CN115304109A - Preparation method and application method of doped spherical nickel-manganese binary precursor - Google Patents
Preparation method and application method of doped spherical nickel-manganese binary precursor Download PDFInfo
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Abstract
The invention relates to a doped spherical nickel-manganese binary precursor, belonging to the technical field of preparation of battery anode materials. The preparation method comprises the following steps: (1) Preparing a mixed metal salt solution of manganese salt, nickel salt and M salt; preparing an organic buffer solution; preparing a surfactant solvent; preparing a mixed solution of ammonium fluoride and sodium carbonate; (2) Mixing mixed metal salt solution with mixed solution of ammonium fluoride and sodium carbonate in N 2 Injecting into a reaction kettle filled with surfactant and buffer solution by means of peristaltic pump under protection, stirring for reaction, and reacting the suspension in the reaction kettle after the addition is finishedAging for 1 to 2h after 20 to 30h; (3) And centrifuging, drying, sieving and removing iron from the obtained material. According to the invention, through the combined action of the buffer solution and the surfactant, the morphology of the lithium nickel manganese oxide positive electrode material can be stabilized, the micron-sized lithium nickel manganese oxide which is not easy to agglomerate is prepared, and the doping elements can improve the specific capacity, the initial charge performance and the cycle performance of the spinel lithium nickel manganese oxide.
Description
Technical Field
The invention belongs to the technical field of battery materials. In particular to a preparation method and an application method of a doped spherical nickel-manganese binary precursor.
Background
The energy storage system plays an important role in promoting the energy power system to advance to a clean, low-carbonization and intelligent process. The rechargeable energy storage system of the lithium ion battery provides a promising solution for the development of the next generation of electric vehicles, and the huge demand for energy stimulates the development of the high-energy density lithium ion battery material, namely spinel LiNi 0.5 Mn 1.5 O 4 Materials have received attention in recent years and are considered to be one of the most promising positive electrode materials. LiNi 0.5 Mn 1.5 O 4 The preparation method comprises a sol-gel method, a solid-phase sintering method, a molten salt method, a microwave heating method, a hydrothermal method, a coprecipitation method and the like, wherein the coprecipitation method can uniformly mix raw materials, has the advantages of simple process, low sintering temperature, excellent product performance and the like, and is most likely to be used for industrial production of LiNi 0.5 Mn 1.5 O 4 A method of (1). The nickel-manganese binary precursor determines LiNi 0.5 Mn 1.5 O 4 Thus, a nickel-manganese precursor pair LiNi with excellent performance is developed 0.5 Mn 1.5 O 4 The preparation of the cathode material is crucial.
Disclosure of Invention
The invention aims to provide a preparation method of a doped spherical nickel-manganese binary precursor, which takes carbonate, nickel salt and manganese salt as main raw materials and adopts chemical precipitation reaction to prepare the nickel-manganese carbonate precursor.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a doped spherical nickel-manganese binary precursor comprises the following steps:
(1) Preparing a mixed metal salt solution of manganese salt, nickel salt and M salt according to a stoichiometric ratio to obtain a mixed solution A; preparing an organic buffer solution with the pH value of 7.3-7.8 to obtain a mixed solution B; preparing a surfactant solution according to 1-3 wt% of the total mass of the mixed metal salt to obtain a mixed solution C; preparing a mixed solution of ammonium fluoride and sodium carbonate according to a stoichiometric ratio to obtain a mixed solution D; m is selected from one or more of Al, Y, zr, cr, zn, bi, la, ti, mg and Nb;
(2) Adding the mixed solution B and the mixed solution C into a reaction kettle, introducing nitrogen, starting stirring, slowly pumping the mixed solution A and the mixed solution D into the reaction kettle by a peristaltic pump at a feeding speed of 0.05-0.15L/h, keeping the pH value of a reaction system at 7.3-7.8 by controlling the dropping speed, controlling the reaction temperature at 45-60 ℃, and after the addition is finished, reacting the suspension in the reaction kettle for 20-30 h and then aging for 1-2 h;
(3) Centrifuging, drying, sieving and removing iron from the material obtained in the step (2) to obtain a nickel-manganese carbonate precursor; the chemical general formula of the nickel manganese carbonate precursor is Ni 0.25-x Mn 0.75-x M 2x (CO 3 ) 1-y F 2y, Wherein x is more than or equal to 0 and less than or equal to 0.05,0 and less than or equal to 0.05.
