CN110556531A - Anode material, preparation method thereof and lithium ion battery containing anode material - Google Patents
Anode material, preparation method thereof and lithium ion battery containing anode material 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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- H01M4/525—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 relates to a positive electrode material, a preparation method thereof and a lithium ion battery containing the positive electrode material, belonging to the technical field of lithium battery materials.A positive electrode material comprises a lithium manganate bulk material and a nickel cobalt lithium manganate surface layer material coated on the surface of lithium manganate, wherein the surface layer material accounts for 0.01 ~ 40% of the mass of the positive electrode material.
Description
Technical Field
The invention relates to a positive electrode material, a preparation method thereof and a lithium ion battery containing the positive electrode material, and belongs to the technical field of lithium battery materials.
Background
lithium manganate LiMn 2 O 4 (LMO) material has a three-dimensional spinel structure, belonging to FD3M space group, and found application in lithium ion batteries by Goodenough group, the university of oxford, uk, the first 1980 s, unlike layered structured materials such as lithium cobaltate LiCoO 2 (LCO) and ternary material Li 1+y (Ni a Co b Mn 1-a-B-z B z) 1-y O 2 (NCM), in FD3M structure, lithium ions occupy the tetrahedral 8a position, while manganese ions and oxygen anions occupy the octahedral 16d and 32e positions, respectively, lithium ions exhibit relatively rapid diffusion through the three-dimensional path of the sites 8a and 16c, and thus lithium manganate has excellent rate capability for use in batteries.
Although the commercial application of electric bicycles, electric tools and electric vehicles has been realized, a problem to be solved before the lithium manganate is commercially used in larger scale in the field of energy storage, that is, the cycle life, is urgently needed. Compared with a layered NCM ternary material and lithium iron phosphate (LFP) with an olivine structure, the cycle life of the spinel lithium manganate material is poor and is generally difficult to exceed 2000 times, and the cycle life of the lithium iron phosphate and the NCM can reach more than 3000 times. The currently discussed mechanisms for the poor cycle life of lithium manganate include three types:
1. due to the action of trace water and electrolyte LiPF 6 contained in the electrolyte solution, the generated HF acts as a catalyst to cause disproportionation of Mn 3+ in LMO to generate Mn 4+ and Mn 2+, resulting in the dissolution of manganese.
The formation of a passivation film of LMO on the particle surface by reaction with the electrolyte results in an increase in the polarization resistance of the electrode and a capacity fade.
3. the Jahn-Teller effect that occurs during deep discharge causes the LMO crystal structure to change, resulting in a reduction in the cyclic ratio capacity.
at present, the main methods for improving the cycle performance of the lithium manganate positive electrode material are element doping (such as metal elements like Li +, Co 3+, Al 3+, Cr 3+ and the like), surface coating (i.e. coating the surface with oxides or non-oxide materials such as SiO 2, MgO, carbon, graphene, fluoride, phosphate, fast ion conductors and the like), however, although the conventional oxide, fluoride and phosphate coating can reduce the chemical reaction and manganese dissolution generated by the direct contact of the positive electrode material and electrolyte, the coating is not full-coverage coating generally, the dissolution of metal manganese cannot be completely reduced, the high-temperature cycle is poor, the coating system per se does not conduct electricity and lithium ions, the interface resistance is increased, the capacity is reduced due to excessive coating, and the capacity is reduced due to excessive coating.
Disclosure of Invention
based on the above problems, the main object of the present invention is to provide a positive electrode material, and the purpose of the present invention is to provide a positive electrode material with complete coating, low interface resistance, good cycle performance, and high specific capacity.
In order to achieve the purpose, the positive electrode material provided by the invention comprises lithium manganate containing and/or not containing doping elements and a coating layer coated on the surface of the lithium manganate, wherein the coating layer is a nickel-cobalt-manganese ternary material containing or not containing doping elements.
