOYAMD-UHFFFAOYSA-N 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 claims description 2
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 claims description 2
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract description 9
- 238000003860 storage Methods 0.000 abstract description 6
- 230000001351 cycling effect Effects 0.000 abstract description 5
- 239000011247 coating layer Substances 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 238000002715 modification method Methods 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 229910052573 porcelain Inorganic materials 0.000 description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 206010016766 flatulence Diseases 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- 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
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
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- 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
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/48—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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- 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 surface pickling coating TiO of a ternary anode material of a lithium ion battery2The method relates to the technical field of lithium ion batteries, and comprises the following steps: dissolving titanyl sulfate and sulfuric acid in deionized water to prepare a saturated titanyl sulfate solution; adding a ternary positive electrode material into a saturated titanium sulfate acyl solution, carrying out ultrasonic mixing to form a suspension, continuously stirring the suspension until the color of the suspension becomes light to obtain a brown precipitate, carrying out suction filtration, washing with alcohol, and carrying out vacuum drying to obtain a dried material; placing the dried material in a muffle furnace for heat treatment, and then cooling along with the furnace to obtain TiO2A coated ternary positive electrode material. The surface modification method carries out surface modification on the ternary cathode material through the controllable pickling coating process, reduces the residual alkali on the surface of the ternary material, and simultaneously forms uniform TiO on the surface2The coating layer can effectively improve the first efficiency, the discharge capacity, the cycling stability and the water absorption characteristic in the storage process of the ternary material, and has great application value.
Description
Technical Field
The invention relates to lithium ionThe technical field of batteries, in particular to a ternary anode material surface pickling coated TiO for a lithium ion battery2The method of (1).
Background
Ternary layered oxide materials have been used as positive electrode materials for lithium ion batteries due to their advantages of high specific capacity, low cost, environmental friendliness, etc., and are widely used in the fields of portable devices, electric vehicles, and energy storage. But the poor thermal stability, cycling stability and storage performance of the composite material have certain potential safety hazards in practical application, and the large-scale application of the composite material is greatly limited.
The poor thermal stability, cycling stability and storage performance of the commercial nickel-cobalt-manganese ternary material are due to the fact that a large amount of free lithium exists on the surface of the ternary material due to the existing mass production process, and the free lithium is easy to react with H in the air2O and CO2Reaction to generate LiOH and Li on the surface of material2CO3Resulting in too high a material pH and surface residual alkali content. LiOH reacts with LiPF in the electrolyte6Reaction to HF, Li2CO3Can cause serious flatulence during high-temperature storage, seriously influences the electrochemical performance of the material and simultaneously causes potential safety hazard.
In the prior art, washing the ternary cathode material with water can effectively reduce the residual alkali on the surface of the material, but a large number of experiments show that the washed material resists H in the air2O/CO2The ability of (a) to decrease. Meanwhile, in the wet coating treatment process of the material, the uncovered areas of the surface of the material, which are not coated, are similar to the material after water washing, and the areas are too much, so that the cycle performance of the material is deteriorated. In addition, in the existing washing or coating process, due to uncontrollable washing and coating processes, lattice defects and uneven coating are easily caused, so that the discharge capacity of the ternary cathode material is reduced, microcracks are easily generated in the storage and discharge processes, and the stability and the storage performance of the material are not improved.
Disclosure of Invention
Based on the technical problems in the prior art, the invention provides a surface pickling coating TiO of a ternary anode material of a lithium ion battery2The method solves the problems of the prior mass production processThe pH value of the surface of the ternary anode material is too high, the residual alkali content of the surface is high, and the problems of lattice defects and uneven coating caused in a water washing coating process are solved.
The surface of the ternary anode material of the lithium ion battery provided by the invention is acid-washed and coated with TiO2The method comprises the following steps:
s1, dissolving titanyl sulfate and sulfuric acid in deionized water to prepare a saturated titanyl sulfate solution;
s2, adding the ternary positive electrode material into a saturated titanium sulfate acyl solution, carrying out ultrasonic mixing to form a suspension, continuously stirring the suspension until the color of the suspension becomes light to obtain brown precipitate, carrying out suction filtration, washing with alcohol, and carrying out vacuum drying to obtain a dried material;
s3, placing the dried material in a muffle furnace for heat treatment, and then cooling along with the furnace to obtain TiO2A coated ternary positive electrode material.
Preferably, in the S1, 1 to 1.2 parts of titanyl sulfate and 60 to 100 parts of 1mol/L sulfuric acid are dissolved in 2000 parts of deionized water to prepare a saturated titanyl sulfate solution.
