Patent Application
20250122093
The present application belongs to a technical field of lithium-rich manganese-based positive electrode materials, and relates to a manganese-based carbonate precursor of a positive electrode material for a secondary battery and a preparation method thereof, a lithium-rich manganese-based positive electrode material and a preparation method thereof, and a lithium-ion secondary battery, in particular to a manganese-based carbonate precursor containing a trace amount of Na element, a lithium-rich manganese-based positive electrode material and a lithium-ion secondary battery.
Short endurance mileage and high cost are two major problems that must be solved to further increase a penetration rate of electric vehicles. Cost of s battery cell accounts for more than 30% of a total cost of an electric vehicle. Therefore, it is of great significance to improve an energy density and reduce a cost of power lithium-ion batteries. Lithium-rich manganese-based positive electrode material is a new type of high-energy-density and low-cost positive electrode material. However, in order for the lithium-rich manganese-based positive electrode material to exert a high specific capacity (>230 mAhg−1), its operating voltage window should be no less than 4.5V vs Li/Li+ to activate lithium-rich phase Li2MnO3. However, this high voltage window will lead to a decreased structural stability of the material, which is manifested as increased capacity attenuation and average discharge voltage attenuation, which is difficult to meet a cycle life standard in commercial scenarios, restricting the lithium-rich manganese-based positive electrode material's use as an industrialized positive electrode material for power lithium-ion battery. Therefore, improving the initial efficiency and the cycling stability of the lithium-rich manganese-based positive electrode material will accelerate an industrialization process of the material, thereby reducing the total cost of electric vehicles and improving the endurance mileage thereof at the same time.
Commonly used technical means of improving performance of the lithium-rich positive electrode material include bulk phase/surface element doping, surface coating, surface structure reconstruction and so on. For example, CN113540458 discloses a Na-doped lithium-rich positive electrode material prepared by a sol-gel method, where a molar content of Na ion is 0.84%-8.7% of a molar content of Li ion, and a capacity retention rate reaches 86% after 100 cycles at 0.5 C; CN113782748 discloses a surface coated cobalt-free lithium-rich positive electrode material with an inner core doped with Na/K metal ion, and the material has improved initial efficiency and cycling stability, where a cobalt-free precursor and a lithium source are mixed and pre-sintered to obtain a pre-sintered material; the pre-sintered material and a metal salt (sodium dihydrogen phosphate, sodium titanate or sodium alginate) are mixed and calcined to obtain a cobalt-free lithium-rich positive electrode particle; the cobalt-free lithium-rich positive electrode particle is mixed with and coated with an organic lithium salt and is roasted, and then is subjected to wet coating, to obtain a modified cobalt-free lithium-rich positive electrode material, and the obtained material has improved capacity and voltage stability to a certain degree. In English articles ACS Appl.Mater. Interfaces 2019, 11, 37842-37849, J.Mater.Chem.A, 2013, 1, 11397-11403, ACS Appl.Energy Mater. 2020, 3, 9, 8953-8959, Electrochimica Acta 253 (2017) 31-38, RSC Adv., 2015, 5, 93048-93056, Int J Energy Res. 2019; 2-11., ChemElectroChem 10.1002/celc.201901846, Electrochimica Acta 349 (2020) 136402 and ACS Appl.Energy Mater. 2018, 1, 4065-4074, etc., sodium carbonate or sodium hydroxide is used as a sodium source to mix with lithium carbonate and a transition metal precursor, and to undergo solid-state sintering, to obtain a Na-doped lithium-rich positive electrode material, and this method improves electrochemical performance of the lithium-rich positive electrode material to varying degrees; in articles RSC Adv., 2016, 6, 57310, Nano Energy 81 (2021) 105622, Journal of Alloys and Compounds 895 (2022) 162613, ACS Sustainable Chem. Eng.2021, 9, 197-206, Nanotechnology 33 (2022) 065705, J. Mater. Chem. A, 2016, DOI: 10.1039/C5TA07764h, etc., other methods such as spray pyrolysis, sol-gel, hydrothermal method, etc. are used to introduce sodium ions for doping, so as to improve the capacity performance and the cycling stability of a lithium-rich positive electrode material. However, the foregoing modification methods either have a low possibility of industrialization, or after the precursor has been synthesized, use an independent sodium-containing compound as a sodium source to introduce a sodium ion for doping, which increases the process complexity and has a long production cycle, leading to an increase in production cost.
Therefore, it is necessary and urgent to design an industrialized modification method of a lithium-rich material that can significantly improve the initial coulombic efficiency and cycling stability of the lithium-rich manganese-based positive electrode material without significantly increasing the cost. This is also one of the urgent problems to be solved by many frontline researchers in the industry.
In view of this, a technical problem to be solved by the present application is to provide a manganese-based carbonate precursor of a positive electrode material for a secondary battery and a preparation method thereof, a lithium-rich manganese-based positive electrode material and a preparation method thereof, and a lithium-ion secondary battery, in particular to a positive electrode material prepared by a manganese-based carbonate precursor containing a trace amount of Na element. The lithium-rich manganese-based positive electrode material provided in the present application can effectively improve the initial coulombic efficiency, capacity, average discharge voltage, and cycling stability. Moreover, the material is simple in process and has mild and easy-to-control preparation conditions, which is more conducive to the promotion and application of industrialized production.
The present application provides a manganese-based carbonate precursor of a positive electrode material for a secondary battery, and the manganese-based carbonate precursor has a chemical formula NixCoyNazMn1-x-y-zCO3;
In an embodiment, the manganese-based carbonate precursor is a secondary spherical precursor formed by aggregation of primary particles;
In an embodiment, the manganese-based carbonate precursor has a complete carbonate crystal structure;
a corresponding position in a X-Ray Diffractometer (XRD) diffraction spectrum of the manganese-based carbonate precursor is consistent with a peak position in a XRD diffraction spectrum of a standard manganese carbonate;
In an embodiment, the manganese-based carbonate precursor contains an insoluble compound of sodium;
The present application provides a preparation method of the manganese-based carbonate precursor of a positive electrode material for a secondary battery as described in any one of the foregoing technical solutions, including the following steps:
In an embodiment, the nickel source includes a nickel salt solution;
In an embodiment, the main precipitant includes sodium carbonate and/or sodium bicarbonate;
In an embodiment, a temperature of the reaction is between 50-60° C.;
The present application provides a lithium-rich manganese-based positive electrode material, and the positive electrode material has a chemical formula Li1+aMO2+a;
In an embodiment, in a XRD diffraction spectrum of the positive electrode material, a relative height and a FWHM of (003) peak are a and b, respectively, and a relative height and a FWHM of (104) peak are c and d, respectively, then 1.0≤(a/c)*(b/d)≤1.25;
In an embodiment, D50 particle diameter of the positive electrode material is 6.0-14.0 μm;
The positive electrode material is a lithium-rich manganese-based positive electrode material containing a trace amount of Na element.
The present application also provides a preparation method of the lithium-rich manganese-based positive electrode material as described in any one of the foregoing technical solutions, including the following steps:
In an embodiment, a heating rate of the sintering is 0.5-10° C./min;
The present application provides a lithium-ion secondary battery, including a positive electrode sheet, a negative electrode sheet, a separator, and an electrolyte;
In an embodiment, a mass of the positive electrode active material accounts for 90-96% of a total mass of a slurry for preparation of a positive electrode;
The present application provides a manganese-based carbonate precursor of a positive electrode material for a secondary battery, the manganese-based carbonate precursor has a chemical formula NixCoyNazMn1-x-y-zCO3; where, 0.25≤x≤0.35, 0≤y≤0.1, 0.25≤x+y≤0.4, 0.005≤z≤0.03. Compared with the state of art, the present application first designs a manganese-based carbonate precursor with a special structure and composition containing a trace amount of uniformly distributed Na element, where a content of Na is in a range of 0.5-3 mol %, which range can ensure that the structural integrity and consistency of carbonate crystals are not affected. Furthermore, the manganese-based carbonate precursor having the trace amount of uniformly distributed Na element inside thereof provided in the present application has precipitable Na, and by means of simple mixing with the lithium source and sintering, a lithium-rich manganese-based material uniformly doped with Na element can be directly obtained without the need for introducing other Na source, which can effectively avoid uneven doping of Na, improve the doping effect, significantly improve the electrical properties of the material, without significant increase in the production cost. Characterization of XRD characteristics is used to ensure high crystallinity degree and good crystal structure of the primary particles of the manganese-based carbonate precursor.