furthermore, the chemical general formula of the lithium manganate is Li (Me x Mn 2-x) O 4, wherein x is more than or equal to 0 and less than or equal to 0.2, Me is one or more of Li 1+, Co 2+, Ni 2+, Zn 2+, Mg 2+, Al 3+, Cr 3+, Sc 3+, Ga 3+, Ti 4+ and Zr 4+, the chemical general formula of the nickel-cobalt-manganese ternary material is Li 1+y (Ni a Co b Mn 1-a-B-z B z) 1-y O 2, wherein y is more than or equal to 0.2 and less than or equal to 0.2, z is more than or equal to 0 and less than or equal to 0.1, a <1, 0< B <1, 0< a + B + y <1, and B is one or more of Zn 2+, Mg 2+, Zn 2+, Al 3+, Cr 3+, Sc 3+, Ga 3+, La 3+, Ti 4+, Zr 4+, Nb 5+ and W 6+.
further, the mass percent of the coating layer in the positive electrode material is 0.01 ~ 40%, preferably, the mass percent of the coating layer in the positive electrode material is 0.05 ~ 10%.
the invention also provides a preparation method of the cathode material, wherein the preparation method is one of a coprecipitation coating method, a solid-phase coating method, a mechanical fusion coating method and an atomic layer deposition coating method.
Further, the co-precipitation coating method comprises the following steps:
(1) Dissolving soluble lithium salt, nickel salt, manganese salt, cobalt salt, complexing agent or other inorganic salt in a solvent to form a mixed solution;
(2) Adjusting the pH value of the mixed solution obtained in the step (1) to 6 ~ 8, then adding lithium manganate, and stirring and mixing to obtain a solid-liquid mixture;
(3) continuously adjusting the pH value of the solid-liquid mixture in the step (2) to 10 ~ 12, and continuously stirring and mixing to obtain a positive electrode material coated by the nickel-cobalt-manganese composite oxide;
(4) And (4) drying the positive electrode material obtained in the step (3), and calcining for 1 ~ 10h in air, oxygen or a mixed atmosphere of air and oxygen at 400 ~ 1000 ℃ to obtain the nickel cobalt lithium manganate coated lithium manganate positive electrode material of the lithium manganate lithium ion battery.
Preferably, the soluble lithium salt is one or more of lithium acetate, lithium nitrate, lithium hydroxide or lithium carbonate.
preferably, the soluble nickel salt is one or more of nickel acetate, nickel nitrate and nickel sulfate.
Preferably, the soluble cobalt salt is one or more of cobalt acetate, cobalt nitrate and nickel cobalt sulfate.
Preferably, the soluble manganese salt is one of manganese acetate, manganese nitrate and manganese sulfate.
preferably, the complexing agent is one or more of oxalic acid, lactic acid, citric acid, tartaric acid and ammonia water.
preferably, the other inorganic salt is one or more of a soluble magnesium salt, an aluminum salt, a titanium salt, and a zirconium salt.
preferably, the solvent is one or more of water, methanol, ethanol, isopropanol, ethylene glycol monomethyl ether, ethylene glycol, propylene glycol, and propylene glycol monomethyl ether.
Preferably, the chemical formula of the lithium manganate is Li (Me x Mn 2-x) O 4, wherein Me is one or more of Li, Ni, Co, Al and Mg.
further, the solid phase coating method comprises the following steps:
(1) sanding the polycrystalline secondary spherical lithium nickel cobalt manganese oxide ternary material until D50 is 50 ~ 100 nm;
(2) Mixing the ternary material obtained in the step (1) with a lithium manganate material according to a certain proportion;
(3) and (3) calcining the mixture obtained in the step (2) for 1 ~ 5h at 400 ~ 1000 ℃ in an air atmosphere or an oxygen atmosphere to obtain the ternary material-coated lithium manganate cathode material.
Further, the mechano-fusion coating method comprises the following steps:
(1) Sanding the polycrystalline secondary spherical lithium nickel cobalt manganese oxide ternary material until D50 is 50 ~ 100 nm;
(2) Mixing the ternary material obtained in the step (1) with a lithium manganate material according to a certain proportion;
(3) And (3) mechanically fusing the mixture obtained in the step (2) for 2 hours to obtain the lithium manganate positive electrode material coated by the ternary material.