The organic buffer solution in the step (1) is one or more of TES, HEPES, BES and MOPS.
The surfactant in the step (1) is one or more of CTAB, SDBS and PVP.
Preference is given to using a combination of HEPES as pH stabilizer and, on the one hand, HEPES as dispersant, protecting against NiCO 3 And MnCO 3 Aggregation of the nanoparticles to provide a mixture ofUniform cation distribution. In addition, it was found that the carbonate precursor having a uniform element distribution can effectively suppress impurity Li x Ni 1-x And O is generated. PVP (polyvinyl pyrrolidone) serving as a nonionic surfactant tends to form a protective layer on the surface of particles in the reaction process, particles with relatively high affinity are separated by repulsive force generated by a steric hindrance effect generated by a hydrophobic long chain of the PVP, aggregation among the particles is prevented, the anionic surfactant cannot achieve the effect, and the phenomenon of uneven particle size exists. Cationic surfactants can present a (110) surface, affecting the cycling stability of the material.
The sum of the metal ion concentrations in the mixed solution A in the step (1) is 0.5-1.5 mol/L; CO in the mixed solution D 3 2- The ion concentration is 0.5-1.5 mol/L.
The nickel manganese carbonate precursor is spherical or quasi-spherical, and the size of the nickel manganese carbonate precursor is 5-7 mu m.
Pretreating a carbonate precursor of a lithium nickel manganese oxide positive electrode material at 850-900 ℃, and then mixing the pretreated precursor with Li 2 CO 3 After being uniformly mixed, the mixture is sintered at the temperature of 750-850 ℃ to obtain the lithium nickel manganese oxide anode material. The ventilation flow rate of the sintering is 1m 3 /h～3m 3 H; the sintering time is 10-18 h.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following positive effects:
1. the invention adopts the organic buffer solution, on one hand, the organic buffer solution can be used as a pH stabilizer, and on the other hand, the organic buffer solution is used as a dispersant to prevent the aggregation of nickel-manganese precursor particles, thereby providing uniform cation distribution and ensuring the stable and compact structure of the nickel-manganese precursor. The most important is that the organic buffer solution is non-toxic, safe and environment-friendly, and the later-stage waste liquid treatment cost is low;
2. the dispersant can be added to prevent the aggregation of the nickel-manganese precursor under the combined action of the organic buffer solution and the dispersant, and can form a layer of carbon coating on the surface of the precursor to form an integral carbon coating structure, thereby being beneficial to the lithium ion deintercalation and the electrolyte infiltration;
3. the stability of the interior and the interface of the lithium nickel manganese oxide material is improved by co-doping of anions and cations, the lattice distortion caused by the Jahn-Teller effect in the charge-discharge process can be fully inhibited, the normal-temperature cycle performance and the rate discharge performance of the material are further improved, and the material has higher gram capacity and longer cycle life.
In conclusion, the nickel-manganese carbonate precursor disclosed by the invention is high in safety, good in stability and low in cost; the prepared lithium nickel manganese oxide positive electrode material has the remarkable advantages of high gram volume, large compacted density, long normal-temperature cycle life, good rate discharge performance, good high-temperature electricity storage performance and the like.
Drawings
FIG. 1 is an XRD pattern of a precursor obtained in example 1;
fig. 2 is an XRD pattern of the cathode material obtained in example 1;
FIG. 3 is an SEM photograph of the cathode material obtained in example 1;
FIG. 4 is a charge/discharge graph of the positive electrode material obtained in example 1;
FIG. 5 is a graph showing rate performance of the lithium manganate battery of example 1;
fig. 6 is a graph showing cycle performance of the lithium manganate battery of example 1.
Detailed Description
The invention is further described with reference to the following drawings and detailed description, wherein the specific embodiments are described herein for the purpose of illustration only, and the scope of the claims is not limited to the description.