The present application also provides a synthesis method of the manganese-based carbonate precursor, including quantitatively adding an auxiliary precipitant according to a designed content of Na for coprecipitation. The method is simple, easy to operate, and has highly controllable result and low cost. Furthermore, the present application obtains a lithium-rich manganese-based positive electrode material containing a trace amount of Na element, where Na element uniformly occupies part of lithium sites of the material, plays a structural support role, improves a bulk phase lithium ion transport coefficient and an activity of a phase with a molar ratio of lithium to transition metal elements of 1:1, and reduces a lithium-rich phase activity, stabilizing lattice oxygen, effectively improving a structure stability of long cycling, and suppressing voltage attenuation and gas production. The lithium-rich manganese-based positive electrode material containing the trace amount of Na element provided in the present application may effectively improve an initial charging-discharging coulombic efficiency, a first-cycle discharge capacity, an average voltage and the energy efficiency of a lithium-rich positive electrode.
To further understand the present application, the following describes the embodiments of the present application with reference to the Examples. However, it should be understood that these descriptions are only intended to further describe the features and advantages of the present application, rather than limiting claims of the present application.
All raw materials of the present application are not particularly limited in their sources, and can be purchased on the market or prepared using conventional methods familiar to the skilled in the art.
The purity of all the raw materials in the present application is not particularly limited, and the application adopts analytical reagents or conventional purity requirements in the field of preparation of a positive electrode material for a secondary battery.
Brands and abbreviations of all the raw materials of the present application are conventional brands and abbreviations in this field, and each brand and abbreviation is clear and definite in the related use field, and the skilled in the art can purchase them from the market or prepare them by conventional methods according to the brands, the abbreviations and corresponding uses.
Abbreviations of processes used in the present application are conventional abbreviations in this field, and specific steps and conventional parameters of the abbreviated processes are clear and definite in the related fields, and the skilled in the art can realize the processes in a conventional way according to the abbreviations.
The present application provides a manganese-based carbonate precursor of a positive electrode material for a secondary battery, and the manganese-based carbonate precursor has a chemical formula NixCoyNazMn1-x-y-zCO3;
In the present application, the manganese-based carbonate precursor is a secondary spherical precursor formed by aggregation of primary particles.
In the present application, a shape of the primary particles includes a spherical shape and/or an irregular shape; or is a spherical shape or an irregular shape.
In the present application, an average particle diameter of the primary particles is 50-100 nm, 60-90 nm, or 70-80 nm.
In the present application, D50 particle diameter of the manganese-based carbonate precursor is 3-15 μm, 7-13 μm, or 9-11 μm.
In the present application, a specific surface area of the manganese-based carbonate precursor is 30-80 m2/g, 40-70 m2/g, or 50-60 m2/g.
In the present application, a tap density of the manganese-based carbonate precursor is 1.6-2.2 g/cm3, 1.7-2.1 g/cm3, or 1.8-2.0 g/cm3.
In the present application, an apparent density of the manganese-based carbonate precursor is 0.7-1.4 g/cm3, 0.8-1.3 g/cm3, 0.9-1.2 g/cm3, or 1.0-1.1 g/cm3.
In the present application, the manganese-based carbonate precursor has a complete carbonate crystal structure.
In the present application, a corresponding position in a XRD diffraction spectrum of the manganese-based carbonate precursor is consistent with a peak position in the XRD diffraction spectrum of a standard manganese carbonate.
In the present application, in the XRD diffraction spectrum of the manganese-based carbonate precursor, a relative height and a FWHM of (012) peak are e and f, respectively, and a relative height and a FWHM of (104) peak are g and h, respectively, then 3.3≤g/e≤4.4 (or 3.5≤g/e≤4.3, or 3.7≤g/e≤4.1), 1.0≤f/h≤1.2 (or 1.04≤f/h≤1.16, or 1.08≤f/h≤1.12), 3.0≤(g*h)/(e*f)≤4.0 (or 3.2≤(g*h)/(e*f)≤3.8, or 3.4≤(g*h)/(e*f)≤3.6).
In the present application, the manganese-based carbonate precursor contains an insoluble compound of sodium.
In the present application, the manganese-based carbonate precursor is prepared by a coprecipitation method.
In the present application, the manganese-based carbonate precursor is a manganese-based carbonate precursor containing a trace amount of Na element.
In the present application, the secondary battery includes a lithium-ion secondary battery.
In the present application, in order to complete and refine an overall technical solution to ensure that a structure and parameters of the lithium-rich manganese-based positive electrode material may better improve performances of the secondary battery, the manganese-based carbonate precursor containing the trace amount of Na element can specifically have the following composition:
Specifically, a peak position of a XRD diffraction spectrum of the manganese-based carbonate precursor is consistent with a peak position of a XRD diffraction spectrum of a standard manganese carbonate, and a relative height and a FWHM of (012) peak are recorded as e and f, respectively, and a relative height and a FWHM of (104) peak are recorded as g and h, respectively, satisfying 3.3≤g/e≤4.4, 1.0≤f/h≤1.2, 3.0≤(g*h)/(e*f)≤4.0. The secondary spherical precursor is formed by aggregation of primary particles, the primary particles are an irregular shape or a sphere-like shape with an average particle diameter of 50-100 nm. A particle diameter of the secondary sphere: 3.0 μm≤D50≤15.0 μm, 0.6≤(D90−D10)/D50≤1.5. the secondary sphere has a specific surface area of 30-80 m2/g, a tap density of 1.6 g/cm3≤TD≤2.2 g/cm3, and an apparent density of 0.7 g/cm3≤AD≤1.4 g/cm3.
The manganese-based carbonate precursor provided in the present application has uniformly distributed of a trace amount of Na element inside thereof, and by means of simply mixing it with a lithium source and sintering, a lithium-rich manganese-based material uniformly doped with Na element can be directly obtained without the need for introducing other Na source, which effectively avoids uneven doping of Na, improves the doping effect, and significantly improves the electrical properties of the material, and having no significant increase in the production cost at the same time. Characterization of XRD is used to ensure the high crystallinity degree and good crystal structure of the primary particle of the manganese-based carbonate precursor. The manganese-based carbonate precursor provided by the present application has precipitable Na.
The present application provides a preparation method of the manganese-based carbonate precursor of the positive electrode material for a secondary battery as described in any one of the foregoing technical solutions, including the following steps:
In the present application, the nickel source includes a nickel salt solution.
In the present application, the manganese source includes a manganese salt solution.
In the present application, the cobalt source includes a cobalt salt solution.
In the present application, the nickel salt includes one or more of nickel sulfate, nickel chloride, and nickel nitrate; or is nickel sulfate, nickel chloride, or nickel nitrate.
In the present application, the cobalt salt includes one or more of cobalt sulfate, cobalt chloride, and cobalt nitrate; or is cobalt sulfate, cobalt chloride, or cobalt nitrate.
In the present application, the manganese salt includes one or more of manganese sulfate, manganese chloride, and manganese nitrate; or is manganese sulfate, manganese chloride, or manganese nitrate.
In the present application, the main precipitant includes sodium carbonate and/or sodium bicarbonate; or is sodium carbonate or sodium bicarbonate.
In the present application, the auxiliary precipitant includes sodium nitrite and/or sodium hexanitritocobaltate; or is sodium nitrite or sodium hexanitritocobaltate.
In the present application, a molar ratio of sodium ions in the auxiliary precipitant to sodium ions in the main precipitant is 0.005-0.03, 0.01-0.025, or 0.015-0.02.
In the present application, the complexing agent includes ammonia and/or glycine; or is ammonia or glycine.
In the present application, a temperature of the reaction is between 50-60° C., 52-58° C., or 54-56° C.
In the present application, a pH value during the reaction is 7.5-8.2, 7.6-8.1, 7.7-8.0, or 7.8-7.9.
In the present application, a method of the reaction is continuously feeding a raw material into a reaction apparatus for reaction.
In the present application, a reaction time is determined based on a particle diameter of the manganese-based carbonate precursor and/or an amount of an overflowed material during the reaction, based on the particle diameter of the manganese-based carbonate precursor or the amount of the overflowed material during the reaction.
In the present application, in order to complete and refine an overall technical solution to ensure that structure and parameters of the lithium-rich manganese-based positive electrode material may better improve the performances of the secondary battery. The preparation method of the manganese-based carbonate precursor containing the trace amount of Na element specifically includes the following steps:
A salt solution with a total concentration of transition metal ions of 2 mol/L is prepared at a preset ratio by a coprecipitation method, where one or more of nickel sulfate, nickel chloride, and nickel nitrate is used as a nickel source, one or more of cobalt sulfate, cobalt chloride, and cobalt nitrate is used as a cobalt source, one or more of manganese sulfate, manganese chloride and manganese nitrate is used as a manganese source. Sodium carbonate and/or sodium bicarbonate are used as a main precipitant to precipitate the transition metal ions, and one or more of sodium nitrite and sodium hexanitritocobaltate is used as an auxiliary precipitant to precipitate a trace amount of Na ions, where the auxiliary precipitant and the main precipitant satisfy a molar ratio of 0.005≤Na(auxiliary precipitant):Na(main precipitant)≤0.03. An alkali solution with Na ion concentration of 2 mol/L is formulated, and if sodium hexanitritocobaltate is used as the auxiliary precipitant, an amount of the cobalt salt in the salt solution should be appropriately reduced to ensure a constant ratio of transition metals in the resulting product. A complexing agent solution with a total concentration of 0.01-0.03 mol/L is prepared by using one or more of ammonia or glycine as the complexing agent. Then, the salt solution, the alkali solution, and the complexing agent solution are simultaneously pumped into a reaction kettle at a certain flow rate. A temperature of the reaction kettle is maintained at 50-60° C., a stirring speed is 600-800 rpm, and during the reaction, a pH is maintained at 7.5-8.2. After a particle diameter of the manganese-based carbonate precursor or an amount of an overflowed material reaches a target value, the feeding of the salt solution, the alkali solution, and the complexing agent solution are stopped, and the material in the reactor kettle and the overflowed material are transferred to an aging kettle for aging and then washed with a deionized water with a temperature of 20-50° C. by using a suction filtration or centrifugation method. After washing, drying is performed in a drying oven at 120-160° C., to obtain the manganese-based carbonate precursor containing a trace amount of Na element.
