CN114300673A - Lithium ion positive electrode composite material and preparation method thereof - Google Patents
Lithium ion positive electrode composite material and preparation method thereof Download PDFInfo
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- CN114300673A CN114300673A CN202111534714.7A CN202111534714A CN114300673A CN 114300673 A CN114300673 A CN 114300673A CN 202111534714 A CN202111534714 A CN 202111534714A CN 114300673 A CN114300673 A CN 114300673A
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- 239000002131 composite material Substances 0.000 title claims abstract description 59
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims description 46
- 238000005245 sintering Methods 0.000 claims description 32
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 27
- 229910052744 lithium Inorganic materials 0.000 claims description 27
- 239000011572 manganese Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 claims description 17
- ZWEKKXQMUMQWRN-UHFFFAOYSA-J manganese(2+);nickel(2+);dicarbonate Chemical compound [Mn+2].[Ni+2].[O-]C([O-])=O.[O-]C([O-])=O ZWEKKXQMUMQWRN-UHFFFAOYSA-J 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 14
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 14
- BLYYANNQIHKJMU-UHFFFAOYSA-N manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Ni++] BLYYANNQIHKJMU-UHFFFAOYSA-N 0.000 claims description 14
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 13
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 13
- 229910003002 lithium salt Inorganic materials 0.000 claims description 13
- 159000000002 lithium salts Chemical class 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 229910052596 spinel Inorganic materials 0.000 claims description 13
- 239000011029 spinel Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 11
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 10
- 239000001099 ammonium carbonate Substances 0.000 claims description 10
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 10
- 239000010406 cathode material Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000012716 precipitator Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 5
- 230000004927 fusion Effects 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000003746 solid phase reaction Methods 0.000 claims description 3
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000843 powder Substances 0.000 description 23
- 238000005303 weighing Methods 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- 239000007774 positive electrode material Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 7
- 238000000137 annealing Methods 0.000 description 6
- 238000005056 compaction Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- 229910001429 cobalt ion Inorganic materials 0.000 description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 3
- 229940044175 cobalt sulfate Drugs 0.000 description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000010344 co-firing Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 238000009766 low-temperature sintering Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of batteries, and particularly relates to a lithium ion anode composite material, wherein the expression of the anode composite material is xLiCoO2·(1‑x)LiNi0.5Mn1.5O4Wherein x is more than or equal to 0.5 and less than 1. The invention has the advantages of high cycle performance under high voltage and low production cost of the battery. In addition, the invention discloses a preparation method of the lithium ion anode composite material.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a lithium ion anode composite material and a preparation method thereof.
Background
Nowadays, in a lithium ion battery, the cost of a positive electrode material accounts for about 40% of the total battery, the specific capacity of the positive electrode material is improved by 50%, the specific capacity of the battery is increased by 28%, the specific capacity of a negative electrode material is improved by 50%, and the specific capacity of the battery is increased by only 13%. Therefore, reducing the cost of the cathode material is particularly important for the development of lithium ion batteries.
The lithium cobaltate positive electrode material has the advantages of high working voltage, high energy density, good cycling stability and the like, and is an irreplaceable positive electrode material in current consumer battery products. However, because of the scarcity of cobalt ore resources in China, the mineral soil sources depend on foreign imports, and the cost of lithium cobaltate is high.
In order to reduce the cost, cobalt-free and cobalt-less materials such as lithium manganate and ternary materials are tried to be used for consumer batteries, but finally, the materials are only used for products below 4.4V because the voltage window and the cycle life of the materials cannot be considered. In recent years, a ternary blend lithium cobaltate material with less cobalt is used for a 4.4V system, and has high gram capacity, high-temperature cycle and low cost. The ternary blended lithium cobaltate material has two preparation modes, wherein the first mode is as follows: the lithium cobaltate and the ternary finished product are physically mixed, the composite material prepared by the method is low in compaction density, and the risk of uneven mixing exists; and the second method comprises the following steps: the ternary precursor, the lithium cobaltate precursor and the lithium salt are uniformly mixed and then are co-fired for preparation, and the lithium cobaltate/ternary composite material generated by the method is high in compaction and good in product uniformity. However, the ternary material has a low discharge platform and obvious high-voltage cycle deterioration, and when the ternary blended lithium cobalt oxide material is used for a system with the voltage of 4.45V or above, the energy density has no obvious advantage and the cycle deterioration is caused.
