CN112993239A - High-pressure-resistant low-cobalt ternary cathode material and preparation method thereof - Google Patents
High-pressure-resistant low-cobalt ternary cathode material and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a high-pressure-resistant low-cobalt ternary cathode material and a preparation method thereof, wherein the cathode material is prepared from a precursor containing nickel, cobalt and manganese, a lithium source and a small amount of additives through the following steps: the high-pressure-resistant low-cobalt ternary cathode material is prepared by pre-treating a precursor, mixing the precursor, a lithium source and an additive, sintering and post-treating.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to an improvement method of a nickel cobalt lithium manganate positive electrode material.
Background
The ternary 5 material is wide in application field at present, and is used in the 3C digital and power fields, but the implementation of national back-up policy, many battery companies take 'cost reduction' as the subject of recent years, and the later development direction of the ternary material becomes great. At present, the production cost of proportional ternary materials such as NMC532 and NMC622 is relatively high, and the price is not advantageous, so that a ternary material with low cost and good performance is urgently sought by many battery companies. In addition, in the 3C digital high voltage field, the pure lithium cobaltate material is adopted to gradually approach to the ternary material, 5-series high voltage material is the first choice, and the market demand for high voltage ternary 5-series material is increasing, so that the development of a 5-series material low cost material for high voltage use is urgent.
Disclosure of Invention
Based on the above technical background, the present inventors have made a keen search and, as a result, have found that: the high-pressure-resistant low-cobalt ternary cathode material is prepared by adopting a precursor containing nickel, cobalt and manganese, a lithium source and a small amount of additive doped with element D through a one-step solid phase sintering process, the cathode material has high morphology regularity and uniform particle size, a lithium ion battery prepared from the cathode material still has low internal resistance and excellent high-temperature cycle performance under high pressure, and the cathode material has the advantages of simple preparation process, wide raw material source, low cost and high process amplification feasibility, thereby completing the invention.
The invention provides a high-pressure-resistant low-cobalt ternary cathode material, which is prepared from a precursor containing nickel, cobalt and manganese, a lithium source and an additive containing a D element;
wherein, the lithium source is selected from one or more of lithium-containing carbonate, organic salt, oxide and hydroxide;
the additive containing the D element is selected from one or more of D-containing oxide, carbonate, organic salt or hydroxide; the D element is one or more selected from metal elements.
The second aspect of the present invention provides a method for preparing the high pressure resistant low cobalt ternary cathode material according to the first aspect of the present invention, the method comprising the following steps:
step 1, pretreating a nickel, cobalt and manganese-containing precursor;
step 2, mixing the pretreated precursor, a lithium source and an additive containing a D element;
step 3, sintering the mixture obtained in the step 2;
and 4, post-treatment.
The third aspect of the invention provides a high-pressure-resistant low-cobalt ternary cathode material prepared by the preparation method of the second aspect of the invention.
The preparation method of the high-pressure-resistant low-cobalt ternary cathode material and the cathode material prepared by the method have the following advantages:
(1) the preparation method of the high-pressure-resistant low-cobalt ternary cathode material is simple and is easy to use in batch production on a production line;
(2) the precursor used by the invention has low cobalt content, and the cost of the material is effectively reduced;
(3) the button cell prepared from the anode material prepared by the invention has lower internal resistance under high voltage, and the internal resistance changes less along with the cycle times;
(4) the button cell prepared from the anode material prepared by the invention has excellent cycle performance at high temperature and high pressure.
Drawings
Fig. 1 shows a scanning electron microscope picture of an Nd-based additive added;
fig. 2 shows a scanning electron microscope picture without the addition of Nd-based additives;
FIG. 3 shows the effect of the addition of Nd-based additives on the plateau pressure drop during cycling (test conditions: 3.0-4.6V for button cell, 1C cycle at 25 ℃);
FIG. 4 shows the effect of the addition of Nd-based additives on the change in internal resistance during cycling (test conditions: 3.0-4.6V for button cells, 1C cycle at 25 ℃);
FIG. 5 shows the effect of the addition of Nd-based additives on high temperature cycling performance (test conditions: 3.0-4.5V for button cell, 1C cycle at 55 ℃).
Detailed Description
The present invention will be described in detail below, and features and advantages of the present invention will become more apparent and apparent with reference to the following description.
The invention provides a high-pressure-resistant low-cobalt ternary cathode material, which is prepared from a precursor containing nickel, cobalt and manganese, a lithium source and an additive containing a D element, wherein the D element is selected from one or more of metal elements.
In the invention, a low-cobalt ternary cathode material with low cost and high pressure resistance is mainly provided, therefore, a material with low cobalt content is preferably adopted as a precursor, and the reduction of the cobalt content greatly reduces the cost of the prepared cathode material, but also causes the rate capability of the battery prepared from the material to be poor, therefore, when the material with low cobalt content is used as the precursor to prepare the cathode material, an additive is required to be added to reduce the mixed arrangement of a crystal structure in the prepared cathode material, improve the structural stability and further improve the rate capability of the material.
The lithium source is selected from lithium-containing compounds, preferably, the lithium source is selected from one or more of lithium-containing carbonate, organic salt, oxide and hydroxide; more preferably, the lithium source is selected from one or more of lithium-containing carbonates and oxides.