Example 1
The embodiment provides an Al and F co-doped nickel-manganese binary precursor, and the chemical general formula of spinel lithium nickel manganese oxide is Ni 0.24 Mn 0.74 Al 0.02 (CO 3 ) 0.99 F 0.02 。
The embodiment also provides a preparation method of the nickel-manganese binary precursor, which comprises the following steps:
(1) Weighing nickel sulfate, manganese sulfate and aluminum sulfate according to the molar ratio of Ni to Mn to Al = 12; preparing HEPES organic buffer solution with the pH value of 7.4 to obtain mixed solution B; preparing CTAB solution according to 1.5wt% of the mass of the mixed metal salt to obtain mixed solution C; preparing a mixed solution D with the concentration of 0.75mol/L of sodium carbonate according to the mol ratio F (ammonium fluoride) to C (sodium carbonate) = 2;
(2) Adding CTAB (mixed solution C) and HEPES (mixed solution B) buffer solution into a reaction kettle, introducing nitrogen, starting stirring at the stirring speed of 350rpm, slowly pumping the mixed solution A and the mixed solution D into a base solution through a peristaltic pump at the feeding speed of 0.06L/h, controlling the dropping speed to keep the pH value of a reaction system at 7.4 and the reaction temperature of 55 ℃, and after the addition is finished, reacting the suspension in a reactor for 24h and then aging for 1h;
(3) And (3) centrifuging the material obtained in the step (2), drying, sieving and removing iron to obtain the spherical nickel-manganese carbonate precursor with the size of 6 microns.
The obtained Ni 0.24 Mn 0.74 Al 0.02 (CO 3 ) 0.99 F 0.02 The precursor is pretreated for 4 hours at 900 ℃ and then is mixed with Li in stoichiometric ratio 2 CO 3 And after uniformly mixing, placing the mixture in an air muffle furnace for sintering, and sintering at 820 ℃ for 12h to obtain the required lithium nickel manganese oxide cathode material.
And (3) electrical property detection: the positive plate adopts the following formula: conductive agent: 1, binder =8, and a lithium metal sheet is used as a negative electrode sheet, an R2032 type battery test is prepared, and a measurement is performed by using a novice tester under a charge-discharge system of charging 4.95V and discharging 3.5V, wherein 1C discharge gram capacity is 133.5mAh/g, tap density: 1.85g/cm 3 And the capacity retention rate is 92.4 percent after 500 weeks of normal-temperature circulation.
Example 2
The embodiment provides a Y, F co-doped nickel-manganese binary precursor, and the chemical general formula of the spinel nickel lithium manganate is Ni 0.24 Mn 0.74 Y 0.02 (CO 3 ) 0.99 F 0.02 。
The embodiment also provides a preparation method of the nickel-manganese binary precursor, which comprises the following steps:
(1) Weighing nickel chloride, manganese chloride and yttrium chloride to prepare a 0.9mol/L metal salt solution A according to the molar ratio of Ni to Mn to Y = 12; preparing a TES organic buffer solution with pH of 7.5 to obtain a mixed solution B; preparing an SDBS solution according to 2wt% of the mass of the mixed metal salt to obtain a mixed solution C; preparing a mixed solution D with the concentration of 0.9mol/L of sodium carbonate according to the mol ratio F (ammonium fluoride) to C (sodium carbonate) = 2;
(2) Adding SDBS and TES buffer solution into a reaction kettle, introducing nitrogen, starting stirring at the stirring speed of 400rpm, slowly pumping the mixed solution A and the mixed solution D into a base solution through a peristaltic pump at the feeding speed of 0.07L/h, controlling the dropping speed to keep the pH value of a reaction system at 7.5 and the reaction temperature of 55 ℃, and after the addition is finished, reacting a suspension in a reactor for 24 hours and then aging for 1 hour;
(3) And (3) centrifuging the material obtained in the step (2), drying, sieving and removing iron to obtain the sphere-like nickel manganese carbonate precursor with the size of 5.5 microns.
The obtained Ni 0.24 Mn 0.74 Y 0.02 (CO 3 ) 0.99 F 0.02 The precursor is pretreated for 4h at 850 ℃ and then is mixed with Li in stoichiometric ratio 2 CO 3 And after uniformly mixing, placing the mixture in an air muffle furnace for sintering, and sintering at 820 ℃ for 12h to obtain the required lithium nickel manganese oxide cathode material.