Preferably, in S2, the ternary positive electrode material is added to a saturated titanyl sulfate solution, ultrasonically mixed for 25-40min to form a suspension, the suspension is continuously stirred for 0.5-5h until the color of the suspension becomes light, a brown precipitate is obtained, the solution is filtered, washed with alcohol, and vacuum-dried at 65-75 ℃ for 6-10h to obtain a dried material.
Preferably, in S2, the ternary positive electrode material is lithium nickel cobalt manganese oxide LiNixCoyMn1-x-yO2Wherein x is more than or equal to 0.6<1,0<y≤0.2。
Preferably, in S2, the addition amount of the ternary cathode material ensures that TiO generated by the reaction2The mass of (A) is 0.1-10% of the mass of the ternary cathode material.
Preferably, in S3, the heat treatment operation is as follows: heating to 150-2A coated ternary positive electrode material.
Preferably, the saturated titanyl sulfate solution can also be a saturated titanyl nitrate solution, and the saturated titanyl nitrate solution is prepared by dissolving titanyl nitrate and nitric acid in deionized water.
Has the advantages that: the invention utilizes the reversible hydrolysis reaction of titanyl sulfate (or titanyl nitrate),preparing saturated titanyl sulfate (or titanyl nitrate) solution, reducing residual alkali on the surface of the nickel-cobalt-manganese ternary material by controlling the amount of added sulfuric acid (nitric acid), promoting hydrolysis reaction to occur rightwards, generating metatitanic acid on the surface, and then filtering, washing, drying, sintering and the like to form TiO uniformly coated on the surface2The ternary material avoids the side reaction and the uneven coating in the wet coating process. In addition, the purpose of regulating and controlling the thickness of the coating layer can be achieved by controlling the pickling time. The surface modification method carries out surface modification on the ternary cathode material through the controllable pickling coating process, reduces the residual alkali on the surface of the ternary material, and simultaneously forms uniform TiO on the surface2The coating layer can effectively improve the first efficiency, discharge capacity and circulation stability of the ternary material and improve the CO resistance of the ternary material in air2And H2The O capacity has great application value in the actual production process.
Drawings
FIG. 1 is a schematic diagram of the acid pickling and coating process of saturated titanyl sulfate solution according to the present invention;
FIG. 2 shows the surface of the ternary cathode material coated with TiO by acid cleaning in example 2 of the present invention2Front and coating TiO2SEM image after the above.
Detailed Description
FIG. 1 is a schematic diagram of the acid pickling and coating process of saturated titanyl sulfate solution according to the present invention. As can be seen from the figure, a large amount of free lithium exists on the surface of the ternary cathode material, and the free lithium is easy to react with H in the air2O and CO2Reaction to generate LiOH and Li on the surface of material2CO3Resulting in too high a material pH and surface residual alkali content. Using saturated titanyl sulfatesAcid washing is carried out on the sulfuric acid solution, on one hand, the sulfuric acid in the solution is mixed with LiOH and Li2CO3Neutralization reaction is carried out to reduce the content of residual alkali on the surface of the material, meanwhile, reversible hydrolysis reaction of titanyl sulfate is promoted to be carried out rightwards, metatitanic acid is generated on the surface of the material, and then uniform coated TiO is formed on the surface of the material through subsequent treatment2The ternary material avoids the side reaction and the uneven coating in the wet coating process.
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
The surface of the ternary anode material of the lithium ion battery provided by the invention is acid-washed and coated with TiO2The method comprises the following steps:
s1, dissolving 1 part of titanyl sulfate and 60 parts of 1mol/L sulfuric acid in 2000 parts of deionized water to prepare a saturated titanyl sulfate solution;
s2, mixing 5 parts of ternary cathode material LiNi0.85Co0.1Mn0.05O2Adding into saturated titanium sulfate acyl solution, ultrasonic mixing for 30min, mixing to obtain suspension, stirring the suspension for 0.5-1 hr until the color of the suspension becomes light to obtain brown precipitate, vacuum filtering, washing with alcohol for 3 times, and vacuum drying at 65 deg.C for 6 hr to obtain dried material;
s3, placing the dried material on a porcelain boat, placing the porcelain boat in a muffle furnace for heat treatment, heating to 150 ℃ at a speed of 2 ℃/min in an air atmosphere, preserving heat for 1.5h, heating to 450 ℃ at a speed of 5 ℃/min, preserving heat for 5h, and cooling with the furnace to obtain TiO2A coated ternary positive electrode material.
For the TiO prepared in this example2And detecting the coated ternary cathode material. The detection shows that the surface Ti content is low, the Ti content is about 0.2 wt%, the surface pH of the ternary electrode material is greatly reduced, the capacity change is not obvious, the circulation stability is improved, and the capacity reaches 190mAh/g after 1C circulation for 100 times. This is illustrated in TiO (OH)2The surface alkali residue is effectively reduced under the protection of the sol, and side reaction in the wet coating process is avoided. Final TiO due to short pickling time2The coating is carried out selectively,under a scanning electron microscope, the surface of the particles can be seen to have obvious fine spots.