Disclosure of Invention
One of the objects of the present invention is: aiming at the defects of the prior art, the lithium ion anode composite material is provided, the cycle performance under high voltage is considered, and the production cost of the battery is reduced.
In order to achieve the purpose, the invention adopts the following technical scheme:
lithium ion anode composite material and packageThe expression including the positive electrode composite material is xLiCoO2·(1-x)LiNi0.5Mn1.5O4Wherein x is more than or equal to 0.5 and less than 1.
The second purpose of the invention is to provide a preparation method of a lithium ion positive electrode composite material, which comprises the following steps:
preparing a Co solution by using soluble salt of cobalt, stirring and aging by using carbonate as a precipitator to obtain a cobalt carbonate precipitate, then carrying out solid-liquid separation on the obtained cobalt carbonate, washing by using deionized water, drying, and sintering at a low temperature to obtain a cobaltosic oxide precursor;
preparing soluble salts of Ni and Mn into a metal mixed solution, stirring and aging by using carbonate as a precipitator to obtain nickel-manganese carbonate precipitate, carrying out solid-liquid separation on the obtained nickel-manganese carbonate, washing by using deionized water, drying, and sintering at a low temperature to obtain a nickel-manganese oxide precursor;
step three, uniformly mixing the precursors prepared in the step one and the step two with lithium salt, sintering at high temperature, and carrying out high-temperature solid-phase reaction to prepare the composite cathode material xLiCoO formed by fusion growth of layered lithium cobaltate and spinel lithium nickel manganese oxide2·(1-x)LiNi0.5Mn1.5O4。
Preferably, the precipitant is one of ammonium carbonate, sodium carbonate, lithium carbonate and potassium carbonate.
Preferably, the lithium salt is one of lithium carbonate, lithium acetate and lithium hydroxide.
Preferably, the sintering temperature of the cobaltosic oxide precursor and the sintering temperature of the nickel manganese oxide precursor are both greater than 400 ℃, and the sintering temperature of the composite cathode material is greater than 800 ℃.
Preferably, the molar ratio of the cobaltosic oxide precursor to the nickel manganese oxide precursor is 0.1-1.5.
Preferably, the ion concentration of the Co solution is 1-2 mol/L, and the ion concentration of the metal mixed solution is 1-2 mol/L.
Preferably, the molar ratio of Ni/Mn is 1: 3, preparing a metal mixed solution.
Preferably, a suction filtration mode is adopted, so that the cobalt carbonate or the nickel manganese carbonate is subjected to solid-liquid separation.
Preferably, the cobaltosic oxide precursor or the nickel-manganese oxide precursor is obtained by low-temperature sintering in a muffle furnace.
The invention has the beneficial effects that:
the invention adopts a precursor co-firing mode to prepare the composite anode material xLiCoO2·(1-x)LiNi0.5Mn1.5O4And x is more than or equal to 0.5 and less than 1, the composite material is formed by melting lithium cobaltate and spinel lithium nickel manganese oxide at high temperature, and compared with a simple blending material, the composite material has the advantages of low production cost and good product consistency.
The composite positive electrode material takes lithium cobaltate as a main framework, and has high compaction density; the lithium nickel manganese oxide with a spinel structure has a three-dimensional lithium ion diffusion channel and can improve low-temperature discharge.
The composite cathode material realizes low cost by a cobalt reduction mode, and the material main body is lithium cobaltate which can give consideration to the cycling stability under high voltage.