And (3) electrical property detection: the positive plate adopts the following formula: conductive agent: 1, binder =8, and a lithium metal sheet is used as a negative electrode sheet, an R2032 type battery test is prepared, and a 1C discharge gram capacity is 131.3mAh/g, a tap density is detected by a novyi tester under a charge-discharge system of charging 4.95V and discharging 3.5V: 1.81g/cm 3 And the capacity retention rate is 91.3 percent after the normal-temperature cycle is 500 weeks.
Example 3
The embodiment provides a Nb and F co-doped nickel-manganese binary precursor, wherein the chemical general formula of spinel nickel lithium manganate is Ni 0.24 Mn 0.74 Al 0.02 (CO 3 ) 0.99 F 0.02 。
The embodiment also provides a preparation method of the nickel-manganese binary precursor, which comprises the following steps:
(1) Weighing nickel sulfate, manganese sulfate and niobium sulfate according to the molar ratio of Ni to Mn to Nb = 12; preparing BES organic buffer solution with pH of 7.6 to obtain mixed solution B; preparing a CTAB solution according to 1.5wt% of the mass of the mixed metal salt to obtain a mixed solution C; preparing a mixed solution D with the concentration of 1.2mol/L of sodium carbonate according to the mol ratio F (ammonium fluoride) to C (sodium carbonate) = 2;
(2) Adding CTAB and BES buffer solution into a reaction kettle, introducing nitrogen, starting stirring at the stirring speed of 400rpm, slowly pumping the mixed solution A and the mixed solution D into a base solution by a peristaltic pump at the feeding speed of 0.08L/h, controlling the dropping speed to keep the pH of a reaction system at 7.6 and the reaction temperature of 55 ℃, and after the addition is finished, reacting the suspension in a reactor for 24 hours and then aging for 1 hour;
(3) And (3) centrifuging the material obtained in the step (2), drying, sieving and removing iron to obtain the spheroidal nickel manganese carbonate precursor with the size of 6.5 microns.
The obtained Ni 0.24 Mn 0.74 Nb 0.02 (CO 3 ) 0.99 F 0.02 The precursor is pretreated for 4 hours at 880 ℃ and then is mixed with Li in stoichiometric ratio 2 CO 3 And after uniformly mixing, placing the mixture in an air muffle furnace for sintering, and sintering at 840 ℃ for 12 hours to obtain the required lithium nickel manganese oxide cathode material.
And (3) electrical property detection: the positive plate adopts the following formula: conductive agent: 1, binder =8, and a lithium metal sheet is used as a negative electrode sheet, an R2032 type battery test is prepared, and a neomycin tester is adopted to test that the 1C discharge gram capacity is 132.4mAh/g, the tap density is: 1.86g/cm 3 And the capacity retention rate is 92.1 percent after the normal-temperature cycle is 500 weeks.
Example 4
The embodiment provides a Cr and F co-doped nickel-manganese binary precursor, and the chemical general formula of spinel nickel lithium manganate is Ni 0.24 Mn 0.74 Cr 0.02 (CO 3 ) 0.99 F 0.02 。
The embodiment also provides a preparation method of the nickel-manganese binary precursor, which comprises the following steps:
(1) Weighing nickel sulfate, manganese sulfate and chromium sulfate according to a molar ratio of Ni to Mn to Cr = 12; preparing MOPS organic buffer solution with the pH value of 7.4 to obtain mixed solution B; preparing a PVP solution according to 1.5wt% of the mass of the mixed metal salt to obtain a mixed solution C; preparing a mixed solution D with the concentration of sodium carbonate of 0.75mol/L according to the mol ratio of F (ammonium fluoride) to C (sodium carbonate) = 2;
(2) Adding PVP and MOPS buffer solution into a reaction kettle, introducing nitrogen, starting stirring at the stirring speed of 320rpm, slowly pumping the mixed solution A and the mixed solution D into a base solution through a peristaltic pump at the feeding speed of 0.06L/h, keeping the pH value of a reaction system at 7.4 by controlling the dropping speed, keeping the reaction temperature at 50 ℃, and after the addition is finished, reacting the suspension in a reactor for 24 hours and then aging for 1 hour;
(3) And (3) centrifuging the material obtained in the step (2), drying, sieving and removing iron to obtain the spheroidal nickel manganese carbonate precursor with the size of 7 microns.