Further, the atomic layer deposition coating method comprises the following steps:
(1) putting the lithium manganate anode material into a reaction chamber of atomic layer deposition equipment filled with dry air in advance, raising the temperature of the reaction chamber, and keeping the temperature of the reaction chamber within a specified range;
(2) introducing a coating material source X into the reaction chamber, reacting within a first specified time, and introducing inert gas into the reaction chamber for cleaning so as to take away excess coating material source X in the reaction chamber; the coating material source X is one of chlorides or organic compounds of Li, Ni, Co and Mn;
(3) introducing a coating material source Y into the reaction chamber, reacting within a second designated time, and introducing inert gas into the reaction chamber for cleaning so as to take away excess coating material source Y and byproducts in the reaction chamber; the coating material source Y is one of oxygen and water;
(4) And (4) repeating the steps (2) - (3) and the step 10 ~ 20 for 20 times to obtain the lithium manganate positive electrode material coated by the ternary material.
The invention also provides a lithium ion battery using the cathode material.
on the basis of the positive electrode material, a positive electrode sheet can be prepared according to the technology known in the field, and a negative electrode sheet, a diaphragm and electrolyte known in the field are selected to assemble different types of lithium ion batteries (such as power-on and the like).
compared with the prior art, the invention has the beneficial effects that: the lithium manganate anode material coated by the nickel cobalt lithium manganate ternary material realizes complete coating, and reduces the side reaction of the lithium manganate anode material and electrolyte, thereby greatly improving the cycle performance, especially high-temperature cycle; and secondly, the ternary material can be used as an active material and has good lithium ion conductivity, so that the interface impedance cannot be increased by introducing the coating material, and the specific capacity of the positive electrode material can be improved and maintained.
Drawings
FIG. 1 XRD patterns of lithium manganate obtained in examples 1, 2, 3 and 5 and comparative example 1;
FIG. 2 is a scanning electron micrograph of lithium manganate produced in example 1;
FIG. 3 is a scanning electron micrograph of lithium manganate produced in example 5;
table 1 chemical composition and electrochemical properties of lithium manganate obtained in each example and comparative example.
Detailed Description
in order to make the objects, technical solutions and process advantages of the present invention more apparent, the present invention will be described in detail with reference to the following examples and accompanying drawings, wherein the technical terms used in the following examples have the same meanings as those commonly understood by those skilled in the art to which the present invention pertains, unless otherwise specified, the test reagents used in the following examples are conventional biochemical reagents, and the test reagents used in the following examples and comparative examples are conventional biochemical reagents, unless otherwise specified, and the materials of pure lithium manganate (LiMn 2 O 4) and doped lithium manganate Li (Me x Mn 2-x) O 4 (wherein Me is one or more of Li +, Co 3+, Al 3+, Ti 4+, Sc 3+) in the following examples and comparative examples are prepared by solid phase synthesis, comprising the following steps:
(1) Mixing Li 2 CO 3, EMD and a compound of a doping element according to a specific proportion, and mechanically ball-milling for 30 minutes;
(2) and (2) sintering the mixture obtained in the step (1) at 500 ℃ for 10 hours, cooling to room temperature, continuing ball milling for 30 minutes, and sintering at 750 ℃ for 24 hours to obtain the final lithium manganate cathode material LiMn 2 O 4 or Li (Me x Mn 2-x) O 4.
example 1
the cathode material provided by this embodiment is a LiMn 2 O 4 lithium manganate material coated with a ternary material Li 0.80 [ Ni 0.59 Co 0.20 Mn 0.20 Al 0.01 ] 1.20 O 2, wherein the mass percentage of the ternary material is 0.1 wt%.
the preparation method of the cathode material comprises the following steps:
(1) Respectively weighing lithium acetate, nickel acetate, cobalt acetate, manganese acetate, aluminum acetate and citric acid with certain mass, adding into 400mL of water, stirring to dissolve to form a lithium nickel cobalt manganese aluminum mixed solution, and adjusting the pH =7.8 of the solution;
(2) Adding 250g of LiMn 2 O 4 powder, and uniformly stirring;
(3) adjusting the pH of the solution to be =11.8, and further stirring and mixing uniformly;
(4) And drying the mixed solution, and roasting for 10 hours at 600 ℃ in an oxygen atmosphere to obtain the lithium manganate anode material coated by the ternary material.