Drawings
Features, advantages and technical effects of exemplary embodiments of the present invention will be described below with reference to the accompanying drawings.
FIG. 1 is an SEM image of a material of the present invention.
Detailed Description
As used in the specification and in the claims, certain terms are used to refer to particular components. As one skilled in the art will appreciate, manufacturers may refer to a component by different names. This specification and claims do not intend to distinguish between components that differ in name but not function. In the following description and in the claims, the terms "include" and "comprise" are used in an open-ended fashion, and thus should be interpreted to mean "include, but not limited to. "substantially" means within an acceptable error range, and a person skilled in the art can solve the technical problem within a certain error range to substantially achieve the technical effect.
Furthermore, the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the present invention, unless otherwise expressly specified or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
The present invention will be described in further detail with reference to fig. 1, but the present invention is not limited thereto.
The expression of the positive electrode composite material is xLiCoO2·(1-x)LiNi0.5Mn1.5O4Wherein x is more than or equal to 0.5 and less than 1. The low cost is realized by less cobalt, the low cost is realized, the main body of the material is lithium cobaltate, and the cycling stability under high voltage can be considered.
The preparation method of the lithium ion positive electrode composite material comprises the following steps: preparing a Co solution by using soluble salt of cobalt, stirring and aging by using carbonate as a precipitator to obtain a cobalt carbonate precipitate, then carrying out solid-liquid separation on the obtained cobalt carbonate, washing by using deionized water, drying, and sintering at a low temperature to obtain a cobaltosic oxide precursor; preparing soluble salts of Ni and Mn into a metal mixed solution, stirring and aging by using carbonate as a precipitator to obtain nickel-manganese carbonate precipitate, carrying out solid-liquid separation on the obtained nickel-manganese carbonate, washing by using deionized water, drying, and sintering at a low temperature to obtain a nickel-manganese oxide precursor; step three, uniformly mixing the precursors prepared in the step one and the step two with lithium salt, sintering at high temperature, and carrying out high-temperature solid-phase reaction to prepare the composite cathode material xLiCoO formed by fusion growth of layered lithium cobaltate and spinel lithium nickel manganese oxide2·(1-x)LiNi0.5Mn1.5O4。
In addition, a precursor is usedPreparation of composite anode material xLiCoO by co-firing method2·(1-x)LiNi0.5Mn1.5O4X is more than or equal to 0.5 and less than 1, the composite material is formed by melting lithium cobaltate and spinel lithium nickel manganese oxide at high temperature, compared with a simple blending material, the composite anode material is low in production cost and good in product consistency, the lithium cobaltate is used as a main framework of the composite anode material, and the compaction density is high; the lithium nickel manganese oxide with a spinel structure has a three-dimensional lithium ion diffusion channel and can improve low-temperature discharge, wherein the lithium cobalt oxide and the lithium nickel manganese oxide are generated by melting through a composite material, and are relatively simple and physically mixed to be more homogeneous, so that the consistency of products is improved.
In the preparation method of the lithium ion cathode composite material, the soluble cobalt salt, the soluble nickel salt and the soluble manganese salt are one or more of acetate, nitrate, sulfate and chloride.
In the preparation method of the lithium ion positive electrode composite material, the precipitator is one of ammonium carbonate, sodium carbonate, lithium carbonate and potassium carbonate.
In the preparation method of the lithium ion positive electrode composite material, the lithium salt is one of lithium carbonate, lithium acetate and lithium hydroxide.
In the preparation method of the lithium ion cathode composite material, the sintering temperature of the cobaltosic oxide precursor or the nickel-manganese oxide precursor is higher than 400 ℃, and the sintering temperature of the composite cathode material is higher than 800 ℃.
According to the preparation method of the lithium ion cathode composite material, the molar ratio of the cobaltosic oxide precursor to the nickel-manganese oxide precursor is 0.1-1.5 according to the given precursor molecular formula and the given composite material proportion range.