Example 2
The surface of the ternary anode material of the lithium ion battery provided by the invention is acid-washed and coated with TiO2The method comprises the following steps:
s1, dissolving 1 part of titanyl sulfate and 60 parts of 1mol/L sulfuric acid in 2000 parts of deionized water to prepare a saturated titanyl sulfate solution;
s2, mixing 5 parts of ternary cathode material LiNi0.85Co0.1Mn0.05O2Adding into saturated titanium sulfate acyl solution, ultrasonic mixing for 30min, mixing to obtain suspension, stirring for 4 hr until the color of suspension becomes light to obtain brown precipitate, vacuum filtering, washing with alcohol for 3 times, and vacuum drying at 70 deg.C for 6 hr to obtain dried material;
s3, placing the dried material on a porcelain boat, placing the porcelain boat in a muffle furnace for heat treatment, heating to 150 ℃ at a speed of 2 ℃/min in an air atmosphere, preserving heat for 1.5h, heating to 500 ℃ at a speed of 5 ℃/min, preserving heat for 5h, and cooling with the furnace to obtain TiO2A coated ternary positive electrode material.
For the TiO prepared in this example2And detecting the coated ternary cathode material. The detection shows that the Ti content on the surface of the ternary electrode material is about 2 wt%, the pH value on the surface of the ternary electrode material is greatly reduced, the capacity and the cycling stability are improved, a figure 2 shows SEM comparison photographs before and after the ternary anode material is coated, the surface of the coated material particles is more compact and the surface of the coated material particles becomes smooth, and the uniform distribution of the Ti element can be detected from the EDS element distribution.
Example 3
The surface of the ternary anode material of the lithium ion battery provided by the invention is acid-washed and coated with TiO2The method comprises the following steps:
s1, dissolving 1 part of titanyl nitrate and 100 parts of 1mol/L nitric acid in 2000 parts of deionized water to prepare a saturated titanyl nitrate solution;
s2, mixing 10 parts of ternary cathode material LiNi0.85Co0.1Mn0.05O2Adding into saturated titanyl nitrate solution, and performing ultrasonic treatmentMixing for 30min, stirring for 2 hr until the color of the suspension becomes light to obtain brown precipitate, vacuum filtering, washing with alcohol for 3 times, and vacuum drying at 75 deg.C for 6 hr to obtain dried material;
s3, placing the dried material on a porcelain boat, placing the porcelain boat in a muffle furnace for heat treatment, heating to 150 ℃ at a speed of 2 ℃/min in an air atmosphere, preserving heat for 1.5h, heating to 500 ℃ at a speed of 5 ℃/min, preserving heat for 5h, and cooling with the furnace to obtain TiO2A coated ternary positive electrode material.
For the TiO prepared in this example2And detecting the coated ternary cathode material. The detection shows that the content of Ti element on the surface is about 0.2 wt%, the pH value is greatly reduced, the capacity and the cycling stability are improved, the discharge capacity of 0.1C, 1C and 2C reaches 215 mAh/g, 198 and 192mAh/g, the first effect of 0.1C reaches 92.1%, and the capacity retention rate reaches 98.5% after 100 cycles. From the SEM photograph after coating, it can be seen that the particle surface is more compact and the surface becomes smooth, and from the EDS element distribution, it can be detected that the Ti element is uniformly distributed. The acid pickling coating effect of this example is better compared to examples 1 and 2, which is probably because dilute nitric acid is less oxidizing than dilute sulfuric acid and has less effect on the surface of the ternary material particles.
Example 4
The surface of the ternary anode material of the lithium ion battery provided by the invention is acid-washed and coated with TiO2The method comprises the following steps:
s1, dissolving 1.2 parts of titanyl sulfate and 100 parts of 1mol/L sulfuric acid in 2000 parts of deionized water to prepare a saturated titanyl sulfate solution;
s2, mixing 6 parts of ternary cathode material LiNi0.85Co0.1Mn0.05O2Adding into saturated titanium sulfate acyl solution, ultrasonic mixing for 25min, mixing to obtain suspension, stirring for 3.5 hr until the color of suspension becomes light to obtain brown precipitate, vacuum filtering, washing with alcohol for 3 times, and vacuum drying at 65 deg.C for 8 hr to obtain dried material;
s3, placing the dried material on a porcelain boat, placing the porcelain boat in a muffle furnace for heat treatment, heating to 180 ℃ at the speed of 2 ℃/min in the air atmosphere, preserving heat for 1.5h, and then carrying out heat treatment on the porcelain boatHeating to 480 ℃ at a speed of 5 ℃/min, preserving heat for 7h, and cooling with the furnace to obtain TiO2A coated ternary positive electrode material.