In the present application, a small amount of sodium nitrite or sodium hexanitritocobaltate is used as the auxiliary precipitant, which can react with ammonium ions during coprecipitation process, and synchronously and slowly generate an insoluble compound containing sodium, so that Na is uniformly distributed on an bulk phase and an surface of the manganese-based carbonate precursor, and finally, after mixing and sintering with the lithium source, a Na uniformly doped lithium-rich positive electrode can be formed, where chemical formulas for Na+ precipitation reaction as below:
6Na(+)+6NO2(−)+6Co(2+)+2NH4(+)=(NH4)2Na[Co(NO2)6]↓+5Na(+) (a)
2NH4(+)+3Na(+)+[Co(NO2)6](3−)=(NH4)2Na[Co(NO2)6]↓+2Na(+) (b)
6xNO2(−)+6xCo(2+)+(2+2x)NH4(+)+(3+6x)Na(+)+[Co(NO2)6](3−)(1+x)(NH4)2Na[Co(NO2)6]↓|+(2+5x)Na(+) (c)
Where, the formula (a) is a reaction chemical formula when sodium nitrite is used as the auxiliary precipitant alone; the formula (b) is a reaction chemical formula when sodium hexanitritocobaltate is used as the auxiliary precipitant alone; the formula (c) is a reaction chemical formula when both of them are used as the auxiliary precipitant, where x is a constant, which characterizes a relative content of the two kinds of auxiliary precipitants. An introduction of a trace amount of auxiliary precipitant will not cause a great fluctuation of a coprecipitation reaction environment, which can ensure that the crystallinity of the manganese-based carbonate precursor and morphology of the primary particle are not affected.
The present application provides a lithium-rich manganese-based positive electrode material, and a chemical formula of the positive electrode material is Li1+aMO2+a;
In the present application, In a XRD diffraction spectrum of the positive electrode material, a relative height and a FWHM of (003) peak are a and b, respectively, and a relative height and the FWHM of (104) peak are c and d, respectively, then 1.0≤(a/c)*(b/d)≤1.25 (or 1.05≤(a/c)*(b/d)≤1.20, or 1.1≤(a/c)*(b/d)≤1.15).
In the present application, the positive electrode material is a secondary spherical positive electrode material formed by aggregation of primary particles.
In the present application, the primary particles are a spherical shape and/or a hexagonal sheet shape, a spherical shape or a hexagonal sheet shape.
In the present application, an average particle diameter of the primary particles is 80-200 nm, 100-180 nm, or 120-160 nm.
In the present application, D50 particle diameter of the positive electrode material is 6.0-14.0 μm, 7.0-13.0 μm, 9.0-12.0 μm, or 10.0-11.0 μm.
In the present application, a specific surface area of the positive electrode material is 2.5-6.0 m2/g, 3.0-5.5 m2/g, 3.5-5.0 m2/g, or 4.0-4.5 m2/g.
In the present application, a tap density of the positive electrode material is 1.8-2.6 g/cm3, 1.9-2.5 g/cm3, 2.0-2.4 g/cm3, or 2.1-2.3 g/cm3.
In the present application, an apparent density of the positive electrode material is 0.8-1.4 g/cm3, 0.9-1.3 g/cm3, or 1.0-1.2 g/cm3.
In the present application, the positive electrode material is a lithium-rich manganese-based positive electrode material containing a trace amount of Na element.
In the present application, in order to complete and refine an overall technical solution to ensure that structure and parameters of the lithium-rich manganese-based positive electrode material may better improve the performances of the secondary battery. The lithium-rich manganese-based positive electrode material can specifically have the following composition:
Specifically, except for superlattice peaks in a 2θ=20−25° region, main peak positions of the XRD diffraction spectrum of the lithium-rich manganese-based positive electrode material are consistent with those of a standard layered ternary layered LiNiO2. A relative height and a FWHM of (003) peak are recorded as a, b, respectively, a relative height and a FWHM of (104) peak are recorded as c, d, respectively, satisfying 1.0≤(a/c)*(b/d)≤1.25.
Specifically, the lithium-rich manganese-based positive electrode material is a secondary spherical positive electrode material formed by aggregation of primary particles. The primary particles are a sphere-like shape or a hexagonal sheet shape, and have an average particle diameter of 80-200 nm. The secondary spheres have a particle diameter of: 6.0 μm≤D50≤14.0 μm, 0.8≤(D90−D10)/D50≤1.6, a specific surface area of 2.5-6.0 m2/g, a tap density of 1.8 g/cm3≤TD≤2.6 g/cm3, and an apparent density of 0.8 g/cm3≤AD≤1.4 g/cm3.
The in-situ doped lithium-rich manganese-based positive electrode described in the present application can improve the lithium ion transport capacity by uniformly replacing some lithium ions at lithium sites in situ with an appropriate amount of Na ions, and appropriately increasing an interlayer spacing between lithium layers. At the same time, Na ions can play a supporting role, improving the stability of the material structure during a deep deintercalation of lithium ions. In addition, by limiting a molar ratio of Li ions to transition metal ions to 1.25-1.4, a proportion of a lithium-rich phase in the material is slightly lower than a proportion of a ternary layered phase, which may ensure that the positive electrode material has good cycling stability while exerting a high capacity. A restriction of the XRD characterization makes an exposure ratio of (003) and (104) crystal faces of the positive electrode material reasonable, to further balance the capacity utilization and the cycling stability of the positive electrode.
The present application provides a preparation method of the lithium-rich manganese-based positive electrode material as described in any one of the foregoing technical solutions, including the following steps:
In the present application, a heating rate of the sintering is 0.5-10° C./min, 2-8° C./min, or 4-6° C./min.
In the present application, a sintering mode includes a two-stage sintering.
In the present application, a temperature of a first stage of the two-stage sintering is 400-700° C., 450-650° C., or 500-600° C.
In the present application, a time for the first stage of the two-stage sintering is 3-8 h, 4-7 h, or 5-6 h.
In the present application, a temperature of a second stage of the two-stage sintering is 800-900° C., 820-880° C., or 840-860° C.
In the present application, a time for the second stage of the two-stage sintering is 10-15 h, 11-14 h, or 12-13 h.
In the present application, in order to complete and refine an overall technical solution to ensure that the structure and parameters of the lithium-rich manganese-based positive electrode material may better improve the performances of the secondary battery, a preparation method of the lithium-rich manganese-based positive electrode material specifically includes the following steps:
The manganese-based carbonate precursor NixCoyNazMn1-x-y-zCO3 (0.005≤z≤0.03) obtained from the foregoing synthesis method is mixed with a lithium source with a certain stoichiometric ratio thoroughly, where one or more of lithium carbonate, lithium hydroxide, and lithium chloride are used as the lithium source. The mixed material is placed in one of a muffle furnace, a box furnace, a tube furnace, a roller kiln, and a rotary kiln and is sintered using a two-stage heat preservation method under a forced airflow condition, where a temperature of a low-temperature stage is 400-700° C. and a holding time thereof is 3-8 h; a temperature of a high-temperature stage is 800-900° C., a holding time thereof is 10-15 h and a heating rate thereof is 0.5-10° C./min. After sintering and naturally cooling to room temperature, a target lithium-rich positive electrode material is obtained.
In the two-stage sintering method of the present application, the heat preservation of the low-temperature stage may ensure complete decomposition of the manganese-based carbonate precursor and the lithium salt, allowing the reaction to occur fully, the heat preservation of the high-temperature stage may appropriately improve the crystallinity and stability of the material, and forced airflow can timely discharge CO2 released from decomposition of the carbonate precursor, improving the reaction efficiency and the local reaction consistency.
The present application provides a lithium-ion secondary battery, including a positive electrode sheet, a negative electrode sheet, a separator, and an electrolyte; where
In the present application, a mass of the positive electrode active material accounts for 90-96% of a total mass of a slurry for preparing a positive electrode, 91-95%, or 92-94%.