In the preparation method of the lithium ion cathode composite material, the proportion of Li/Me (Me-Co +2Ni) is 1.05-1.2
In the preparation method of the lithium ion cathode composite material, the ion concentration of the Co solution is 1-2 mol/L, and the ion concentration of the metal mixed solution is 1-2 mol/L.
In the preparation method of the lithium ion cathode composite material according to the invention, the ratio of Ni/Mn in a molar ratio of 1: 3, preparing a metal mixed solution.
In the preparation method of the lithium ion cathode composite material, a suction filtration mode is adopted to separate the cobalt carbonate or the nickel manganese carbonate into solid and liquid. Filtering to quickly filter, and washing out surface impurity elements with deionized water.
In the preparation method of the lithium ion cathode composite material, a muffle furnace is adopted for low-temperature sintering to obtain a cobaltosic oxide precursor or a nickel-manganese oxide precursor.
Example 1
Step one, cobaltosic oxide (Co)3O4) Precursor preparation
Preparing cobalt sulfate into a cobalt sulfate solution with the cobalt ion concentration of 2mol/L, preparing ammonium carbonate into an ammonium carbonate solution with the cobalt ion concentration of 0.5mol/L, adding an ammonium carbonate solution with the volume ratio of 5 times into the cobalt sulfate solution under the action of magnetic stirring, fully precipitating cobalt ions by using an excessive ammonium carbonate solution, stirring and aging for 2 hours to obtain a cobalt carbonate precipitate, filtering the cobalt carbonate precipitate by using a suction filtration device, washing the cobalt carbonate precipitate with deionized water until the pH value is 7.5, drying the cobalt carbonate precipitate for 12 hours by using an oven with the temperature of 80 ℃, and sintering the dried lithium carbonate in a muffle furnace at the temperature of 450 ℃ for 10 hours to fully decompose the cobalt carbonate to prepare a cobaltosic oxide precursor.
Step two, nickel manganese oxide (Mn)0.75Ni0.25O) precursor preparation
Nickel sulfate and manganese sulfate are mixed according to the molar ratio of Ni/Mn of 1: 3, preparing a mixed solution with metal ion concentration of 2mol/L, preparing ammonium carbonate into an ammonium carbonate solution with the concentration of 0.5mol/L, fully precipitating nickel ions and manganese ions by using excessive ammonium carbonate solution, stirring and aging for 2 hours to obtain nickel manganese carbonate precipitate (Mn)0.75Ni0.25CO3) Performing suction filtration on the obtained nickel manganese carbonate to separate solid from liquid, washing the nickel manganese carbonate with deionized water until the pH value is 7.5, drying the nickel manganese carbonate in an oven at 80 ℃ for 12h, and sintering the dried nickel manganese carbonate in a muffle furnace at 450 ℃ for 10h to fully decompose the nickel manganese carbonate to prepare the nickel manganese oxide (Mn)0.75Ni0.25O) a precursor.
Step three: preparation of composite cathode material
Weighing the 3mol Co prepared in the step one3O4Precursor, weighing 2mol of Mn prepared in the second step0.75Ni0.25Weighing 11mol of lithium carbonate (considering that lithium salt volatilizes in the sintering process, and Li/Me (Me ═ Co +2Ni) ═ 1.1) according to the O precursor, uniformly mixing the powder through a ball mill, transferring the powder into a muffle furnace, sintering the powder at the high temperature of 850 ℃ for 12h, and naturally annealing the powder to prepare 0.9LiCoO formed by fusing and growing layered lithium cobaltate and spinel lithium nickel manganese oxide2·0.1LiNi0.5Mn1.5O4And (3) compounding the positive electrode material.