Example 5
The surface of the ternary anode material of the lithium ion battery provided by the invention is acid-washed and coated with TiO2The method comprises the following steps:
s1, dissolving 1 part of titanyl sulfate and 60 parts of 1mol/L sulfuric acid in 2000 parts of deionized water to prepare a saturated titanyl sulfate solution;
s2, mixing 5 parts of ternary cathode material LiNi0.85Co0.1Mn0.05O2Adding into saturated titanium sulfate acyl solution, ultrasonic mixing for 40min, mixing to obtain suspension, stirring for 5 hr until the color of suspension becomes light to obtain brown precipitate, vacuum filtering, washing with alcohol for 3 times, and vacuum drying at 70 deg.C for 10 hr to obtain dried material;
s3, placing the dried material on a porcelain boat, placing the porcelain boat in a muffle furnace for heat treatment, heating to 200 ℃ at a speed of 2 ℃/min in an air atmosphere, preserving heat for 2h, heating to 490 ℃ at a speed of 5 ℃/min, preserving heat for 8h, and cooling with the furnace to obtain TiO2A coated ternary positive electrode material.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. Surface pickling coating TiO of ternary anode material of lithium ion battery2The method is characterized by comprising the following steps:
s1, dissolving titanyl sulfate and sulfuric acid in deionized water to prepare a saturated titanyl sulfate solution;
s2, adding the ternary positive electrode material into a saturated titanium sulfate acyl solution, carrying out ultrasonic mixing to form a suspension, continuously stirring the suspension until the color of the suspension becomes light to obtain brown precipitate, carrying out suction filtration, washing with alcohol, and carrying out vacuum drying to obtain a dried material;
s3, placing the dried material in a muffle furnace for heat treatment, and then cooling along with the furnace to obtain TiO2A coated ternary positive electrode material.
2. The surface acid-washing coated TiO of the ternary cathode material of the lithium ion battery of claim 12The method of (5), in the S1, dissolving 1-1.2 parts of titanyl sulfate and 60-100 parts of 1mol/L sulfuric acid in 2000 parts of deionized water to prepare a saturated titanyl sulfate solution.
3. The surface acid-washing coated TiO of the ternary cathode material of the lithium ion battery of claim 12The method is characterized in that in S2, a ternary positive electrode material is added into a saturated titanium sulfate acyl solution, ultrasonic mixing is carried out for 25-40min to form a suspension, the suspension is continuously stirred for 0.5-5h until the color of the suspension becomes light, a brown precipitate is obtained, the filtration is carried out, the washing is carried out by alcohol, and the vacuum drying is carried out for 6-10h at the temperature of 65-75 ℃ to obtain a dry material.
4. The surface acid-washing coated TiO of the ternary cathode material of the lithium ion battery of claim 12The method is characterized in that in S2, the ternary positive electrode material is lithium nickel cobalt manganese LiNixCoyMn1-x-yO2Wherein x is more than or equal to 0.6<1,0<y≤0.2。
5. The surface acid-washing coated TiO of the ternary cathode material of the lithium ion battery of claim 12The method of (1), wherein in S2, the addition amount of ternary positive electrode material ensures the TiO generated by the reaction2The mass of (A) is 0.1-10% of the mass of the ternary cathode material.
6. The surface acid-washing coated TiO of the ternary cathode material of the lithium ion battery of claim 12In S3, the heat treatment operation is as follows: heating to 150-Keeping the temperature for 5-8h at 500 ℃ to 450-2A coated ternary positive electrode material.
7. Surface pickling coating TiO of ternary anode material of lithium ion battery2The method is characterized by comprising the following steps:
s1, dissolving titanyl nitrate and nitric acid in deionized water to prepare a saturated titanyl nitrate solution;
s2, adding the ternary positive electrode material into a saturated titanyl nitrate solution, carrying out ultrasonic mixing to form a suspension, continuously stirring the suspension until the color of the suspension becomes light to obtain brown precipitate, carrying out suction filtration, washing with alcohol, and carrying out vacuum drying to obtain a dried material;
s3, placing the dried material in a muffle furnace for heat treatment, and then cooling along with the furnace to obtain TiO2A coated ternary positive electrode material.
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CN112194199A (en) * | 2020-08-27 | 2021-01-08 | 浙江美都海创锂电科技有限公司 | Preparation method of long-cycle ternary cathode material |
CN112086679B (en) * | 2020-09-30 | 2022-02-18 | 合肥国轩高科动力能源有限公司 | High-nickel ternary material, surface modification method and lithium ion battery |
CN112993258B (en) * | 2021-05-12 | 2021-08-17 | 蜂巢能源科技有限公司 | Doping and coating method of ternary cathode material, ternary cathode material and lithium ion battery |
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