the lithium ion battery of the embodiment is prepared by mixing the lithium manganate positive electrode material coated by the ternary material, a binder polyvinylidene fluoride PVDF, a conductive agent carbon black Super, P and Li according to a weight ratio of 94:3:3, and taking N-methyl pyrrolidone as a solvent, preparing positive electrode slurry, coating the positive electrode slurry on a battery-grade aluminum foil by adopting a scraper technology, drying for 16H in a 120 ℃ vacuum oven, punching into a positive electrode sheet with a diameter of 12mm by using a punching machine, heating for 24H under a vacuum condition of 100 ℃, assembling in an MB200 glove box of MBraun (Ar atmosphere, H 2 O and O 2 concentration is less than 0.1 ppm), and performing primary cycle efficiency and discharge capacity rate of the positive electrode sheet, a metal lithium electrode (ϕ 16 mm) and self-prepared electrolyte (the volume ratio of 1M LiPF 6 is 1:1 ethylene carbonate and dimethyl carbonate solution) to obtain a CR2025 battery, wherein the primary cycle efficiency and discharge capacity rate of the battery are 10 mA/g, and the normal temperature cycle is performed under a multiplying power of 100mA/g (25 ℃ C), and the high temperature cycle rate is also performed under a high temperature cycle rate of 55 ℃ under 100 mA/g.
example 2
The cathode material provided by this embodiment is a Li (Li 0.18 Co 0.02 Mn 1.80) O 4 lithium manganate material coated with a ternary material Li 1.02 (Ni 0.34 Co 0.30 Mn 0.33 Mg 0.03) 0.98 O 2, wherein the mass percentage of the ternary material is 1.0 wt%.
The preparation method of the cathode material comprises the following steps:
(1) respectively weighing a certain amount of lithium nitrate, nickel sulfate, cobalt sulfate, manganese sulfate, magnesium sulfate and tartaric acid, adding the lithium nitrate, nickel sulfate, cobalt sulfate, manganese sulfate, magnesium sulfate and tartaric acid into 500mL of water/glycol solution (volume ratio of 1/1), stirring to dissolve the mixture to form a lithium-nickel-cobalt-manganese-magnesium mixed solution, and adjusting the pH of the solution to be = 6.5;
(2) Adding 250g of Li (Li 0.18 Co 0.02 Mn 1.80) O 4 powder, and uniformly stirring;
(3) Adjusting the pH of the solution to be =10.2, and further stirring and mixing uniformly;
(4) and drying the mixed solution, and roasting for 5 hours at 800 ℃ in an oxygen atmosphere to obtain the lithium manganate positive electrode material coated by the ternary material.
the lithium ion battery of this example was prepared by using the positive electrode material of this example and referring to example 1.
Example 3
The cathode material provided by this embodiment is a Li (Li 0.10 Ni 0.02 Mn 1.88) O 4 lithium manganate material coated with a ternary material Li 1.08 (Ni 0.40 Co 0.18 Mn 0.40 Ti 0.02) 0.92 O 2, wherein the mass percentage of the ternary material is 5.0 wt%.
The preparation method of the cathode material comprises the following steps:
(1) Respectively weighing a certain amount of lithium hydroxide, nickel nitrate, cobalt nitrate, manganese nitrate, titanyl sulfate and tartaric acid, adding into 500mL of water and propylene glycol solution (volume ratio of 1/1), stirring to dissolve to form a lithium-nickel-cobalt-manganese-titanium mixed solution, and adjusting the pH of the solution to be = 6.5;
(2) Adding 250g of Li (Li 0.10 Ni 0.02 Mn 1.88) O 4 powder, and uniformly stirring;
(3) Adjusting the pH of the solution to be =11.2, and further stirring and mixing uniformly;
(4) And drying the mixed solution, and roasting for 5 hours at 900 ℃ in an air atmosphere to obtain the lithium manganate cathode material coated by the ternary material.
the lithium ion battery of this example was prepared by using the positive electrode material of this example and referring to example 1.
Example 4
The cathode material provided by this embodiment is a Li [ Li 0.05 Cr 0.05 Mn 1.90 ] O 4 lithium manganate material coated by a Li 1.12 (Ni 0.33 Co 0.30 Mn 0.33 W 0.04) 0.88 ternary material, wherein the mass percentage of the ternary material is 10.0 wt%.