Example 2
Unlike embodiment 1, in the third step of this embodiment,
weighing 8/3mol Co prepared in the first step3O4Precursor, weighing 4mol of Mn prepared in the second step0.75Ni0.25Weighing 11mol of lithium carbonate (considering that lithium salt volatilizes in the sintering process, and Li/Me (Me ═ Co +2Ni) ═ 1.1) according to the O precursor, uniformly mixing the powder through a ball mill, transferring the powder into a muffle furnace, sintering the powder at the high temperature of 850 ℃ for 12h, and naturally annealing the powder to prepare 0.8LiCoO formed by fusing and growing layered lithium cobaltate and spinel lithium nickel manganese oxide2·0.2LiNi0.5Mn1.5O4And (3) compounding the positive electrode material.
Example 3
Unlike embodiment 1, in the third step of this embodiment,
weighing 7/3mol Co prepared in the first step3O4Precursor, weighing 6mol Mn prepared in the second step0.75Ni0.25Weighing 11mol of lithium carbonate (considering that lithium salt volatilizes in the sintering process, and Li/Me (Me ═ Co +2Ni) ═ 1.1) according to the O precursor, uniformly mixing the powder through a ball mill, transferring the powder into a muffle furnace, sintering the powder at the high temperature of 850 ℃ for 12h, and naturally annealing the powder to prepare 0.7LiCoO formed by fusing and growing layered lithium cobaltate and spinel lithium nickel manganese oxide2·0.3LiNi0.5Mn1.5O4And (3) compounding the positive electrode material.
Example 4
Unlike embodiment 1, in the third step of this embodiment,
weighing 2mol of Co prepared in the step one3O4Precursor, weighing 8mol of Mn prepared in the second step0.75Ni0.25Weighing 11mol of lithium carbonate (considering that lithium salt volatilizes in the sintering process, and Li/Me (Me ═ Co +2Ni) ═ 1.1) according to the O precursor, uniformly mixing the powder through a ball mill, transferring the powder into a muffle furnace, sintering the powder at the high temperature of 850 ℃ for 12h, and naturally annealing the powder to prepare 0.6LiCoO formed by fusing and growing layered lithium cobaltate and spinel lithium nickel manganese oxide2·0.4LiNi0.5Mn1.5O4And (3) compounding the positive electrode material.
Example 5
Unlike embodiment 1, in the third step of this embodiment,
weighing 5/3mol Co prepared in the first step3O4Precursor, weighing 10mol Mn prepared in the second step0.75Ni0.25Weighing 11mol of lithium carbonate (considering that lithium salt volatilizes in the sintering process, and Li/Me (Me ═ Co +2Ni) ═ 1.1) according to the O precursor, uniformly mixing the powder through a ball mill, transferring the powder into a muffle furnace, sintering the powder at the high temperature of 850 ℃ for 12h, and naturally annealing the powder to prepare 0.5LiCoO formed by fusing and growing layered lithium cobaltate and spinel lithium nickel manganese oxide2·0.5LiNi0.5Mn1.5O4And (3) compounding the positive electrode material.