The obtained Ni 0.24 Mn 0.74 Cr 0.02 (CO 3 ) 0.99 F 0.02 The precursor is pretreated for 4 hours at 900 ℃ and then is mixed with Li in stoichiometric ratio 2 CO 3 And after uniformly mixing, placing the mixture in an air muffle furnace for sintering, and sintering at 750 ℃ for 18h to obtain the required lithium nickel manganese oxide cathode material.
And (3) electrical property detection: the positive plate adopts the following formula: conductive agent: 1, binder =8, and a lithium metal sheet is used as a negative electrode sheet, an R2032 type battery test is prepared, and a neomycin tester is adopted to test that the 1C discharge gram capacity is 132.4mAh/g, the tap density is: 1.83g/cm 3 The capacity retention rate is 91.2% after being cycled for 500 weeks at normal temperature.
Example 5
The embodiment provides a Ti and F co-doped nickel-manganese binary precursor, and the chemical general formula of the spinel nickel lithium manganate is Ni 0.24 Mn 0.74 Ti 0.02 (CO 3 ) 0.99 F 0.02 。
The embodiment also provides a preparation method of the nickel-manganese binary precursor, which comprises the following steps:
(1) Weighing nickel acetate, manganese acetate and titanium acetate according to a molar ratio of Ni to Mn to Ti =12 =1 to prepare a metal salt solution A of 1.5mol/L; preparing HEPES organic buffer solution with the pH value of 7.3 to obtain mixed solution B; preparing a PVP solution according to 2wt% of the mass of the mixed metal salt to obtain a mixed solution C; preparing a mixed solution D with the concentration of 1.5mol/L of sodium carbonate according to the mol ratio F (ammonium fluoride) to C (sodium carbonate) = 2;
(2) Adding PVP and HEPES buffer solution into a reaction kettle, introducing nitrogen, starting stirring at the stirring speed of 350rpm, slowly pumping the mixed solution A and the mixed solution D into a base solution through a peristaltic pump at the feeding speed of 0.08L/h, keeping the pH value of a reaction system at 7.3 by controlling the dropping speed, keeping the reaction temperature at 55 ℃, and after the addition is finished, reacting the suspension in a reactor for 24 hours and then aging for 1 hour;
(3) And (3) centrifuging the material obtained in the step (2), drying, sieving and removing iron to obtain the spheroidal nickel manganese carbonate precursor with the size of 6 microns.
The obtained Ni 0.24 Mn 0.74 Ti 0.02 (CO 3 ) 0.99 F 0.02 The precursor is pretreated for 4h at 850 ℃ and then is mixed with Li in stoichiometric ratio 2 CO 3 And after uniformly mixing, placing the mixture in an air muffle furnace for sintering, and sintering at 850 ℃ for 10h to obtain the required lithium nickel manganese oxide cathode material.
And (3) electrical property detection: the positive plate adopts the following formula: conductive agent: 1, binder =8, and a lithium metal sheet is used as a negative electrode sheet, an R2032 type battery test is prepared, and a test is performed by using a novice tester under a charge-discharge system of charging 4.95V and discharging 3.5V, wherein 1C discharge gram capacity is 132.1mAh/g, tap density: 1.81g/cm 3 And the capacity retention rate is 91.2 percent after the normal-temperature cycle is 500 weeks.