In the present application, a negative electrode active material on the negative electrode sheet includes one or more of metal lithium, graphite, and silicon oxide; or is metal lithium, graphite, or silicon oxide.
In the present application, the lithium-ion secondary battery is a lithium-ion secondary battery of a lithium-rich manganese-based positive electrode material containing a trace amount of Na element.
In the lithium-ion secondary battery of using the lithium-rich manganese-based positive electrode material containing the trace amount of Na element as an active material of the positive electrode sheet in the present application, a battery cell of the lithium-ion secondary battery includes a positive electrode sheet, a negative electrode sheet, a separator, an electrolyte, and a shell. Where, a ratio of a mass of the active material in the positive electrode sheet to a total mass of the slurry of the positive electrode is 90-96%, and the negative electrode active material is one of metallic lithium, graphite and SiO or a combination thereof.
The foregoing steps of the present application provide a manganese-based carbonate precursor containing a trace amount of Na element and a preparation method thereof, a lithium-rich manganese-based positive electrode material and a preparation method thereof, and a secondary battery. In the manganese-based carbonate precursor with a specific structure and composition containing a trace amount of uniformly distributed Na element as designed in the present application, a content of Na is in a range of 0.5-3 mol %, which range can ensure that the structural integrity and consistency of carbonate crystals are not affected. Furthermore, the manganese-based carbonate precursor having the trace amount of uniformly distributed Na element inside thereof provided in the present application has precipitable Na, and by means of simple mixing with a lithium source and sintering, the lithium-rich manganese-based material uniformly doped with Na element can be directly obtained without the need for introducing other Na source, which may effectively avoid uneven doping of Na element, improve the doping effect, and significantly improve the electrical properties of the material, without a significant increase in the production cost at the same time, so it is more conducive to the promotion and application of industrialized production. Characterization of XRD is used to ensure the high crystallinity degree and good crystal structure of the primary particles of the manganese-based carbonate precursor.
The present application also provides a synthesis method for the manganese-based carbonate precursor, including quantitatively adding an auxiliary precipitant according to a designed content of Na to allow coprecipitation. The method is simple and easy to operate, and has a highly controllable result and low cost. Furthermore, the present application obtains a lithium-rich manganese-based positive electrode material containing a trace amount of Na element, where Na element uniformly occupies some of lithium sites of the material, plays a structural support role, improves a bulk phase lithium ion transport coefficient and an activity of a phase with a molar ratio of lithium to transition metal elements of 1:1, reduces a lithium-rich phase activity, stabilizing lattice oxygen, effectively improving a structure stability of long cycling, and suppressing voltage attenuation and gas production.
The lithium-rich manganese-based positive electrode material containing the trace amount of Na element provided in the present application may effectively improve an initial charging-discharging coulombic efficiency, a first-cycle discharge capacity and an average voltage, and the energy efficiency.
To further describe the present application, the following describes a manganese-based carbonate precursor of a positive electrode material for a secondary battery and a preparation method thereof, a lithium-rich manganese-based positive electrode material and a preparation method thereof, and a lithium-ion secondary battery, as provided by the present application, in detail with reference to examples. However, it should be understood that these examples, which are implemented based on the technical solutions of the present application, provide detailed implementation methods and specific operation processes, which are only to further describe the features and advantages of the present application, rather than limiting claims of the present application, and scope of protection of the present application is not limited to the following examples.
The present example is used to describe preparation of a lithium-rich manganese-based positive electrode material containing a trace amount of Na element and a secondary battery using the positive electrode material as provided in the present application.
A salt solution with a total concentration of transition metal ions of 2 mol/L was prepared at a molar ratio of nickel, cobalt and manganese of 20:10:70, where nickel sulfate is used as a nickel source, cobalt sulfate is used as a cobalt source, and manganese sulfate is used as a manganese source. An alkali solution with a Na ion concentration of 2 mol/L was prepared using sodium carbonate as a main precipitant and sodium nitrite as an auxiliary precipitant at a molar ratio of Na(auxiliary precipitant):Na(main precipitant)=0.02. A complexing agent solution with a total concentration of 0.01 mol/L was prepared using ammonia as a complexing agent. Then, the salt solution, the alkali solution and the complexing agent solution were pumped into a reaction kettle at the same time in a flow rate ratio of 1:1.02:1, where a temperature of the reaction kettle is kept at 55° C., a stirring speed is 800 rpm, and a pH is kept at 8.0 during the reaction. After a particle diameter of a precursor was grown to 9.0 μm and an amount of an overflowed material reached 5 kg, a feeding of the salt solution, the alkali solution and the complexing agent solution was stopped, and the material in the reactor kettle and the overflowed material were transferred to an aging kettle for aging. Afterwards, deionized water was used for washing the aged material via suction filtration at atmospheric temperature. After washing was completed, drying was performed in a drying oven at 120° C., to obtain a manganese-based carbonate precursor containing a trace amount of Na element, Ni0.196Co0.098Mn0.686Na0.02CO3, i.e., a matrix material.
Ni0.196Co0.098Mn0.686Na0.02CO3 was mixed with lithium carbonate in a molar ratio of 1:1.4 thoroughly. The mixed material was placed in a muffle furnace and sintered using a two-stage heat preservation method under a forced airflow condition, where a temperature of a low-temperature stage is 450° C. and a holding time thereof is 5 h; a temperature of a high-temperature stage is 850° C., a holding time thereof is 13 h and a heating rate thereof is 5° C./min. After sintering and naturally cooling to room temperature, a lithium-rich manganese-based positive electrode material was obtained.
A secondary battery was prepared by using the lithium-rich manganese-based positive electrode material containing a trace amount of Na element prepared in the present example as a positive electrode active material by the following specific steps: a positive electrode powder was mixed with an conductive agent Super-P and a binder polyvinylidene fluoride (PVDF) in a mass ratio of 92:4:4, an appropriate amount of a N-Methyl pyrrolidone (NMP) solution was added to form a slurry, the slurry was coated to an aluminum foil, dried, and then baked in a vacuum oven at 120° C. for 12 h. Afterwards, a secondary battery was assembled in a glove box under an Ar atmosphere, where a metallic lithium used as a negative electrode and 1 mol/L of LiPF6 was dissolved in a mixed organic solvent in a volume ratio of EC:EMC=3:7 as an electrolyte, to assemble a button type CR2032 battery. The battery was subjected to a first-cycle charging-discharging test at a voltage window of 2.5-4.55 V at a current density of 50 mAg−1 in a constant current charging-discharging mode, then a 200-cycles cycling test at 250 mAg−1. The test results are shown in Table 1. Table 1 shows the physical and chemical parameters and electrical performance of each group of samples provided in the examples and comparative examples of the present application.
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As can be seen from the radial EDS spectrum of Na on the cross-section of the matrix material of the present example and the point distribution thereof as shown in
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As shown in Table 4, Table 4 shows average particle diameters of the primary particles, D50 particle diameters, specific surface areas, tap densities and apparent densities of the manganese-based carbonate precursors provided by the examples and comparative examples of the present application.
The present example is used to describe preparation of a lithium-rich manganese-based positive electrode material containing a trace amount of Na element and a secondary battery using the positive electrode material as provided in the present application.
A salt solution with a total concentration of transition metal ions of 2 mol/L was prepared at a molar ratio of nickel, cobalt and manganese of 20:10:70, where nickel sulfate is used as a nickel source, cobalt sulfate is used as a cobalt source, and manganese sulfate is used as a manganese source. An alkali solution with a Na ion concentration of 2 mol/L was prepared using sodium carbonate as a main precipitant and sodium nitrite as an auxiliary precipitant at a molar ratio of Na(auxiliary precipitant):Na(main precipitant)=0.005. A complexing agent solution with a total concentration of 0.01 mol/L was prepared using ammonia as a complexing agent. Then, the salt solution, the alkali solution and the complexing agent solution were pumped into a reaction kettle at the same time in a flow rate ratio of 1:1.005:1, where a temperature of the reaction kettle is kept at 55° C., a stirring speed is 800 rpm, and a pH is kept at 8.0 during the reaction. After a particle diameter of a precursor was grown to 9.0 μm and an amount of an overflowed material reached 5 kg, feeding of the salt solution, the alkali solution and the complexing agent solution was stopped, and the material in the reactor kettle and the overflowed material were transferred to an aging kettle for aging. Afterwards, deionized water was used for washing the aged material via suction filtration at atmospheric temperature. After washing was completed, drying was performed in a drying oven at 120° C., to obtain a manganese-based carbonate precursor containing a trace amount of Na element, Ni0.199Co0.0995Mn0.6965Na0.005CO3.