Comparative example 1
Unlike embodiment 1, in the third step of this embodiment,
weighing 2mol of Co prepared in the step one3O4Weighing 6.6mol of lithium carbonate (considering the volatilization of lithium salt in the sintering process, Li/Co is 1.1), uniformly mixing the powder materials by a ball mill, transferring the powder materials into a muffle furnace for sintering at 850 ℃ for 12h, and naturally annealing to prepare the layered lithium cobaltate LiCoO2。
The composite positive electrode materials xLiCoO prepared in examples 1 to 5 prepared above were used2·(1-x)LiNi0.5Mn1.5O4Lithium cobaltate prepared in comparative example 1 was assembled into lithium ion buttonThe battery is subjected to an electrical property test at room temperature, the charging and discharging conditions are 0.1C, and the charging and discharging range is 3.0V-4.5V. And low-temperature discharging is carried out at the temperature of minus 10 ℃, the charging and discharging conditions are 0.1C, and the charging and discharging range is 3.0V-4.5V. The results of the electrical properties are shown in Table 1, and the results of the electrical properties
According to the data shown in Table 1, the composite cathode material xLiCoO2·(1-x)LiNi0.5Mn1.5O4Low temperature discharge is superior to lithium cobaltate and with LiNi0.5Mn1.5O4The proportion is increased, and the low-temperature advantage is more obvious; the three-dimensional lithium ion diffusion channel provided by the spinel lithium nickel manganese oxide in the composite anode material is illustrated, the ion diffusion coefficient of the material is improved, and low-temperature discharge is facilitated. Compared with lithium cobaltate, the composite material has equivalent powder compaction and 25 ℃ circulation, and the composite positive electrode takes the lithium cobaltate as a main body and has good compaction density and circulation performance. Along with the increase of the proportion of the lithium nickel manganese oxide, the composite gram capacity is reduced, and mainly lithium ions which can be deintercalated from the lithium nickel manganese oxide are fewer than lithium cobaltate, so that the gram capacity exertion is influenced. In practical application, the proportion of the composite material needs to be reasonably designed according to the performance requirements of different systems.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. A lithium ion positive electrode composite material characterized in that: the expression of the positive electrode composite material is xLiCoO2·(1-x)LiNi0.5Mn1.5O4Which isIn the formula, x is more than or equal to 0.5 and less than 1.
2. A preparation method of a lithium ion positive electrode composite material is characterized by comprising the following steps:
preparing a Co solution by using soluble salt of cobalt, stirring and aging by using carbonate as a precipitator to obtain a cobalt carbonate precipitate, then carrying out solid-liquid separation on the obtained cobalt carbonate, washing by using deionized water, drying, and sintering at a low temperature to obtain a cobaltosic oxide precursor;
preparing soluble salts of Ni and Mn into a metal mixed solution, stirring and aging by using carbonate as a precipitator to obtain nickel-manganese carbonate precipitate, carrying out solid-liquid separation on the obtained nickel-manganese carbonate, washing by using deionized water, drying, and sintering at a low temperature to obtain a nickel-manganese oxide precursor;
step three, uniformly mixing the precursors prepared in the step one and the step two with lithium salt, sintering at high temperature, and carrying out high-temperature solid-phase reaction to prepare the composite cathode material xLiCoO formed by fusion growth of layered lithium cobaltate and spinel lithium nickel manganese oxide2·(1-x)LiNi0.5Mn1.5O4。
3. The method of preparing a lithium ion positive electrode composite material according to claim 2, wherein: the precipitator is one of ammonium carbonate, sodium carbonate, lithium carbonate and potassium carbonate.
4. The method of preparing a lithium ion positive electrode composite material according to claim 2, wherein: the lithium salt is one of lithium carbonate, lithium acetate and lithium hydroxide.
5. The method of preparing a lithium ion positive electrode composite material according to claim 2, wherein: the sintering temperature of the cobaltosic oxide precursor and the sintering temperature of the nickel manganese oxide precursor are both larger than 400 ℃, and the sintering temperature of the composite cathode material is larger than 800 ℃.
6. The method of preparing a lithium ion positive electrode composite material according to claim 2, wherein: the molar ratio of the cobaltosic oxide precursor to the nickel manganese oxide precursor is 0.1-1.5.
7. The method of preparing a lithium ion positive electrode composite material according to claim 2, wherein: the ion concentration of the Co solution is 1-2 mol/L, and the ion concentration of the metal mixed solution is 1-2 mol/L.
8. The method of preparing a lithium ion positive electrode composite material according to claim 2, wherein: according to the molar ratio of Ni to Mn of 1: 3, preparing a metal mixed solution.
9. The method of preparing a lithium ion positive electrode composite material according to claim 2, wherein: and (3) performing solid-liquid separation on the cobalt carbonate or the nickel-manganese carbonate by adopting a suction filtration mode.
10. The method of preparing a lithium ion positive electrode composite material according to claim 2, wherein: and sintering at low temperature by adopting a muffle furnace to obtain the cobaltosic oxide precursor or the nickel-manganese oxide precursor.
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