The preparation method of the cathode material comprises the following steps:
(1) respectively weighing a certain mass of lithium acetate, nickel nitrate, cobalt nitrate, manganese nitrate, ammonium tungstate and ammonia water, adding the weighed materials into 500mL of water/ethylene glycol monomethyl ether solution (volume ratio of 1/1), stirring to dissolve the materials to form a lithium-nickel-cobalt-manganese-tungsten mixed solution, and adjusting the pH of the mixed solution to be = 6.5;
(2) Adding 250g of Li (Li 0.10 Ni 0.02 Mn 1.88) O 4 powder, and uniformly stirring;
(3) adjusting the pH of the solution to be 12.1, and further stirring and mixing uniformly;
(4) and drying the mixed solution, and roasting for 2 hours at 1000 ℃ in an air atmosphere to obtain the lithium manganate positive electrode material coated by the ternary material.
The lithium ion battery of this example was prepared by using the positive electrode material of this example and referring to example 1.
Example 5
The cathode material provided by this embodiment is a Li (Li 0.05 Mn 1.95) O 4 lithium manganate material coated with a ternary material Li 1.20 (Ni 0.50 Co 0.22 Mn 0.25 Zn 0.03) 0.80 O 2, wherein the mass percentage of the ternary material is 40.0 wt%.
The preparation method of the cathode material comprises the following steps:
(1) respectively weighing a certain mass of lithium acetate, nickel sulfate, cobalt sulfate, manganese sulfate, zinc acetate and ammonia water, adding the weighed materials into 500mL of water and a methanol solution (with a volume ratio of 1/1), stirring to dissolve the materials to form a lithium nickel cobalt manganese zinc mixed solution, and adjusting the pH of the solution to be = 7.6;
(2) Adding 250g of Li (Li 0.05 Mn 1.95) O 4 powder, and uniformly stirring;
(3) Adjusting the pH of the solution to be =11.1, and further stirring and mixing uniformly;
(4) and drying the mixed solution, and roasting for 3 hours at 700 ℃ in an oxygen atmosphere to obtain the lithium manganate positive electrode material coated by the ternary material.
the lithium ion battery of this example was prepared by using the positive electrode material of this example and referring to example 1.
Example 6
The cathode material provided by this embodiment is a Li (Li 0.18 Al 0.02 Mn 1.80) O 4 lithium manganate material solid-phase-coated with a Li 1.15 (Ni 0.333 Co 0.333 Mn 0.334) 0.85 O 2 ternary material, wherein the mass percentage of the ternary material is 2.0 wt%.
The preparation method of the cathode material comprises the following steps:
(1) Weighing a certain mass of Li 1.15 (Ni 0.333 Co 0.333 Mn 0.334) 0.85 O 2 ternary material, and sanding until D50 is 50 ~ 100 nm;
(2) mixing a proper amount of Li (Li 0.05 Mn 1.95) O 4 powder with a nano-grade Li 1.15 (Ni 0.333 Co 0.333 Mn 0.334) 0.85 O 2 ternary material, and uniformly stirring;
(3) And roasting the mixed material for 2 hours at 900 ℃ in an oxygen atmosphere to obtain the lithium manganate positive electrode material coated by the ternary material.
the lithium ion battery of this example was prepared by using the positive electrode material of this example and referring to example 1.
example 7
The cathode material provided by the embodiment is a Li (Li 0.18 Sc 0.02 Mn 1.80) O 4 lithium manganate material mechanically fused and coated by a Li 1.01 (Ni 0.88 Co 0.04 Mn 0.06 Zr 0.02) 0.99 O 2 ternary material, wherein the mass percent of the ternary material is 15.0 wt%.
The preparation method of the cathode material comprises the following steps:
(1) Sanding a polycrystalline secondary spherical nickel-cobalt-manganese ternary material Li 1.01 (Ni 0.88 Co 0.04 Mn 0.06 Zr 0.02) 0.99 O 2 to D50 about 50 nm;
(2) Mixing the ternary material obtained in the step (1) with a lithium manganate material according to a certain proportion;
(3) And (3) mechanically fusing the mixture obtained in the step (2) for 2 hours to obtain the lithium manganate positive electrode material coated by the ternary material.
The lithium ion battery of this example was prepared by using the positive electrode material of this example and referring to example 1.