Ni0.199Co0.0995Mn0.6965Na0.005CO3 was mixed with lithium carbonate in a molar ratio of 1:1.4 thoroughly. The mixed material was placed in a muffle furnace and sintered using a two-stage heat preservation method under a forced airflow condition, where a temperature of a low-temperature stage is 450° C. and a holding time thereof is 5 h; a temperature of a high-temperature stage is 850° C., a holding time thereof is 13 h and a heating rate thereof is 5° C./min. After sintering and naturally cooling to room temperature, a lithium-rich manganese-based positive electrode material was obtained.
A secondary battery was prepared by using the lithium-rich manganese-based positive electrode material containing a trace amount of Na element prepared in the present example as a positive electrode active material, and the electrical performance of the secondary battery was tested with the same specific steps as Example 1. The test results are shown in Table 1.
The present example is used to describe preparation of a lithium-rich manganese-based positive electrode material containing a trace amount of Na element and a secondary battery using the positive electrode material as provided in the present application.
A salt solution with a total concentration of transition metal ions of 2 mol/L was prepared at a molar ratio of nickel, cobalt and manganese of 20:10:70, where nickel sulfate is used as a nickel source, cobalt sulfate is used as a cobalt source, and manganese sulfate is used as a manganese source. An alkali solution with a Na ion concentration of 2 mol/L was prepared using sodium carbonate as a main precipitant and sodium nitrite as an auxiliary precipitant at a molar ratio of Na(auxiliary precipitant):Na(main precipitant)=0.03. A complexing agent solution with a total concentration of 0.01 mol/L was prepared using ammonia as a complexing agent. Then, the salt solution, the alkali solution and the complexing agent solution were pumped into a reaction kettle at the same time in a flow rate ratio of 1:1.03:1, where a temperature of the reaction kettle is kept at 55° C., a stirring speed is 800 rpm, and a pH is kept at 8.0 during the reaction. After a particle diameter of a precursor was grown to 9.0 μm and an amount of an overflowed material reached 5 kg, feeding of the salt solution, the alkali solution and the complexing agent solution was stopped, and the material in the reactor kettle and the overflowed material were transferred to an aging kettle for aging. Afterwards, deionized water was used for washing the aged material via suction filtration at atmospheric temperature. After washing was completed, drying was performed in a drying oven at 120° C., to obtain a manganese-based carbonate precursor containing a trace amount of Na element, Ni0.194Co0.097Mn0.679 Na0.03CO3.
Ni0.194Co0.097Mn0.679 Na0.03 CO3 was mixed with lithium carbonate in a molar ratio of 1:1.4 thoroughly. The mixed material was placed in a muffle furnace and sintered using a two-stage heat preservation method under a forced airflow condition, where a temperature of a low-temperature stage is 450° C. and a holding time thereof is 5 h; a temperature of a high-temperature stage is 850° C., a holding time thereof is 13 h and a heating rate thereof is 5° C./min. After sintering and naturally cooling to room temperature, a lithium-rich manganese-based positive electrode material was obtained.
A secondary battery was prepared by using the lithium-rich manganese-based positive electrode material containing a trace amount of Na element prepared in the present example as a positive electrode active material, and the electrical performance of the secondary battery was tested with the same specific steps as Example 1. The test results are shown in Table 1.
The present example is used to describe preparation of a lithium-rich manganese-based positive electrode material containing a trace amount of Na element and a secondary battery using the positive electrode material as provided in the present application.
A salt solution with a total concentration of transition metal ions of 2 mol/L was prepared at a molar ratio of nickel to manganese of 25:75, where nickel sulfate is used as a nickel source, and manganese sulfate is used as a manganese source. An alkali solution with a Na ion concentration of 2 mol/L was prepared using sodium carbonate as a main precipitant and sodium nitrite as an auxiliary precipitant at a molar ratio of Na(auxiliary precipitant):Na(main precipitant)=0.02. A complexing agent solution with a total concentration of 0.02 mol/L was prepared using ammonia as a complexing agent. Then, the salt solution, the alkali solution and the complexing agent solution were pumped into a reaction kettle at the same time in a flow rate ratio of 1:1.02:1, where a temperature of the reaction kettle is kept at 60° C., a stirring speed is 700 rpm, and a pH is kept at 8.1 during the reaction. After a particle diameter of a precursor was grown to 7.0 μm and an amount of an overflowed material reached 5 kg, feeding of the salt solution, the alkali solution and the complexing agent solution was stopped, and the material in the reactor kettle and the overflowed material were transferred to an aging kettle for aging. Afterwards, deionized water was used for washing the aged material via suction filtration at atmospheric temperature. After washing was completed, drying was performed in a drying oven at 120° C., to obtain a manganese-based carbonate precursor containing a trace amount of Na element, Ni0.245Mn0.735Na0.02CO3.
Ni0.245Mn0.735 Na0.02CO3 was mixed with lithium carbonate in a molar ratio of 1:1.4 thoroughly. The mixed material was placed in a muffle furnace and sintered using a two-stage heat preservation method under a forced airflow condition, where a temperature of a low-temperature stage is 500° C. and a holding time thereof is 4 h; a temperature of a high-temperature stage is 830° C., a holding time thereof is 15 h and a heating rate thereof is 2° C./min. After sintering and naturally cooling to room temperature, a lithium-rich manganese-based positive electrode material was obtained.
A secondary battery was prepared by using the lithium-rich manganese-based positive electrode material containing a trace amount of Na element prepared in the present example as a positive electrode active material, and the electrical performance of the secondary battery was tested with the same specific steps as Example 1. The test results are shown in Table 1.
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The present example is used to describe preparation of a lithium-rich manganese-based positive electrode material containing a trace amount of Na element and a secondary battery using the positive electrode material as provided in the present application.
A salt solution with a total concentration of transition metal ions of 2 mol/L was prepared at a molar ratio of nickel, cobalt and manganese of 30:2.1:70, where nickel sulfate is used as a nickel source, cobalt sulfate is used as a cobalt source, and manganese sulfate is used as a manganese source. An alkali solution with a Na ion concentration of 2 mol/L was prepared using sodium bicarbonate as a main precipitant and sodium hexanitritocobaltate as an auxiliary precipitant at a molar ratio of Na(auxiliary precipitant):Na(main precipitant)=0.02. A complexing agent solution with a total concentration of 0.03 mol/L was prepared using glycine as a complexing agent. Then, the salt solution, the alkali solution and the complexing agent solution were pumped into a reaction kettle at the same time in a flow rate ratio of 1:1.02:1, where a temperature of the reaction kettle is kept at 50° C., a stirring speed is 800 rpm, and a pH is kept at 7.8 during the reaction. After a particle diameter of a precursor was grown to 9.5 μm and an amount of an overflowed material reached 5 kg, feeding of the salt solution, the alkali solution and the complexing agent solution was stopped, and the material in the reactor kettle and the overflowed material were transferred to an aging kettle for aging. Afterwards, deionized water was used for washing the aged material via suction filtration at atmospheric temperature. After washing was completed, drying was performed in a drying oven at 140° C., to obtain a manganese-based carbonate precursor containing a trace amount of Na element, Ni0.288Co0.02Mn0.672Na0.02CO3.
Ni0.288Co0.02Mn0.672Na0.02CO3 was mixed with lithium carbonate in a molar ratio of 1:1.35 thoroughly. The mixed material was placed in a box furnace and sintered using a two-stage heat preservation method under a forced airflow condition, where a temperature of a low-temperature stage is 500° C. and a holding time thereof is 4 h; a temperature of a high-temperature stage is 860° C., a holding time thereof is 12 h and a heating rate thereof is 4° C./min. After sintering and naturally cooling to room temperature, a lithium-rich manganese-based positive electrode material was obtained.
A secondary battery was prepared by using the lithium-rich manganese-based positive electrode material containing a trace amount of Na element prepared in the present example as a positive electrode active material, and the electrical performance of the secondary battery was tested with the same specific steps as Example 1. The test results are shown in Table 1.
The present example is used to describe preparation of a lithium-rich manganese-based positive electrode material containing a trace amount of Na element and a secondary battery using the positive electrode material as provided in the present application.
A salt solution with a total concentration of transition metal ions of 2 mol/L was prepared at a molar ratio of nickel, cobalt and manganese of 35:2.1:65, where nickel sulfate is used as a nickel source, cobalt sulfate is used as a cobalt source, and manganese sulfate is used as a manganese source. An alkali solution with a Na ion concentration of 2 mol/L was prepared using sodium bicarbonate as a main precipitant and sodium hexanitritocobaltate as an auxiliary precipitant at a molar ratio of Na(auxiliary precipitant):Na(main precipitant)=0.02. A complexing agent solution with a total concentration of 0.02 mol/L was prepared using glycine as a complexing agent. Then, the salt solution, the alkali solution and the complexing agent solution were pumped into a reaction kettle at the same time in a flow rate ratio of 1:1.02:1, where a temperature of the reaction kettle is kept at 50° C., a stirring speed is 800 rpm, and a pH is kept at 7.9 during the reaction. After a particle diameter of a precursor was grown to 12.0 μm and an amount of an overflowed material reached 5 kg, feeding of the salt solution, the alkali solution and the complexing agent solution was stopped, and the material in the reactor kettle and the overflowed material were transferred to an aging kettle for aging. Afterwards, deionized water was used for washing the aged material via suction filtration at atmospheric temperature. After washing was completed, drying was performed in a drying oven at 140° C., to obtain a manganese-based carbonate precursor containing a trace amount of Na element, Ni0.336Co0.02Mn0.624Na0.02CO3.
