CN113178566A - Spinel type monocrystal cobalt-free high-voltage lithium nickel manganese oxide positive electrode material, preparation method thereof and lithium ion battery - Google Patents
Spinel type monocrystal cobalt-free high-voltage lithium nickel manganese oxide positive electrode material, preparation method thereof and lithium ion battery Download PDFInfo
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Abstract
The invention provides a preparation method of a spinel type monocrystal cobalt-free high-voltage lithium nickel manganese oxide positive electrode material, which comprises the following steps: A) adding a nickel source and a manganese source under the action of a precipitator, ammonia water and a complexing agent, and carrying out coprecipitation reaction to obtain Ni0.5Mn1.5(OH)4A binary precursor; B) adding the Ni0.5Mn1.5(OH)4Mixing the binary precursor with a lithium source, and calcining at high temperatureSintering, then annealing at low speed and preserving heat, and finally naturally cooling to obtain the single crystal LiNi0.5Mn1.5O4And (3) a positive electrode material. The material has the main appearance of combination of regular octahedrons and truncated octahedrons, so that the material has the advantages of low price, simple preparation process, high compaction density, excellent electrochemical performance and the like. The invention also provides a spinel type monocrystal cobalt-free high-voltage lithium nickel manganese oxide positive electrode material and a lithium ion battery.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a spinel type single crystal cobalt-free high-voltage lithium nickel manganese oxide positive electrode material, a preparation method thereof and a lithium ion battery.
Background
In recent years, with the rapid development of new energy industries, development of lithium ion battery materials having high capacity and high energy density has been attracting attention. With the rapid increase of new energy automobile sales in 2014, the power battery cell exceeds the 3C battery cell and the energy storage battery cell, and the automobile industry has become the largest market of the lithium ion battery so far.
At present, the lithium ion battery material which has been commercialized is mainly layered lithium cobaltate (LiCoO)2) Layered ternary materials (LiNi)xCoyMnzO2) Olivine-like lithium iron phosphate (LiFePO)4) And spinel-like lithium manganate (LiMn)2O4). The lithium cobaltate battery has high working voltage, large volume energy density and high price; the ternary material is a main material of the current power battery, gradually moves to the trend of high nickel, and has safety problem although the capacity is high; the lithium iron phosphate is low in price and good in circulation, but the volume energy density is low and the multiplying power is poor; the lithium manganate is cheap in price, but low in capacity, and more suitable for electric bicycles.
Based on spinel-type LiMn2O4The improvement and enhancement of the performance can keep the spinel LiMn in the material by proper element doping2O4On the basis of the advantages of basic frame structure and electrochemical performance, the de-intercalation/intercalation potential of lithium ions is changed to obtain a specific capacity (146.7mAh/g) and LiMn2O4Equivalent, but voltage plateau ratio LiMn2O4Spinel-type LiNi as 5V lithium ion anode material with over 15% of lithium ion concentration0.5Mn1.5O4(ii) a More importantly, this variation in elemental tuning fundamentally alters the overlap of the inner electron orbitals of the material andsurface property, greatly improving the cycle performance. The material has the advantages of low price, environment-friendly and cobalt-free raw materials, high energy density, excellent rate capability, good cycle performance and the like.
The preparation methods of spinel-type lithium nickel manganese oxide are more, and mainly include a high-temperature solid phase method, a coprecipitation method, a sol-gel method and the like. In the existing lithium nickel manganese oxide synthesis technology, two times of sintering (pre-oxidation and high temperature sintering) are mainly used in the synthesis process (CN201811621732.7), or additives and the like (CN201910642708.X) are required to be added, and the realization of large-scale mass production is difficult.
Disclosure of Invention
The invention aims to provide a spinel type monocrystal cobalt-free high-voltage lithium nickel manganese oxide positive electrode material, a preparation method thereof and a lithium ion battery.