Example 8
The cathode material provided by this embodiment is a Li (Li 0.18 Al 0.02 Mn 1.80) O 4 lithium manganate material coated by atomic layer deposition of a Li 1.08 (Ni 0.50 Co 0.20 Mn 0.30) 0.92 O 2 ternary material, wherein the mass percentage of the ternary material is 0.05 wt%.
The preparation method of the cathode material comprises the following steps:
(1) putting Li (Li 0.18 Al 0.02 Mn 1.80) O 4 lithium manganate cathode material into a reaction chamber of an atomic layer deposition device filled with dry air in advance, raising the temperature of the reaction chamber, and keeping the temperature of the reaction chamber within a specified range of 400 +/-10 ℃;
(2) introducing a coating material source into the reaction chamber, reacting within a first specified time, and introducing inert gas into the reaction chamber for cleaning so as to take away excess coating material source LiCl in the reaction chamber;
(3) Introducing a coating substance source H 2 O into the reaction chamber, reacting within a second designated time, and introducing inert gas into the reaction chamber for cleaning so as to take away excess coating substance source H 2 O and byproducts in the reaction chamber;
(4) and (4) repeating the steps (2) to (3) to respectively coat the nickel, the cobalt and the manganese, and repeating the steps for 15 times to obtain the lithium manganate anode material coated by the ternary material.
The lithium ion battery of this example was prepared by using the positive electrode material of this example and referring to example 1.
Comparative example 1
The positive electrode material provided by the comparative example is an undoped uncoated LiMn 2 O 4 lithium manganate material.
the lithium ion battery of the comparative example was prepared by using the positive electrode material of the comparative example and referring to example 1.
Comparative example 2
The positive electrode material provided by the comparative example is an uncoated Li (Li 0.18 Co 0.02 Mn 1.80) O 4 lithium manganate material.
The lithium ion battery of the comparative example was prepared by using the positive electrode material of the comparative example and referring to example 1.
Comparative example 3
The positive electrode material provided by the comparative example is a Li 2 O 4 lithium manganate material coated with Li 2 O B 2 O 3, wherein the mass percent of Li 2 O B 2 O 3 is 0.2 wt%.
The preparation method of the cathode material comprises the following steps:
(1) Respectively weighing a certain mass of lithium acetate and boric acid, adding the lithium acetate and boric acid into 50mL of methanol solution, and stirring to dissolve the lithium acetate and boric acid to form methanol solution of lithium acetate and boric acid;
(2) Adding 250g of LiMn 2 O 4 powder, and uniformly stirring;
(3) and drying the mixed solution, and roasting for 3 hours at 500 ℃ in an air atmosphere to obtain the Li 2 O B 2 O 3 -coated LiMn 2 O 4 lithium manganate cathode material.
The lithium ion battery of the comparative example was prepared by using the positive electrode material of the comparative example and referring to example 1.
comparative example 4
The positive electrode material provided by the comparative example is a Li (Li 0.18 Co 0.02 Mn 1.80) O 4 lithium manganate material coated with Li 2 O B 2 O 3, wherein the mass percent of Li 2 O B 2 O 3 is 5.0 wt%.
The preparation method of the cathode material comprises the following steps:
(1) respectively weighing a certain mass of lithium hydroxide and boric acid, adding the lithium hydroxide and boric acid into 50mL of methanol and ethylene glycol methyl ether (volume ratio is 1: 1) solution, and stirring to dissolve the lithium hydroxide and boric acid to form a solution of lithium hydroxide and boric acid;
(2) Adding 250g of Li (Li 0.18 Co 0.02 Mn 1.80) O 4 powder, and uniformly stirring;
(3) and drying the mixed solution, and roasting for 3 hours at 500 ℃ in an air atmosphere to obtain the Li (Li 0.18 Co 0.02 Mn 1.80) O 4 lithium manganate positive electrode material coated with Li 2 O B 2 O 3.