Ni0.336Co0.02Mn0.624Na0.02CO3 was mixed with lithium carbonate in a molar ratio of 1:1.3 thoroughly. The mixed material was placed in a tube furnace and sintered using a two-stage heat preservation method under a forced airflow condition, where a temperature of a low-temperature stage is 500° C. and a holding time thereof is 4 h; a temperature of a high-temperature stage is 870° C., a holding time thereof is 10 h and a heating rate thereof is 2° C./min. After sintering and naturally cooling to room temperature, a lithium-rich manganese-based positive electrode material was obtained.
A secondary battery was prepared by using the lithium-rich manganese-based positive electrode material containing a trace amount of Na element prepared in the present example as a positive electrode active material, and the electrical performance of the secondary battery was tested with the same specific steps as Example 1. The test results are shown in Table 1.
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The present example is used to describe preparation of a lithium-rich manganese-based positive electrode material containing a trace amount of Na element and a secondary battery using the positive electrode material as provided in the present application.
A salt solution with a total concentration of transition metal ions of 2 mol/L was prepared at a molar ratio of nickel, cobalt and manganese of 35:5:65, where nickel chloride is used as a nickel source, cobalt chloride is used as a cobalt source, and manganese chloride is used as a manganese source. An alkali solution with a Na ion concentration of 2 mol/L was prepared using sodium bicarbonate as a main precipitant and sodium nitrite as an auxiliary precipitant at a molar ratio of Na(auxiliary precipitant):Na(main precipitant)=0.02. A complexing agent solution with a total concentration of 0.01 mol/L was prepared using ammonia as a complexing agent. Then, the salt solution, the alkali solution and the complexing agent solution were pumped into a reaction kettle at the same time in a flow rate ratio of 1:1.02:1, where a temperature of the reaction kettle is kept at 50° C., a stirring speed is 600 rpm, and a pH is kept at 7.8 during the reaction. After a particle diameter of a precursor was grown to 7.5 μm and an amount of an overflowed material reached 5 kg, feeding of the salt solution, the alkali solution and the complexing agent solution was stopped, and the material in the reactor kettle and the overflowed material were transferred to an aging kettle for aging. Afterwards, deionized water was used for washing the aged material via suction filtration at atmospheric temperature. After washing was completed, drying was performed in a drying oven at 120° C., to obtain a manganese-based carbonate precursor containing a trace amount of Na element, Ni0.294Co0.049Mn0.637Na0.02CO3.
Ni0.294Co0.049Mn0.637Na0.02CO3 was mixed with lithium carbonate in a molar ratio of 1:1.34 thoroughly. The mixed material was placed in a roller kiln and sintered using a two-stage heat preservation method under a forced airflow condition, where a temperature of a low-temperature stage is 530° C. and a holding time thereof is 3 h; a temperature of a high-temperature stage is 840° C., a holding time thereof is 14 h and a heating rate thereof is 2° C./min. After sintering and naturally cooling to room temperature, a lithium-rich manganese-based positive electrode material was obtained.
A secondary battery was prepared by using the lithium-rich manganese-based positive electrode material containing a trace amount of Na element prepared in the present example as a positive electrode active material, and the electrical performance of the secondary battery was tested with the same specific steps as Example 1. The test results are shown in Table 1.
The present example is used to describe preparation of a lithium-rich manganese-based positive electrode material containing a trace amount of Na element and a secondary battery using the positive electrode material as provided in the present application.
A salt solution with a total concentration of transition metal ions of 2 mol/L was prepared at a molar ratio of nickel, cobalt and manganese of 25:5:70, where nickel nitrate is used as a nickel source, cobalt nitrate is used as a cobalt source, and manganese nitrate is used as a manganese source. An alkali solution with a Na ion concentration of 2 mol/L was prepared using sodium bicarbonate as a main precipitant and sodium nitrite as an auxiliary precipitant at a molar ratio of Na(auxiliary precipitant):Na(main precipitant)=0.02. A complexing agent solution with a total concentration of 0.01 mol/L was prepared using ammonia as a complexing agent. Then, the salt solution, the alkali solution and the complexing agent solution were pumped into a reaction kettle at the same time in a flow rate ratio of 1:1.02:1, where a temperature of the reaction kettle is kept at 50° C., a stirring speed is 600 rpm, and a pH is kept at 7.8 during the reaction. After a particle diameter of a precursor was grown to 9.0 μm and an amount of an overflowed material reached 5 kg, feeding of the salt solution, the alkali solution and the complexing agent solution was stopped, and the material in the reactor kettle and the overflowed material were transferred to an aging kettle for aging. Afterwards, deionized water was used for washing the aged material via suction filtration at atmospheric temperature. After washing was completed, drying was performed in a drying oven at 120° C., to obtain a manganese-based carbonate precursor containing a trace amount of Na element, Ni0.245Co0.049Mn0.686Na0.02CO3.
Ni0.245Co0.049Mn0.686Na0.02CO3 was mixed with lithium hydroxide in a molar ratio of 1:1.38 thoroughly. The mixed material was placed in a roller kiln and sintered using a two-stage heat preservation method under a forced airflow condition, where a temperature of a low-temperature stage is 500° C. and a holding time thereof is 3 h; a temperature of a high-temperature stage is 830° C., a holding time thereof is 13 h and a heating rate thereof is 2° C./min. After sintering and naturally cooling to room temperature, a lithium-rich manganese-based positive electrode material was obtained.
A secondary battery was prepared by using the lithium-rich manganese-based positive electrode material containing a trace amount of Na element prepared in the present example as a positive electrode active material, and the electrical performance of the secondary battery was tested with the same specific steps as Example 1. The test results are shown in Table 1.
The present example is used to describe preparation of a lithium-rich manganese-based positive electrode material containing a trace amount of Na element and a secondary battery using the positive electrode material as provided in the present application.
A salt solution with a total concentration of transition metal ions of 2 mol/L was prepared at a molar ratio of nickel, cobalt and manganese of 25:5:70, where nickel nitrate is used as a nickel source, cobalt nitrate is used as a cobalt source, and manganese nitrate is used as a manganese source. An alkali solution with a Na ion concentration of 2 mol/L was prepared using sodium bicarbonate and sodium carbonate mixed in a molar ratio of 1:1 as a main precipitant, and sodium nitrite as an auxiliary precipitant at a molar ratio of Na(auxiliary precipitant):Na(main precipitant)=0.02. A complexing agent solution with a total concentration of 0.01 mol/L was prepared using glycine as a complexing agent. Then, the salt solution, the alkali solution and the complexing agent solution were pumped into a reaction kettle at the same time in a flow rate ratio of 1:1.02:1, where a temperature of the reaction kettle is kept at 50° C., a stirring speed is 600 rpm, and a pH is kept at 7.8 during the reaction. After a particle diameter of a precursor was grown to 9.0 μm and an amount of an overflowed material reached 5 kg, feeding of the salt solution, the alkali solution and the complexing agent solution was stopped, and the material in the reactor kettle and the overflowed material were transferred to an aging kettle for aging. Afterwards, deionized water was used for washing the aged material via suction filtration at atmospheric temperature. After washing was completed, drying was performed in a drying oven at 120° C., to obtain a manganese-based carbonate precursor containing a trace amount of Na element, Ni0.245Co0.049Mn0.686Na0.02CO3.
Ni0.245Co0.049Mn0.686Na0.02CO3 was mixed with lithium hydroxide in a molar ratio of 1:1.38 thoroughly. The mixed material was placed in a roller kiln and sintered using a two-stage heat preservation method under a forced airflow condition, where a temperature of a low-temperature stage is 500° C. and a holding time thereof is 3 h; a temperature of a high-temperature stage is 850° C., a holding time thereof is 12 h and a heating rate thereof is 2° C./min. After sintering and naturally cooling to room temperature, a lithium-rich manganese-based positive electrode material was obtained.
A secondary battery was prepared by using the lithium-rich manganese-based positive electrode material containing a trace amount of Na element prepared in the present example as a positive electrode active material, and the electrical performance of the secondary battery was tested with the same specific steps as Example 1. The test results are shown in Table 1.
The present example is used to describe preparation of a lithium-rich manganese-based positive electrode material containing a trace amount of Na element and a secondary battery using the positive electrode material as provided in the present application.