The invention provides a preparation method of a spinel type monocrystal cobalt-free high-voltage lithium nickel manganese oxide positive electrode material, which comprises the following steps:
A) adding a nickel source and a manganese source under the action of a precipitator, ammonia water and a complexing agent, and carrying out coprecipitation reaction to obtain Ni0.5Mn1.5(OH)4A binary precursor;
B) adding the Ni0.5Mn1.5(OH)4Mixing the binary precursor with a lithium source, performing one-step high-temperature calcination, then performing low-speed annealing and heat preservation, and finally naturally cooling to obtain the single crystal LiNi0.5Mn1.5O4A positive electrode material;
the high-temperature calcination temperature is 850-1000 ℃, the heating rate is 2-5 ℃/min, and the high-temperature calcination time is 6-15 hours.
Preferably, the precipitant is an alkali hydroxide; the complexing agent is one or more of acetic acid, ammonium oxalate, glycine, ethylenediamine and pentaerythritol.
Preferably, the nickel source is one or more of nickel sulfate, nickel nitrate, nickel chloride, nickel acetate, nickel bromide and nickel sulfamate;
the manganese source is one or more of manganese sulfate, manganese nitrate, manganese chloride, manganese acetate and manganese perchlorate;
the molar ratio of Ni in the nickel source to Mn in the manganese source is 2.8-3.2.
Preferably, the temperature of the coprecipitation reaction is 40-60 ℃; the coprecipitation reaction is carried out under the stirring condition of the rotating speed of 300-800 rpm.
Preferably, the lithium source is one or more of lithium hydroxide, lithium carbonate and lithium acetate;
the ratio of the total amount of Ni in the nickel source and Mn in the manganese source to the amount of Li in the lithium source is (0.5-0.55): 1.
preferably, the temperature is reduced to the low-speed annealing temperature at the cooling rate of 0.1-0.5 ℃/min, the temperature of the low-speed annealing is 650-750 ℃, and the heat preservation time is 1-8 h.
Preferably, air is introduced during the high-temperature calcination and the low-speed annealing.
The invention provides a spinel type monocrystal cobalt-free high-voltage lithium nickel manganese oxide positive electrode material which is prepared according to the preparation method,
the spinel type single crystal cobalt-free high-voltage nickel lithium manganate positive electrode material is a single crystal with double-distribution of large and small particles, and has the shape of a regular octahedron and a truncated octahedron.
Preferably, the spinel type single crystal cobalt-free high-voltage lithium nickel manganese oxide cathode material has P4332 type crystal structure and Fd-3m type crystal structure, and mainly Fd-3m type crystal structure.
The invention provides a lithium ion battery which comprises the positive electrode material.
The invention provides a preparation method of a spinel type monocrystal cobalt-free high-voltage lithium nickel manganese oxide positive electrode material, which comprises the following steps: A) adding a nickel source and a manganese source under the action of a precipitator, ammonia water and a complexing agent, and carrying out coprecipitation reaction to obtain Ni0.5Mn1.5(OH)4A binary precursor; B) adding the Ni0.5Mn1.5(OH)4Mixing the binary precursor with a lithium source, calcining at high temperature, annealing at low speed, keeping the temperature, and naturally coolingObtaining a single crystal LiNi0.5Mn1.5O4A positive electrode material; the high-temperature calcination temperature is 850-1000 ℃, the heating rate is 2-5 ℃/min, and the high-temperature calcination time is 6-15 hours. The material is mainly characterized by being a combination of regular octahedrons and truncated octahedrons. Wherein, the binary cobalt-free precursor synthesized by the coprecipitation method has uniform components; the one-step high-temperature calcination method is simple, and single crystal particles mixed with large and small particles are synthesized; the crystal structure type of the material can be adjusted by low-speed annealing heat preservation and proper enhancement of gas exchange. The method has the advantages of low price, simple preparation process, high compaction density, excellent electrochemical performance (including high capacity, high energy density, good rate performance and good cycle performance) and the like.