Example 6
The embodiment provides a La and F co-doped nickel-manganese binary precursor, and the chemical general formula of the spinel nickel lithium manganate is Ni 0.24 Mn 0.74 La 0.02 (CO 3 ) 0.99 F 0.02 。
The embodiment also provides a preparation method of the nickel-manganese binary precursor, which comprises the following steps:
(1) Weighing nickel sulfate, manganese sulfate and lanthanum sulfate to prepare a metal salt solution A with the molar ratio of Ni to Mn to La = 12; preparing MOPS organic buffer solution with pH of 7.5 to obtain mixed solution B; preparing an SDBS solution according to 3wt% of the mixed metal salt to obtain a mixed solution C; preparing a mixed solution D with the concentration of 1.5mol/L of sodium carbonate according to the mol ratio F (ammonium fluoride) to C (sodium carbonate) = 2;
(2) Adding SDBS and MOPS solution into a reaction kettle, introducing nitrogen, starting stirring at the stirring speed of 450rpm, slowly pumping the mixed solution A and the mixed solution D into a base solution through a peristaltic pump at the feeding speed of 1.5L/h, keeping the pH value of a reaction system at 7.5 by controlling the dropping speed, keeping the reaction temperature at 60 ℃, and after the addition is finished, reacting the suspension in a reactor for 20h and then aging for 2h;
(3) And (3) centrifuging the material obtained in the step (2), drying, sieving and removing iron to obtain a spherical nickel-manganese carbonate precursor with the size of 5 microns.
The obtained Ni 0.24 Mn 0.74 La 0.02 (CO 3 ) 0.99 F 0.02 The precursor is pretreated for 4 hours at 900 ℃ and then is mixed with Li in stoichiometric ratio 2 CO 3 And after uniformly mixing, placing the mixture in an air muffle furnace for sintering, and sintering at 840 ℃ for 10h to obtain the required lithium nickel manganese oxide cathode material.
And (3) electrical property detection: the positive plate adopts the following formula: conductive agent: 1, binder =8, and a lithium metal sheet is used as a negative electrode sheet, an R2032 type battery test is prepared, and a 1C discharge gram capacity is 131.2mAh/g, a tap density is detected by a novyi tester under a charge-discharge system of charging 4.95V and discharging 3.5V: 1.81g/cm 3 And the capacity retention rate is 90.9 percent after 500 weeks of normal-temperature circulation.
Example 7
The embodiment provides a Mg and F co-doped nickel-manganese binary precursor, and the chemical general formula of spinel nickel lithium manganate is Ni 0.24 Mn 0.74 Mg 0.02 (CO 3 ) 0.99 F 0.02 。
The embodiment also provides a preparation method of the nickel-manganese binary precursor, which comprises the following steps:
(1) Weighing nickel sulfate, manganese sulfate and magnesium sulfate according to a molar ratio of Ni to Mn to Mg = 12; preparing a TES organic buffer solution with pH of 7.8 to obtain a mixed solution B; preparing a CTAB solution according to 1.5wt% of the mass of the mixed metal salt to obtain a mixed solution C; preparing a mixed solution D with the concentration of 0.75mol/L of sodium carbonate according to the mol ratio F (ammonium fluoride) to C (sodium carbonate) = 2;
(2) Adding CTAB and TES buffer solution into a reaction kettle, introducing nitrogen, starting stirring, slowly pumping the mixed solution A and the mixed solution D into a base solution by a peristaltic pump at a feeding speed of 0.05L/h, controlling the dropping speed to keep the pH of a reaction system at 7.8 and the reaction temperature at 60 ℃, and after the addition is finished, reacting the suspension in the reactor for 30 hours and then aging for 1 hour;
(3) And (3) centrifuging the material obtained in the step (2), drying, sieving and removing iron to obtain the spheroidal nickel manganese carbonate precursor with the size of 6.5 microns.
The obtained Ni 0.24 Mn 0.74 Mg 0.02 (CO 3 ) 0.99 F 0.02 The precursor is pretreated for 4 hours at 830 ℃, and then is mixed with Li in stoichiometric ratio 2 CO 3 And after uniformly mixing, placing the mixture in an air muffle furnace for sintering, and sintering at 830 ℃ for 11h to obtain the required lithium nickel manganese oxide cathode material.
And (3) electrical property detection: the positive plate adopts the following formula: conductive agent: 1, binder =8, and a lithium metal sheet is used as a negative electrode sheet, an R2032 type battery test is prepared, and a 1C discharge gram capacity is 131.5mAh/g, a tap density is detected by a novyi tester under a charge-discharge system of charging 4.95V and discharging 3.5V: 1.82g/cm 3 And the capacity retention rate is 91.4 percent after the normal-temperature cycle is 500 weeks.