A salt solution with a total concentration of transition metal ions of 2 mol/L was prepared at a molar ratio of nickel, cobalt and manganese of 25:5:70, where nickel nitrate is used as a nickel source, cobalt nitrate is used as a cobalt source, and manganese nitrate is used as a manganese source. An alkali solution with a Na ion concentration of 2 mol/L was prepared using sodium bicarbonate and sodium carbonate mixed in a molar ratio of 1:1 as a main precipitant, and sodium nitrite as an auxiliary precipitant at a molar ratio of Na(auxiliary precipitant):Na(main precipitant)=0.02. A complexing agent solution with a total concentration of 0.01 mol/L was prepared using ammonia and glycine mixed in a molar ratio of 1:1 as a complexing agent. Then, the salt solution, the alkali solution and the complexing agent solution were pumped into a reaction kettle at the same time in a flow rate ratio of 1:1.02:1, where a temperature of the reaction kettle is kept at 50° C., a stirring speed is 600 rpm, and a pH is kept at 7.8 during the reaction. After a particle diameter of a precursor was grown to 9.0 μm and an amount of an overflowed material reached 5 kg, feeding of the salt solution, the alkali solution and the complexing agent solution was stopped, and the material in the reactor kettle and the overflowed material were transferred to an aging kettle for aging. Afterwards, deionized water was used for washing the aged material via suction filtration at atmospheric temperature. After washing was completed, drying was performed in a drying oven at 120° C., to obtain a manganese-based carbonate precursor containing a trace amount of Na element, Ni0.245Co0.049Mn0.686 Na0.02CO3.
Ni0.245Co0.049Mn0.686Na0.02CO3 was mixed with lithium hydroxide in a molar ratio of 1:1.38 thoroughly. The mixed material was placed in a roller kiln and sintered using a two-stage heat preservation method under a forced airflow condition, where a temperature of a low-temperature stage is 500° C. and a holding time thereof is 3 h; a temperature of a high-temperature stage is 830° C., a holding time thereof is 13 h and a heating rate thereof is 2° C./min. After sintering and naturally cooling to room temperature, a lithium-rich manganese-based positive electrode material was obtained.
A secondary battery was prepared by using the lithium-rich manganese-based positive electrode material containing a trace amount of Na element prepared in the present example as a positive electrode active material, and the electrical performance of the secondary battery was tested with the same specific steps as Example 1. The test results are shown in Table 1.
The present example is used to describe preparation of a lithium-rich manganese-based positive electrode material containing a trace amount of Na element and a secondary battery using the positive electrode material as provided in the present application.
A salt solution with a total concentration of transition metal ions of 2 mol/L was prepared at a molar ratio of nickel, cobalt and manganese of 25:5.2:75, where nickel nitrate is used as a nickel source, cobalt nitrate is used as a cobalt source, and manganese nitrate is used as a manganese source. An alkali solution with a Na ion concentration of 2 mol/L was prepared using sodium bicarbonate and sodium carbonate mixed in a molar ratio of 1:1 as a main precipitant, and using sodium hexanitritocobaltate and sodium nitrite mixed in a molar ratio of 1:3 as an auxiliary precipitant at a molar ratio of Na(auxiliary precipitant):Na(main precipitant)=0.03. A complexing agent solution with a total concentration of 0.02 mol/L was prepared using ammonia and glycine mixed in a molar ratio of 1:1 as a complexing agent. Then, the salt solution, the alkali solution and the complexing agent solution were pumped into a reaction kettle at the same time in a flow rate ratio of 1:1.02:1, where a temperature of the reaction kettle is kept at 50° C., a stirring speed is 600 rpm, and a pH is kept at 7.8 during the reaction. After a particle diameter of a precursor was grown to 9.0 μm and an amount of an overflowed material reached 5 kg, feeding of the salt solution, the alkali solution and the complexing agent solution was stopped, and the material in the reactor kettle and the overflowed material were transferred to an aging kettle for aging. Afterwards, deionized water was used for washing the aged material via suction filtration at atmospheric temperature. After washing was completed, drying was performed in a drying oven at 120° C., to obtain a manganese-based carbonate precursor containing a trace amount of Na element, Ni0.24125Co0.005Mn0.72375 Na0.03CO3.
Ni0.24125Co0.005Mn0.72375Na0.03CO3 was mixed with lithium hydroxide in a molar ratio of 1:1.38 thoroughly. The mixed material was placed in a roller kiln and sintered using a two-stage heat preservation method under a forced airflow condition, where a temperature of a low-temperature stage is 500° C. and a holding time thereof is 4 h; a temperature of a high-temperature stage is 840° C., a holding time thereof is 13 h and a heating rate thereof is 2° C./min. After sintering and naturally cooling to room temperature, a lithium-rich manganese-based positive electrode material was obtained.
A secondary battery was prepared by using the lithium-rich manganese-based positive electrode material containing a trace amount of Na element prepared in the present example as a positive electrode active material, and the electrical performance of the secondary battery was tested with the same specific steps as Example 1. The test results are shown in Table 1.
The present example is used to describe preparation of a lithium-rich manganese-based positive electrode material containing a trace amount of Na element and a secondary battery using the positive electrode material as provided in the present application.
A salt solution with a total concentration of transition metal ions of 2 mol/L was prepared at a molar ratio of nickel to manganese of 32:68, where nickel nitrate is used as a nickel source, and manganese nitrate is used as a manganese source. An alkali solution with a Na ion concentration of 2 mol/L was prepared using sodium bicarbonate and sodium carbonate mixed in a molar ratio of 1:1 as a main precipitant, and sodium nitrite as an auxiliary precipitant at a molar ratio of Na(auxiliary precipitant):Na(main precipitant)=0.01. A complexing agent solution with a total concentration of 0.02 mol/L was prepared using ammonia and glycine mixed in a molar ratio of 1:1 as a complexing agent. Then, the salt solution, the alkali solution and the complexing agent solution were pumped into a reaction kettle at the same time in a flow rate ratio of 1:1.01:1, where a temperature of the reaction kettle is kept at 50° C., a stirring speed is 600 rpm, and a pH is kept at 7.8 during the reaction. After a particle diameter of a precursor was grown to 9.0 μm and an amount of an overflowed material reached 5 kg, feeding of the salt solution, the alkali solution and the complexing agent solution was stopped, and the material in the reactor kettle and the overflowed material were transferred to an aging kettle for aging. Afterwards, deionized water was used for washing the aged material via suction filtration at atmospheric temperature. After washing was completed, drying was performed in a drying oven at 120° C., to obtain a manganese-based carbonate precursor containing a trace amount of Na element, Ni0.3168Mn0.6732Na0.01CO3.
Ni0.3168Mn0.6732Na0.01CO3 was mixed with lithium hydroxide in a molar ratio of 1:1.37 thoroughly. The mixed material was placed in a roller kiln and sintered using a two-stage heat preservation method under a forced airflow condition, where a temperature of a low-temperature stage is 500° C. and a holding time thereof is 4 h; a temperature of a high-temperature stage is 855° C., a holding time thereof is 13 h and a heating rate thereof is 2° C./min. After sintering and naturally cooling to room temperature, a lithium-rich manganese-based positive electrode material was obtained.
A secondary battery was prepared by using the lithium-rich manganese-based positive electrode material containing a trace amount of Na element prepared in the present example as a positive electrode active material, and the electrical performance of the secondary battery was tested with the same specific steps as Example 1. The test results are shown in Table 1.
The present comparative example is used to describe preparation of a lithium-rich manganese-based positive electrode material without a trace amount of Na element and a secondary battery using the positive electrode material.
A salt solution with a total concentration of transition metal ions of 2 mol/L was prepared at a molar ratio of nickel, cobalt and manganese of 20:10:70, where nickel sulfate is used as a nickel source, cobalt sulfate is used as a cobalt source, and manganese sulfate is used as a manganese source. An alkali solution with a Na ion concentration of 2 mol/L was prepared using sodium carbonate as a precipitant. A complexing agent solution with a total concentration of 0.01 mol/L was prepared using ammonia as a complexing agent. Then, the salt solution, the alkali solution and the complexing agent solution were pumped into a reaction kettle at the same time in a flow rate ratio of 1:1:1, where a temperature of the reaction kettle is kept at 55° C., a stirring speed is 800 rpm, and a pH is kept at 8.0 during the reaction. After a particle diameter of a precursor was grown to 9.0 μm and an amount of an overflowed material reached 5 kg, feeding of the salt solution, the alkali solution and the complexing agent solution was stopped, and the material in the reactor kettle and the overflowed material were transferred to an aging kettle for aging. Afterwards, deionized water was used for washing the aged material via suction filtration at atmospheric temperature. After washing was completed, drying was performed in a drying oven at 120° C., obtaining a manganese-based carbonate precursor without a trace amount of Na element, Ni0.2Co0.1Mn0.7CO3.