The invention controls the process, temperature and time of one-step high-temperature calcination to synthesize LiNi0.5Mn1.5O4The material is a single crystal material with double distribution of large and small particles, the appearance is the combination of regular octahedron and truncated octahedron, so that the material has higher pole piece compaction density more than 3.2g/cm3. Meanwhile, the regular octahedron exposes the crystal (111) surface, and the truncated octahedron exposes the crystal (100) and the crystal (110) surface, so that the material has the advantages of high capacity, high multiplying power, good cycle performance and the like. Wherein the surface energy of the (111) plane is low, the cycle performance is good, and the gaps are larger in the directions of the (100) plane and the (110) plane, which is beneficial to Li+Better transmission, capacity and rate performance.
Experiments show that the first effect of the single-crystal high-voltage lithium nickel manganese oxide material is more than 94%, the 1C g capacity is more than 133mAh/g, the 1C normal-temperature 100-time circulation capacity retention rate is more than 97%, the 2C g capacity is more than 126mAh/g, and the 3C g capacity is more than 120 mAh/g. The 1C capacity of the soft package full battery is larger than 125mAh/g, and the 1C normal temperature 200-time circulation capacity retention rate is larger than 80%.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 shows Ni prepared in example 1 of the present invention0.5Mn1.5(OH)4SEM image of binary cobalt-free precursor;
FIG. 2 shows Ni prepared in example 1 of the present invention0.5Mn1.5(OH)4XRD pattern of binary cobalt-free precursor;
FIG. 3 is a LiNi prepared in example 1 of the present invention0.5Mn1.5O4SEM images of single crystal high voltage materials;
FIG. 4 is a LiNi prepared in example 1 of the present invention0.5Mn1.5O4XRD pattern of single crystal high voltage material;
FIG. 5 is a LiNi prepared in example 1 of the present invention0.5Mn1.5O4A grain size distribution curve of the single crystal high voltage material;
FIG. 6 is a LiNi prepared in example 1 of the present invention0.5Mn1.5O4The charge curve of the button cell of single crystal high voltage material;
FIG. 7 is a LiNi prepared in example 1 of the present invention0.5Mn1.5O4Cycling and rate curves for single crystal high voltage button cells;
FIG. 8 is a LiNi prepared in example 1 of the present invention0.5Mn1.5O4Cycling profile for soft-packed full cells of single crystal high voltage material.
Detailed Description
The invention provides a preparation method of a spinel type monocrystal cobalt-free high-voltage lithium nickel manganese oxide positive electrode material, which comprises the following steps:
A) adding a nickel source and a manganese source under the action of a precipitator, ammonia water and a complexing agent, and carrying out coprecipitation reaction to obtain Ni0.5Mn1.5(OH)4A binary precursor;
B) adding the Ni0.5Mn1.5(OH)4Mixing the binary precursor with a lithium source, calcining at high temperature, annealing at low speed, keeping the temperature, and naturally cooling to obtain the single crystal LiNi0.5Mn1.5O4A positive electrode material;
the high-temperature calcination temperature is 850-1000 ℃, the heating rate is 2-5 ℃/min, and the high-temperature calcination time is 6-15 hours.
Under the action of precipitant, ammonia water and other complexing agent, metal salt solution containing Ni and Mn is added into high-temperature reactor and through coprecipitation reaction, Ni is synthesized0.5Mn1.5(OH)4A binary cobalt-free precursor.
In the invention, the precipitant is preferably an alkaline hydroxide, such as one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide and aluminum hydroxide; the complexing agent is preferably one or more of acetic acid, ammonium oxalate, glycine, ethylenediamine and pentaerythritol; the nickel-containing metal salt is preferably one or more of nickel sulfate, nickel nitrate, nickel chloride, nickel acetate, nickel bromide and nickel sulfamate; the manganese-containing metal salt is preferably one or more of manganese sulfate, manganese nitrate, manganese chloride, manganese acetate and manganese perchlorate.