The lithium ion battery of the comparative example was prepared by using the positive electrode material of the comparative example and referring to example 1.
comparative example 5
The positive electrode material provided in this embodiment is a lithium iron phosphate solid-phase coated LiMn 2 O 4 lithium manganate material, wherein the mass percentage of lithium iron phosphate is 10 wt%.
the preparation method of the cathode material comprises the following steps:
(1) weighing a certain mass of LiFePO 4 material, and sanding until the D50 is about 50 nm;
(2) Mixing nano lithium iron phosphate powder and LiMn 2 O 4 lithium manganate according to a certain proportion, and uniformly stirring;
(3) And roasting the mixed material for 2 hours at 700 ℃ in a nitrogen atmosphere to obtain a lithium manganate positive electrode material coated by 10wt% LiFePO 4.
The lithium ion battery of this comparative example was prepared by using the positive electrode material of this example and referring to example 1.
the various parameters of the above embodiments, such as various roasting temperatures, roasting times, various mass or volume ratios, various solution stirring times, drying temperatures, etc., are only used for illustration and explanation, and the scheme of the present invention is not limited to the above values, and is not limited to the combination of the above values, and the scope of the present invention is only within the scope of the parameters described in the claims.
FIG. 1 shows XRD patterns obtained in examples 1, 2, 3 and 5 and comparative example 1. comparative example 1 is undoped and coated LiMn 2 O 4, and the XRD pattern is a typical spinel structure. in the lithium manganate coated with ternary materials of examples 1, 2, 3 and 5, as can be seen from FIG. 1, the coated lithium manganate maintains the spinel structure, diffraction peaks of the ternary materials appear as the coating amount increases, and the diffraction peaks of the ternary materials are stronger as the coating amount is larger, which indicates that the ternary materials are uniformly coated on the surface of the lithium manganate.
Fig. 2 and fig. 3 are scanning electron micrographs of lithium manganate obtained in example 1 and example 5, respectively, and it can be seen from the graphs that the coating amount of the ternary material in example 5 is 40%, the particle morphology is relatively consistent, the ternary material is basically formed by agglomeration of polycrystalline particles, and the particles are larger than those in example 1, which indicates that the ternary material completely and completely coats the lithium manganate material, so that the particle size of the ternary material is increased.
table 1 shows the chemical composition and electrochemical performance information of the lithium manganate obtained in each example and comparative example, as can be seen from the table, the first coulombic efficiency of the lithium manganate obtained in example 1 ~ 8 is 97.1% at least and 99.5% at most, the capacity retention rate after 100 cycles at room temperature is 96.7% at most and 99.5% at most, the capacity retention rate after 100 cycles at high temperature is 94.1% at most and 97.2% at most, in the comparative example, the lithium manganate coated with 5.0wt% of LiO 2 B 2 O 3 has the best performance, the first coulombic efficiency is 98.4% at most, the capacity retention rate after 100 cycles at room temperature is 96.1% at most and the capacity retention rate after 100 cycles at high temperature is 92.1% at most, which are not the lithium manganate material obtained in the present invention, especially the high temperature cycle performance.
TABLE 1 chemical composition and electrochemical performance information of lithium manganate obtained in each example and comparative example
Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention.
Claims (10)
1. the utility model provides a positive electrode material, includes the coating that contains and/or does not contain doping element's lithium manganate and cladding at the lithium manganate surface which characterized in that: the coating layer is made of nickel cobalt lithium manganate ternary material containing or not containing doping elements.
2. the positive electrode material according to claim 1, wherein the chemical formula of lithium manganate is one or more of Li (Me x Mn x) O x, where x is 0. ltoreq. x.ltoreq.0.2, Me is Li x, Co x, Ni x, Zn x, Mg x, Al x, Cr x, Sc x, Ga x, Ti x, and Zr x, and the chemical formula of the nickel cobalt manganese ternary material is Li x (Ni x Co x Mn x B x) x O x, where-0.2. ltoreq. y.ltoreq.0.2, 0. ltoreq. z.ltoreq.0.1, 0< a <1, 0< B <1, 0< a + B + z <1, and B is Zn x, Mg x, Zn x, Al x, Sc x, Ga x, La x, Ti x, Zr x, Cr x, Nb x, W x, and W x.
3. the positive electrode material according to claim 1, wherein the coating layer accounts for 0.01 ~ 40% by mass of the positive electrode material, and preferably 0.05 ~ 10% by mass of the positive electrode material.
4. A method for preparing the positive electrode material of claim 1, characterized in that: the method is one of a coprecipitation coating method, a solid phase coating method, a mechanical fusion coating method and an atomic layer deposition coating method.