Ni0.2Co0.1Mn0.7CO3 was mixed with lithium carbonate in a molar ratio of 1:1.4 thoroughly. The mixed material was placed in a muffle furnace and sintered using a two-stage heat preservation method under a forced airflow condition, where a temperature of a low-temperature stage is 450° C. and a holding time thereof is 5 h; a temperature of a high-temperature stage is 850° C., a holding time thereof is 13 h and a heating rate thereof is 5° C./min. After sintering and naturally cooling to room temperature, a lithium-rich manganese-based positive electrode material was obtained.
As shown in
A secondary battery was prepared by using the lithium-rich manganese-based positive electrode material prepared in the present comparative example as a positive electrode active material, and the electrical performance of the secondary battery was tested with the same specific steps as Example 1. The test results are shown in Table 1.
The present comparative example is used to describe a preparation of a manganese-based positive electrode material containing a trace amount of Na element by single stage heat preservation sintering and a secondary battery using the positive electrode material.
A salt solution with a total concentration of transition metal ions of 2 mol/L was prepared at a molar ratio of nickel, cobalt and manganese of 20:10:70, where nickel sulfate is used as a nickel source, cobalt sulfate is used as a cobalt source, and manganese sulfate is used as a manganese source. An alkali solution with a Na ion concentration of 2 mol/L was prepared using sodium carbonate as a main precipitant and sodium nitrite as an auxiliary precipitant at a molar ratio of Na(auxiliary precipitant):Na(main precipitant)=0.005. A complexing agent solution with a total concentration of 0.01 mol/L was prepared using ammonia as a complexing agent. Then, the salt solution, the alkali solution and the complexing agent solution were pumped into a reaction kettle at the same time in a flow rate ratio of 1:1.005:1, where a temperature of the reaction kettle is kept at 55° C., a stirring speed is 800 rpm, and a pH is kept at 8.0 during the reaction. After a particle diameter of a precursor was grown to 9.0 μm and an amount of an overflowed material reached 5 kg, feeding of the salt solution, the alkali solution and the complexing agent solution was stopped, and the material in the reactor kettle and the overflowed material were transferred to an aging kettle for aging. Afterwards, deionized water was used for washing the aged material via suction filtration at atmospheric temperature. After washing was completed, drying was performed in a drying oven at 120° C., to obtain a manganese-based carbonate precursor containing a trace amount of Na element, Ni0.199Co0.0995Mn0.6965Na0.005CO3.
Ni0.199Co0.0995Mn0.6965Na0.005CO3 was mixed with lithium carbonate in a molar ratio of 1:1.4 thoroughly. The mixed material was placed in a muffle furnace and sintered heating up to 850° C. at 5° C./min under a forced airflow condition, with a holding time of 13 h at this temperature. After sintering and naturally cooling to room temperature, a lithium-rich manganese-based positive electrode material was obtained.
A secondary battery was prepared by using the lithium-rich manganese-based positive electrode material prepared in the present comparative example as a positive electrode active material, and the electrical performance of the secondary battery was tested with the same specific steps as Example 1. The test results are shown in Table 1.
The present comparative example is used to describe preparation of a lithium-rich manganese-based positive electrode material without a trace amount of Na element and a secondary battery using the positive electrode material.
A salt solution with a total concentration of transition metal ions of 2 mol/L was prepared at a molar ratio of nickel to manganese of 25:75, where nickel sulfate is used as a nickel source, and manganese sulfate is used as a manganese source. An alkali solution with a Na ion concentration of 2 mol/L was prepared using sodium carbonate as a precipitant. A complexing agent solution with a total concentration of 0.02 mol/L was prepared using ammonia as a complexing agent. Then, the salt solution, the alkali solution and the complexing agent solution were pumped into a reaction kettle at the same time in a flow rate ratio of 1:1:1, where a temperature of the reaction kettle is kept at 60° C., a stirring speed is 700 rpm, and a pH is kept at 8.1 during the reaction. After a particle diameter of a precursor was grown to 7.0 μm and an amount of an overflowed material reached 5 kg, feeding of the salt solution, the alkali solution and the complexing agent solution was stopped, and the material in the reactor kettle and the overflowed material were transferred to an aging kettle for aging. Afterwards, deionized water was used for washing the aged material via suction filtration at atmospheric temperature. After washing was completed, drying was performed in a drying oven at 120° C., to obtain a manganese-based carbonate precursor without a trace amount of Na element, Ni0.25Mn0.75CO3.
Ni0.25Mn0.75CO3 was mixed with lithium carbonate in a molar ratio of 1:1.4 thoroughly. The mixed material was placed in a muffle furnace and sintered using a two-stage heat preservation method under a forced airflow condition, where a temperature of a low-temperature stage is 500° C. and a holding time thereof is 4 h; a temperature of a high-temperature stage is 830° C., a holding time thereof is 15 h and a heating rate thereof is 2° C./min. After sintering and naturally cooling to room temperature, a lithium-rich manganese-based positive electrode material was obtained.
As shown in
A secondary battery was prepared by using the lithium-rich manganese-based positive electrode material without a trace amount of Na element prepared in the present comparative example as a positive electrode active material, and its electrical performance was tested with the same specific steps as Example 1. The test results are shown in Table 1.
The present comparative example is used to describe preparation of a manganese-based positive electrode material without a trace amount of Na element and a secondary battery using the positive electrode material.
A salt solution with a total concentration of transition metal ions of 2 mol/L was prepared at a molar ratio of nickel to manganese of 35:65, where nickel sulfate is used as a nickel source, and manganese sulfate is used as a manganese source. An alkali solution with a Na ion concentration of 2 mol/L was prepared using sodium bicarbonate as a precipitant. A complexing agent solution with a total concentration of 0.02 mol/L was prepared using glycine as a complexing agent. Then, the salt solution, the alkali solution and the complexing agent solution were pumped into a reaction kettle at the same time in a flow rate ratio of 1:1:1, where a temperature of the reaction kettle is kept at 50° C., a stirring speed is 800 rpm, and a pH is kept at 7.9 during the reaction. After a particle diameter of a precursor was grown to 12.0 μm and an amount of an overflowed material reached 5 kg, feeding of the salt solution, the alkali solution and the complexing agent solution was stopped, and the material in the reactor kettle and the overflowed material were transferred to an aging kettle for aging. Afterwards, deionized water was used for washing the aged material via suction filtration at atmospheric temperature. After washing was completed, drying was performed in a drying oven at 140° C., to obtain a manganese-based carbonate precursor without a trace amount of Na element, which is Ni0.35Mn0.65CO3.
Ni0.35Mn0.65CO3 was mixed with lithium carbonate in a molar ratio of 1:1.3 thoroughly. The mixed material was placed in a tube furnace and sintered heating up to 870° C. at 2° C./min under a forced airflow condition, with a holding time of 10 h at this temperature. After sintering and naturally cooling to room temperature, a lithium-rich manganese-based positive electrode material was obtained.
As shown in
A secondary battery was prepared by using the lithium-rich manganese-based positive electrode material prepared in the present comparative example as a positive electrode active material, and its electrical performance was tested with the same specific steps as Example 1. The test results are shown in Table 1.
As shown in Table 5, Table 5 shows main XRD parameters of samples provided by the examples and comparative examples of the present application.
The values of (a/c)*(b/d) can be calculated from Table 5. It can be seen that the values of (a/c)*(b/d) of the positive electrodes in Examples 1, 4, and 6 are all less than 1.25, and the values of (a/c)*(b/d) of the comparative examples are all higher than 1.25.
The foregoing provides a detailed introduction of a manganese-based carbonate precursor containing a trace amount Na element, a lithium-rich manganese-based positive electrode material, and a secondary battery as provided by the present application. Specific examples are applied in the present text to explain the principles and embodiments of the present application. The foregoing examples are only used to help understanding the methods and core ideas of the present application, including the best embodiments, and also enable any skilled in the art to practice the present application, including manufacturing and using any apparatus or system, and implementing any combined method. It should be noted that for ordinary skilled in the art, without departing from the principle of the present application, improvements and modifications can be made to the present application, and these improvements and modifications also fall within the scope of protection of the claims of the present application. The scope of protection of the present application is defined by the claims and may include other embodiments that can be thought of by the skilled in the art. If these other embodiments have structural elements that are not different from the textual expression of the claims, or if they include equivalent structural elements that are not substantially different from the textual expression of the claims, then these other embodiments should also be included within the scope of the claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202210759671.0 | Jun 2022 | CN | national |
This application is a continuation of International Application No. PCT/CN2023/077787, filed on Feb. 23, 2023, which claims priority to Chinese Patent Application No. 202210759671.0, filed on Jun. 30, 2022 with China National Intellectual Property Administration. Both of the aforementioned applications are hereby incorporated by reference in their entireties.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/CN2023/077787 | Feb 2023 | WO |
| Child | 19000117 | US |