In the system for carrying out the coprecipitation, the content of ammonia water is preferably 0.05-0.4 mol/L, more preferably 0.1-0.3 mol/L, and most preferably 0.2-0.25 mol/L, and the content of a complexing agent is preferably 0.01-0.2 mol/L, more preferably 0.05-0.15 mol/L, and most preferably 0.1 mol/L; the molar ratio of Ni in the nickel source to Mn in the manganese source is preferably 2.8 to 3.2, more preferably 2.9 to 3.1, and most preferably 3.0.
In the invention, the pH value of the metal salt solution containing nickel and manganese is preferably 3-5, and more preferably 4; and the pH value of the system after the precipitator, the ammonia water and the complexing agent are added is controlled to be 10.5-11.5.
In the invention, the temperature of the coprecipitation reaction is preferably 40-60 ℃, more preferably 45-55 ℃, such as 40 ℃, 45 ℃, 50 ℃, 55 ℃ or 60 ℃; the coprecipitation reaction is preferably carried out under the condition of stirring, and the rotating speed of the stirring is preferably 300-800 rpm, more preferably 400-700 rpm, and most preferably 500-600 rpm.
After the coprecipitation reaction is finished, the reaction product is preferably aged for 12-24 hours to obtain Ni0.5Mn1.5(OH)4Two elementsAnd (3) cobalt-free precursor. Synthesized Ni0.5Mn1.5(OH)4The particle size of the precursor is 3-5 μm, and the specific surface area (BET) is 15-25 m2(ii) g, tap density of 0.9-1.1g/cm3. The precursor is used for preparing single crystal materials, the shape of the precursor is controlled to be similar to a sphere, the crystal whisker is thin, and the precursor has proper porosity and is convenient for being sintered into single crystals subsequently.
Obtaining Ni0.5Mn1.5(OH)4After the binary cobalt-free precursor, Ni is added in the invention0.5Mn1.5(OH)4Uniformly mixing the precursor and a lithium source, then carrying out one-step high-temperature calcination, carrying out low-speed annealing and heat preservation, and naturally cooling to obtain single crystal LiNi with double-distribution large and small particles0.5Mn1.5O4A material.
In the present invention, the lithium source is preferably lithium hydroxide and/or lithium carbonate; the ratio of the total amount of Ni in the nickel source and Mn in the manganese source to the amount of Li in the lithium source is preferably (0.5 to 0.55): 1.
in the invention, the temperature of the one-step high-temperature calcination is preferably 800-1000 ℃, more preferably 850-950 ℃, such as 800 ℃, 850 ℃, 880 ℃, 900 ℃, 920 ℃, 940 ℃, 960 ℃, 980 ℃, 1000 ℃, and the time of the high-temperature calcination is preferably 6-15 hours, more preferably 8-12 hours, such as 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours. The heating rate for realizing the high-temperature calcination temperature is preferably 2-5 ℃/min, and more preferably 3-4 ℃/min.
The invention only carries out one-step calcination, and the temperature and time of one-step high-temperature calcination by regulating and controlling the calcination procedure, so that the synthesized LiNi0.5Mn1.5O4The material is a single crystal material with double distribution of large and small particles, the appearance is the combination of regular octahedron and truncated octahedron, so that the material has higher pole piece compaction density more than 3.2g/cm3. Meanwhile, the regular octahedron exposes the crystal (111) surface, and the truncated octahedron exposes the crystal (100) and the crystal (110) surface, so that the material has the advantages of high capacity, high multiplying power, good cycle performance and the like. Wherein the surface energy of the (111) surface is low, the cycle performance is good, the gaps are larger in the (100) and (110) surface directions,benefit from Li+Better transmission, capacity and rate performance.