Example 8
The embodiment provides a Ti and F co-doped nickel-manganese binary precursor, and the chemical general formula of the spinel nickel lithium manganate is Ni 0.24 Mn 0.74 Ti 0.02 (CO 3 ) 0.99 F 0.02 。
The embodiment also provides a preparation method of the nickel-manganese binary precursor, which comprises the following steps:
(1) Weighing nickel acetate, manganese acetate and lanthanum acetate according to a molar ratio of Ni to Mn to La = 12; preparing HEPES organic buffer solution with the pH value of 7.3 to obtain mixed solution B; preparing a PVP solution according to 2wt% of the mass of the mixed metal salt to obtain a mixed solution C; preparing a mixed solution D with the concentration of 1.5mol/L of sodium carbonate according to the mol ratio of F (ammonium fluoride) to C (sodium carbonate) = 2;
(2) Adding PVP and HEPES buffer solution into a reaction kettle, introducing nitrogen, starting stirring at the stirring speed of 350rpm, slowly pumping the mixed solution A and the mixed solution D into a base solution through a peristaltic pump at the feeding speed of 0.08L/h, keeping the pH value of a reaction system at 7.3 by controlling the dropping speed, keeping the reaction temperature at 55 ℃, and after the addition is finished, reacting the suspension in a reactor for 24 hours and then aging for 1 hour;
(3) And (3) centrifuging the material obtained in the step (2), drying, sieving and removing iron to obtain the spheroidal nickel manganese carbonate precursor with the size of 6 microns.
The obtained Ni 0.24 Mn 0.74 La 0.02 (CO 3 ) 0.99 F 0.02 The precursor is pretreated for 4h at 850 ℃ and then mixed with Li in stoichiometric ratio 2 CO 3 And after uniformly mixing, placing the mixture in an air muffle furnace for sintering, and sintering at 850 ℃ for 10 hours to obtain the required lithium nickel manganese oxide cathode material.
And (3) electrical property detection: the positive plate adopts the following formula: conductive agent: 1, binder =8, and a lithium metal sheet is used as a negative electrode sheet, an R2032 type battery test is prepared, and a neomycin tester is adopted to test that the 1C discharge gram capacity is 133.2mAh/g, the tap density is: 1.84g/cm 3 And the capacity retention rate is 92.0 percent after 500 weeks of normal-temperature circulation.
Comparative example 1
The embodiment provides an Al and F co-doped nickel-manganese binary precursor, and the chemical general formula of spinel lithium nickel manganese oxide is Ni 0.24 Mn 0.74 Al 0.02 (CO 3 ) 0.99 F 0.02 。
The embodiment also provides a preparation method of the nickel-manganese binary precursor, which comprises the following steps:
(1) Weighing nickel sulfate, manganese sulfate and aluminum sulfate according to the molar ratio of Ni to Mn to Mg = 12; preparing an ammonium bicarbonate buffer solution with the pH value of 7.8 to obtain a mixed solution B; preparing CTAB solution according to 1.5wt% of the mass of the mixed metal salt to obtain mixed solution C; preparing a mixed solution D with the concentration of 0.75mol/L of sodium carbonate according to the mol ratio F (ammonium fluoride) to C (sodium carbonate) = 2;
(2) Adding CTAB and ammonium bicarbonate buffer solution into a reaction kettle, introducing nitrogen, starting stirring, slowly pumping the mixed solution A and the mixed solution D into a base solution by a peristaltic pump at a feeding speed of 0.05L/h, keeping the pH value of a reaction system at 7.8 by controlling a dropping speed, keeping the reaction temperature at 60 ℃, and after the addition is finished, reacting the suspension in the reactor for 24 hours and then aging for 1 hour;
(3) And (3) centrifuging the material obtained in the step (2), drying, sieving and removing iron to obtain the nickel-manganese carbonate precursor.
The obtained Ni 0.24 Mn 0.74 Al 0.02 (CO 3 ) 0.99 F 0.02 The precursor is pretreated for 4 hours at 830 ℃, and then is mixed with Li in stoichiometric ratio 2 CO 3 And after uniformly mixing, placing the mixture in an air muffle furnace for sintering, and sintering at 830 ℃ for 11h to obtain the required lithium nickel manganese oxide cathode material.