5. the method of claim 4, wherein: the coprecipitation coating method comprises the following steps:
(1) dissolving soluble lithium salt, nickel salt, manganese salt, cobalt salt, complexing agent or other doped salt in a solvent to form a mixed solution;
(2) Adjusting the pH value of the mixed solution obtained in the step (1) to 6.0-8.0, then adding lithium manganate, and stirring and mixing to obtain a solid-liquid mixture;
(3) continuously adjusting the pH value of the solid-liquid mixture in the step (2) to 10.0-12.0, and continuously stirring and mixing to obtain a positive electrode material coated by the nickel-cobalt-manganese composite oxide;
(4) and (4) drying the positive electrode material obtained in the step (3), and calcining for 1 ~ 10h in air, oxygen or a mixed atmosphere of air and oxygen at 400 ~ 1000 ℃ to obtain the nickel cobalt lithium manganate coated lithium manganate battery positive electrode material.
6. the method according to claim 5, wherein the soluble lithium salt is one or more of lithium acetate, lithium nitrate, lithium hydroxide or lithium carbonate, the soluble nickel salt is one or more of nickel acetate, nickel nitrate and nickel sulfate, the soluble cobalt salt is one or more of cobalt acetate, cobalt nitrate and nickel cobalt sulfate, the soluble manganese salt is one or more of manganese acetate, manganese nitrate and manganese sulfate, the complexing agent is one or more of oxalic acid, lactic acid, citric acid, tartaric acid and ammonia water, the other inorganic salt is one or more of soluble magnesium salt, aluminum salt, titanium salt and zirconium salt, the solvent is one or more of water, methanol, ethanol, isopropanol, ethylene glycol monomethyl ether, ethylene glycol, propylene glycol monomethyl ether and propylene glycol monomethyl ether, the chemical formula of the lithium manganate is Li (Me x Mn 2-x) O 4, wherein Me is one or more of Li +, Co 3+, Al 3+, Ti 4+ and Sc 3+.
7. The method of claim 4, wherein: the solid phase coating method comprises the following steps:
(1) Sanding the polycrystalline secondary spherical lithium nickel cobalt manganese oxide ternary material until D50 is 50 ~ 100 nm;
(2) Mixing the ternary material obtained in the step (1) with a lithium manganate material according to a certain proportion;
(3) And (3) calcining the mixture obtained in the step (2) for 1 ~ 10h at 400 ~ 1000 ℃ in an air atmosphere or an oxygen atmosphere to obtain the ternary material-coated lithium manganate cathode material.
8. the method of claim 4, wherein: the mechano-fusion coating method comprises the following steps:
(1) Sanding the polycrystalline secondary spherical lithium nickel cobalt manganese oxide ternary material until D50 is 50 ~ 100 nm;
(2) mixing the ternary material obtained in the step (1) with a lithium manganate material according to a certain proportion;
(3) And (3) mechanically fusing the mixture obtained in the step (2) for 2 hours to obtain the lithium manganate positive electrode material coated by the ternary material.
9. The method of claim 4, wherein: the atomic layer deposition coating method comprises the following steps:
(1) Putting the lithium manganate anode material into a reaction chamber of atomic layer deposition equipment filled with dry air in advance, raising the temperature of the reaction chamber, and keeping the temperature of the reaction chamber within a specified range;
(2) Introducing a coating material source X into the reaction chamber, reacting within a first specified time, and introducing inert gas into the reaction chamber for cleaning so as to take away excess coating material source X in the reaction chamber; preferably, the coating material source X is one of organic compounds and chlorides of Li, Ni, Co and Mn;
(3) Introducing a coating material source Y into the reaction chamber, reacting within a second designated time, and introducing inert gas into the reaction chamber for cleaning so as to take away excess coating material source Y and byproducts in the reaction chamber; preferably, the coating substance source Y is one of oxygen and water;
(4) and (4) repeating the steps (2) to (3) for 10 ~ 20 times to obtain the lithium manganate positive electrode material coated with the nickel cobalt lithium manganate layer, so as to realize coating modification of the lithium manganate positive electrode material.
10. A lithium ion battery using the positive electrode material according to any one of claims 1 to 3.
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