After the one-step high-temperature calcination is completed, the low-speed cooling is carried out, the heat preservation is carried out after the annealing temperature is reached, in the invention, the cooling, namely the low-speed annealing speed is preferably 0.1-0.5 ℃/min, more preferably 0.2-0.4 ℃/min, most preferably 0.3 ℃/min, and the annealing temperature is preferably 650-750 ℃, more preferably 700 ℃; the heat preservation time is preferably 1-8 hours, more preferably 2-6 hours, and most preferably 3-5 hours.
In the invention, the high-temperature calcination stage and the low-speed annealing stage need to be properly blown with air, particularly the annealing heat preservation stage, and the crystal structure of the material is adjusted by properly enhancing gas exchange and controlling the annealing process (P4)3Type 32 to Fd-3 m) to a suitable ratio, but predominantly Fd-3 m.
The invention provides a spinel type monocrystal cobalt-free high-voltage lithium nickel manganese oxide positive electrode material which is prepared according to the preparation method.
The positive electrode material is a single crystal material with double-distribution of large and small particles, and the shape of the positive electrode material is a combination of a regular octahedron and a truncated octahedron, so that the positive electrode material has higher pole piece compaction density of more than 3.2g/cm3. Meanwhile, the regular octahedron exposes the crystal (111) surface, and the truncated octahedron exposes the crystal (100) and the crystal (110) surface, so that the material has the advantages of high capacity, high multiplying power, good cycle performance and the like. Wherein the surface energy of the (111) plane is low, the cycle performance is good, and the gaps are larger in the directions of the (100) plane and the (110) plane, which is beneficial to Li+Better transmission, capacity and rate performance.
The invention also provides a lithium ion battery, wherein the used positive electrode comprises the positive electrode material.
In the present invention, the negative electrode, the separator, the electrolyte, or the like in the lithium ion battery may be a negative electrode, a separator, or an electrolyte that is commonly used by those skilled in the art, and the present invention is not particularly limited thereto.
The invention provides a preparation method of a spinel type monocrystal cobalt-free high-voltage lithium nickel manganese oxide positive electrode material, which comprises the following steps: A) in a precipitating agent, ammonia water and complexingUnder the action of the agent, adding a nickel source and a manganese source, and carrying out coprecipitation reaction to obtain Ni0.5Mn1.5(OH)4A binary precursor; B) adding the Ni0.5Mn1.5(OH)4Mixing the binary precursor with a lithium source, calcining at high temperature, annealing at low speed, keeping the temperature, and naturally cooling to obtain the single crystal LiNi0.5Mn1.5O4A positive electrode material; the high-temperature calcination temperature is 850-1000 ℃, the heating rate is 2-5 ℃/min, and the high-temperature calcination time is 6-15 hours. The material is mainly characterized by being a combination of regular octahedrons and truncated octahedrons. Wherein, the binary cobalt-free precursor synthesized by the coprecipitation method has uniform components; the one-step high-temperature calcination method is simple, and single crystal particles mixed with large and small particles are synthesized; the crystal structure type of the material can be adjusted by low-speed annealing heat preservation and proper enhancement of gas exchange. The method has the advantages of low price, simple preparation process, high compaction density, excellent electrochemical performance (including high capacity, high energy density, good rate performance and good cycle performance) and the like.
The invention controls the process, temperature and time of one-step high-temperature calcination to synthesize LiNi0.5Mn1.5O4The material is a single crystal material with double distribution of large and small particles, the appearance is the combination of regular octahedron and truncated octahedron, so that the material has higher pole piece compaction density more than 3.2g/cm3. Meanwhile, the regular octahedron exposes the crystal (111) surface, and the truncated octahedron exposes the crystal (100) and the crystal (110) surface, so that the material has the advantages of high capacity, high multiplying power, good cycle performance and the like. Wherein the surface energy of the (111) plane is low, the cycle performance is good, and the gaps are larger in the directions of the (100) plane and the (110) plane, which is beneficial to Li+Better transmission, capacity and rate performance.