And (3) electrical property detection: the positive plate adopts the following formula: conductive agent: 1, binder =8, and a lithium metal sheet is used as a negative electrode sheet to prepare an R2032 type battery for testing, and a Xinwei tester is adopted to test the battery under a charge-discharge system of charging 4.95V and discharging 3.5V, wherein 1C discharge gram capacity is 128.6mAh/g, tap density: 1.81g/cm 3 And the capacity retention rate is 86.4 percent after 500 weeks of normal-temperature circulation.
The above-mentioned embodiments are only used for explaining the inventive concept of the present invention, and do not limit the protection of the claims of the present invention, and any insubstantial modifications of the present invention using this concept shall fall within the protection scope of the present invention.
Claims (7)
1. A preparation method of a doped spherical nickel-manganese binary precursor is characterized by comprising the following steps:
(1) Preparing a mixed metal salt solution of manganese salt, nickel salt and M salt according to a stoichiometric ratio to obtain a mixed solution A; preparing an organic buffer solution with the pH value of 7.3-7.8 to obtain a mixed solution B; preparing a surfactant solution according to 1-3 wt% of the total mass of the mixed metal salt to obtain a mixed solution C; preparing a mixed solution of ammonium fluoride and sodium carbonate according to a stoichiometric ratio to obtain a mixed solution D; m is selected from one or more of Al, Y, zr, cr, zn, bi, la, ti, mg and Nb;
(2) Adding the mixed solution B and the mixed solution C into a reaction kettle, introducing nitrogen, starting stirring, slowly pumping the mixed solution A and the mixed solution D into the reaction kettle by a peristaltic pump at a feeding speed of 0.05-0.15L/h, keeping the pH value of the reaction system at 7.3-7.8 by controlling the dropping speed, controlling the reaction temperature at 45-60 ℃, and after the addition is finished, reacting the suspension in the reaction kettle for 20-30 h and then aging for 1-2 h;
(3) Centrifuging, drying, sieving and removing iron from the material obtained in the step (2) to obtain a nickel-manganese carbonate precursor; the chemical general formula of the nickel manganese carbonate precursor is Ni 0.25-x Mn 0.75-x M 2x (CO 3 ) 1-y F 2y, Wherein x is more than or equal to 0 and less than or equal to 0.05,0 and less than or equal to 0.05.
2. The method for preparing the doped spherical nickel-manganese binary precursor as claimed in claim 1, wherein the method comprises the following steps: the organic buffer solution in the step (1) is one or more of TES, HEPES, BES and MOPS.
3. The preparation method of the doped spherical nickel-manganese binary precursor as claimed in claim 1, wherein: the surfactant in the step (1) is one or more of CTAB, SDBS and PVP.
4. The preparation method of the doped spherical nickel-manganese binary precursor as claimed in claim 1, wherein: the metal in the mixed solution A in the step (1)The sum of the ion concentrations is 0.5 to 1.5mol/L; CO in the mixed solution D 3 2- The ion concentration is 0.5-1.5 mol/L.
5. The preparation method of the doped spherical nickel-manganese binary precursor as claimed in claim 1, wherein: the nickel manganese carbonate precursor is spherical or quasi-spherical, and the size of the nickel manganese carbonate precursor is 5-7 mu m.
6. A preparation method for preparing a lithium nickel manganese oxide positive electrode material by using the doped spherical nickel manganese binary precursor obtained by the method of claim 1 is characterized by comprising the following steps: pretreating a carbonate precursor of a lithium nickel manganese oxide positive electrode material at 850-900 ℃, and then mixing the pretreated precursor with Li 2 CO 3 After being uniformly mixed, the mixture is sintered at the temperature of 750-850 ℃ to obtain the lithium nickel manganese oxide anode material.
7. The method for preparing the lithium nickel manganese oxide positive electrode material of claim 6, wherein the method comprises the following steps: the ventilation flow rate of the sintering is 1m 3 /h～3m 3 H; the sintering time is 10-18 h.
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