Experiments show that the first effect of the single-crystal high-voltage lithium nickel manganese oxide material is more than 94%, the 1C g capacity is more than 133mAh/g, the 1C normal-temperature 100-time circulation capacity retention rate is more than 97%, the 2C g capacity is more than 126mAh/g, and the 3C g capacity is more than 120 mAh/g. The 1C capacity of the soft package full battery is larger than 125mAh/g, and the 1C normal temperature 200-time circulation capacity retention rate is larger than 80%.
For further illustration of the present invention, the spinel-type single-crystal cobalt-free high-voltage lithium nickel manganese oxide cathode material, the preparation method thereof and the lithium ion battery provided by the present invention are described in detail below with reference to the examples, but the present invention should not be construed as being limited to the scope of the present invention.
Example 1
Mixing NiSO4·6H2O and MnSO4·H2O according to the molar ratio of Ni/Mn of 1/3, preparing a mixed solution with the metal ion concentration of 1.5mol/L, controlling the initial pH to be 4, adding 0.04mol/L ethylenediamine and 0.3mol/L ammonia water as complexing agents, adding 4mol/L NaOH as precipitating agents, controlling the pH to be 11 and the reaction temperature to be 55 ℃, controlling the sphericity of the mixture in a continuous feeding mode, reacting for 8 hours, finally aging the reaction product for 12 hours, filtering, centrifuging, washing and drying to obtain Ni with the particle size of 4 mu m0.5Mn1.5(OH)4A binary cobalt-free precursor.
Mixing the above Ni0.5Mn1.5(OH)4Precursors with Li2CO3According to a molar ratio of 1: 0.52, loading the mixture into a boat, placing the boat in a muffle furnace for high-temperature calcination, and properly blowing air in the period to control the atmosphere. Heating from room temperature at a rate of 2 deg.C/min, adding heat to 980 deg.C, and holding for 8 hr. Cooling to 715 deg.C at a cooling rate of 0.3 deg.C/m, maintaining the temperature for 5 hr, and naturally cooling to room temperature to obtain LiNi with particle size of 1.5 μm and 8 μm0.5Mn1.5O4A single crystal positive electrode material.
Ni prepared in example 10.5Mn1.5(OH)4The precursor, after SEM and XRD examination, obtained the examination results of fig. 1 and fig. 2, respectively, in which the precursor can be seen.
LiNi prepared in example 10.5Mn1.5O4The positive electrode material is detected by SEM and XRD, and detection results are respectively obtained as shown in fig. 3 and fig. 4.
LiNi prepared in example 10.5Mn1.5O4The positive electrode material was passed through a particle size tester to obtain a test result, fig. 5.
LiNi prepared in example 10.5Mn1.5O4The anode material is prepared into a buttonAfter the battery is subjected to electrochemical tests, a charge-discharge curve (figure 6) and a cycle rate curve (figure 7) of the material are obtained respectively.
LiNi prepared in example 10.5Mn1.5O4After the positive electrode material is prepared into a soft package full cell, a cycle curve of the material is obtained after electrochemical tests (figure 8).
Experiments show that the single-crystal high-voltage lithium nickel manganese oxide material has the first effect of 94 percent, the 1C gram capacity of 135.2mAh/g, the 1C normal-temperature 100-time circulation capacity retention rate of 97.2 percent, the 2C gram capacity of 128.2mAh/g and the 3C gram capacity of 126.3 mAh/g. The 1C gram capacity of the soft package full battery is 126mAh/g, and the 1C normal temperature 200 times circulation capacity retention rate is 83%.
Example 2
Reacting Ni (Ac)2And Mn (Ac)2Preparing a mixed solution with the metal ion concentration of 1.5mol/L according to the molar ratio of Ni/Mn of 1/3, setting the initial pH to be 4.5, adding 0.05mol/L glycine and 0.3mol/L ammonia water as complexing agents, adding 2mol/L NaOH as precipitating agents, controlling the pH to be 11 and the reaction temperature to be 55 ℃, controlling the sphericity of the mixed solution in a continuous feeding mode, reacting for 8 hours, finally aging the reaction product for 12 hours, filtering, centrifuging, washing and drying to obtain Ni with the particle size of 4 mu m0.5Mn1.5(OH)4A binary cobalt-free precursor.
Mixing the above Ni0.5Mn1.5(OH)4Precursor and LiOH. H2O is mixed according to a molar ratio of 1: 1.04, loading the mixture into a boat, placing the boat in a muffle furnace for high-temperature calcination, properly blowing air in the period, and controlling the atmosphere. Heating from room temperature at a heating rate of 2 deg.C/min, adding heat to 960 deg.C, and maintaining for 10 hr. Cooling to 710 ℃ at a cooling rate of 0.3 ℃/m, keeping the temperature for 5 hours, and finally naturally cooling to room temperature to obtain LiNi0.5Mn1.5O4A single crystal positive electrode material.
Example 3
Mixing NiCl2And MnCl2Preparing a mixed solution with the metal ion concentration of 1.5mol/L according to the molar ratio of Ni to Mn of 1/3, wherein the initial pH is 4.2, adding 0.08mol/L ammonium oxalate and 0.4mol/L ammonia water as complexing agents, adding 2mol/L NaOH as precipitating agents,controlling the pH value to be 11 and the reaction temperature to be 55 ℃, controlling the sphericity of the Ni by a continuous feeding mode, reacting for 8 hours, finally aging the reaction product for 12 hours, filtering, centrifugally washing and drying to obtain Ni with the granularity of 4um0.5Mn1.5(OH)4A binary cobalt-free precursor.
Mixing the above Ni0.5Mn1.5(OH)4Precursor and LiOH. H2O is mixed according to a molar ratio of 1: 1.04, loading the mixture into a boat, placing the boat in a muffle furnace for high-temperature calcination, properly blowing air in the period, and controlling the atmosphere. Heating from room temperature at a heating rate of 2 deg.C/min, adding heat to 940 deg.C, and holding for 10 hr. Cooling to 700 ℃ at a cooling rate of 0.3 ℃/m, keeping the temperature for 8 hours, and finally naturally cooling to room temperature to obtain LiNi0.5Mn1.5O4A single crystal positive electrode material.
Example 4
Mixing Ni (NO)3)2And Mn (NO)3)2Preparing a mixed solution with the metal ion concentration of 1.5mol/L according to the molar ratio of Ni/Mn of 1/3, setting the initial pH to be 4.0, adding 0.1mol/L pentaerythritol and 0.4mol/L ammonia water as complexing agents, adding 4mol/L NaOH as precipitating agents, controlling the pH to be 11 and the reaction temperature to be 55 ℃, controlling the sphericity of the mixed solution in a continuous feeding mode, reacting for 8 hours, aging the reaction product for 12 hours, filtering, centrifuging, washing and drying to obtain Ni with the particle size of 4 mu m0.5Mn1.5(OH)4A binary cobalt-free precursor.
Mixing the above Ni0.5Mn1.5(OH)4Precursors with Li2CO3According to a molar ratio of 1: 0.53, loading the mixture into a boat, placing the boat in a muffle furnace for high-temperature calcination, and properly blowing air in the period to control the atmosphere. Heating to 920 ℃ from room temperature at a heating rate of 2 ℃/min, and keeping the temperature for 10 hours. Cooling to 720 ℃ at a cooling rate of 0.1 ℃/m, keeping the temperature for 8 hours, and finally naturally cooling to room temperature to obtain LiNi0.5Mn1.5O4A single crystal positive electrode material.
Example 5
Reacting NiBr2And Mn (ClO)4)2In terms of moles of Ni/MnPreparing a mixed solution with metal ion concentration of 1.5mol/L according to a ratio of 1/3, wherein the initial pH is 4.0, adding 0.1mol/L acetic acid and 0.4mol/L ammonia water as complexing agents, adding 4mol/L NaOH as precipitating agents, controlling the pH to be 11 and the reaction temperature to be 55 ℃, controlling the sphericity of the mixed solution in a continuous feeding mode, reacting for 8 hours, finally aging the reaction product for 12 hours, filtering, centrifugally washing and drying to obtain Ni with the particle size of 4 mu m0.5Mn1.5(OH)4A binary cobalt-free precursor.
Mixing the above Ni0.5Mn1.5(OH)4Precursors with Li2CO3According to a molar ratio of 1: 0.55, loading the mixture into a boat, placing the boat in a muffle furnace for high-temperature calcination, and properly blowing air during the calcination, wherein the atmosphere is controlled. Heating from room temperature at a heating rate of 2 deg.C/min, adding heat to 880 deg.C, and maintaining for 10 hr. Cooling to 730 deg.C at a cooling rate of 0.1 deg.C/m, maintaining the temperature for 8h, and naturally cooling to room temperature to obtain LiNi0.5Mn1.5O4A single crystal positive electrode material.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a spinel type monocrystal cobalt-free high-voltage lithium nickel manganese oxide positive electrode material comprises the following steps:
A) adding a nickel source and a manganese source under the action of a precipitator, ammonia water and a complexing agent, and carrying out coprecipitation reaction to obtain Ni0.5Mn1.5(OH)4A binary precursor;
B) adding the Ni0.5Mn1.5(OH)4Mixing the binary precursor with a lithium source, performing one-step high-temperature calcination, then performing low-speed annealing and heat preservation, and finally naturally cooling to obtain the single crystal LiNi0.5Mn1.5O4A positive electrode material;
the high-temperature calcination temperature is 850-1000 ℃, the heating rate is 2-5 ℃/min, and the high-temperature calcination time is 6-15 hours.
2. The production method according to claim 1, wherein the precipitant is an alkali hydroxide; the complexing agent is one or more of acetic acid, ammonium oxalate, glycine, ethylenediamine and pentaerythritol.
3. The preparation method of claim 1, wherein the nickel source is one or more of nickel sulfate, nickel nitrate, nickel chloride, nickel acetate, nickel bromide and nickel sulfamate;
the manganese source is one or more of manganese sulfate, manganese nitrate, manganese chloride, manganese acetate and manganese perchlorate;
the molar ratio of Ni in the nickel source to Mn in the manganese source is 2.8-3.2.
4. The preparation method according to claim 1, wherein the temperature of the coprecipitation reaction is 40-60 ℃; the coprecipitation reaction is carried out under the stirring condition of the rotating speed of 300-800 rpm.
5. The preparation method according to claim 1, wherein the lithium source is one or more of lithium hydroxide, lithium carbonate and lithium acetate;
the ratio of the total amount of Ni in the nickel source and Mn in the manganese source to the amount of Li in the lithium source is (0.5-0.55): 1.
6. the preparation method according to claim 1, wherein the temperature is reduced to the low-speed annealing temperature at a cooling rate of 0.1-0.5 ℃/min, the temperature of the low-speed annealing is 650-750 ℃, and the holding time is 1-8 h.
7. The method according to claim 1, wherein air is introduced during both the high-temperature calcination and the low-speed annealing.
8. A spinel type monocrystal cobalt-free high-voltage lithium nickel manganese oxide positive electrode material is prepared by the preparation method according to any one of claims 1 to 7,
the spinel type single crystal cobalt-free high-voltage nickel lithium manganate positive electrode material is a single crystal with double-distribution of large and small particles, and has the shape of a regular octahedron and a truncated octahedron.
9. The cathode material of claim 8, wherein the spinel-type single crystal cobalt-free high voltage lithium nickel manganese oxide cathode material has P4332 type crystal structure and Fd-3m type crystal structure, and mainly Fd-3m type crystal structure.
10. A lithium ion battery comprising the positive electrode material of claim 8 or 9.
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