The additive containing the D element is selected from one or more of D-containing oxide, carbonate, organic salt or hydroxide; preferably one or more of D-containing oxide and carbonate; more preferably an oxide containing D.
In the invention, D is selected from one or more of elements in the subgroup.
The invention aims to provide the anode material used under the high-voltage state, and the phenomena of more oxygen vacancies, poor crystal result stability and the like easily occur under the high voltage, so that the phenomena of material rate capability reduction, poor capacitance and the like occur, and potential safety hazards occur even when the anode material is used under the high voltage.
Therefore, when the additive containing the element D is selected, the element with the radius equivalent to that of the atoms of nickel, cobalt and manganese and the larger electronegativity is preferred, and the element with the radius equivalent to that of the atoms of Ni, Co and Mn is selected, so that the element can enter the transition metal layer in the synthesis process, the structure of the transition metal layer is stabilized, the elution of the transition metal atoms of Ni, Co and Mn is further inhibited, the structural collapse of the material in the charge and discharge cycle process is prevented, the structural stability is protected, and the material rate capability is improved.
The elements with larger electronegativity are selected, so that the bond energy formed between the elements and oxygen elements is stronger than that of Ni-O, Co-O, Mn-O, and when the elements are used under high voltage, a large number of vacancies do not occur in oxygen atoms, thereby improving the stability of the material structure.
According to the invention, D is one or more of rare earth elements Y, W and Mo, preferably one or more of Nd, Y, W and Mo.
The additive containing Nd element is selected, mainly used for improving the stability of a crystal structure and reducing mixed row, especially under high voltage, the oxygen vacancy in the crystal structure is increased, and because the electronegativity of the Nd element is larger, the Nd-O bond energy is stronger than that of Ni-O, Co-O, Mn-O bond energy, the addition of the Nd element can play a role of pulling oxygen under high voltage, the increase of the oxygen vacancy is avoided, and the function of protecting the stability of the structure is played.
In the invention, an additive containing Nd element is selected, a multi-element co-doping mode is adopted, other elements are added to be mutually promoted with Nd, and more lithium ions are diffused into the material, so that the electric capacity of the prepared battery is improved.
When the co-doping element is selected, the element with the same radius and electronegativity as Nd is preferably selected, so that the co-doping element and Nd form a mutual synergistic promotion effect, the lattice stability of the prepared positive pole material sheet is improved, the mixed arrangement is reduced, the charge transfer and ion transport characteristics are improved, and the multiplying power performance of the material is improved.
In the present invention, the precursor containing nickel, cobalt, and manganese is preferably a precursor having a low cobalt content, and more preferably a precursor having an empirical formula (Ni)0.5Co0.1Mn0.4)(OH)2The precursor of (1).
In the invention, the molar ratio of lithium in the nickel, cobalt and manganese-containing precursor and the lithium source to D in the additive is 1: (1.0-1.1): (0.00005 to 0.001); preferably 1: (1.02-1.08): (0.00008 to 0.0008); more preferably 1: (1.03-1.07): (0.0001 to 0.0005);
when more than one doping element is present, the other elements are also added in the above molar ratios.
In the invention, the doping amount of the additive is controlled within a proper range, the addition of the additive can enable doping elements to enter crystal lattices, reduce the phenomenon of ion mixing, improve the structural stability and improve the electrochemical performance of the anode material, and the doping effect cannot be achieved when the addition amount of the dopant is too small. If the addition amount of the additive is too large, the doped metal ions are replaced to reduce the capacity or the cycle performance of the lithium battery, and redundant metal ions can not enter material lattices to greatly reduce the capacity.
The high-pressure-resistant low-cobalt ternary cathode material is spherical, the particle size is 3-6 mu m, and the 50-week circulation capacity retention rate is higher under the conditions of 55 ℃/4.6V and 1C; preferably, the retention rate of the 50-week circulation capacity is more than 95% under the conditions of 55 ℃/4.6V and 1C; more preferably, the capacity retention rate of the resin is more than 97% under the conditions of 55 ℃/4.6V and 1C for 50 weeks.
The high-voltage-resistant low-cobalt ternary cathode material can be applied to a high-voltage environment.
The second aspect of the present invention provides a method for preparing the high pressure resistant low cobalt ternary cathode material according to the first aspect of the present invention, the method comprising the following steps:
step 1, pretreating a precursor containing nickel, cobalt and manganese.
In the invention, the precursor containing nickel, cobalt and manganese is preferably a precursor with low cobalt content,more preferably has the empirical formula (Ni)0.5Co0.1Mn0.4)(OH)2The precursor of (1).
The invention adopts a one-time solid phase sintering process to prepare the high-pressure-resistant low-cobalt ternary cathode material, and the preparation method has the advantages of simple process, lower cost, convenient operation and easy realization of large-scale industrial production.
In the present invention, the pretreatment of the precursor includes pulverization and sieving. And (3) crushing the precursor to obtain the precursor with uniform particle size.
According to the present invention, the pulverization is carried out by a pulverization method commonly used in the art, preferably by mechanical pulverization, more preferably by a pulverizer.
In order to ensure that the anode material prepared from the precursor has excellent performance, the particle size of the precursor needs to be uniform and kept in a smaller particle size range.
In the invention, the crushed precursor is screened, preferably by a 100-300 mesh screen, and more preferably by a 150-200 mesh screen.
And 2, mixing the pretreated precursor, a lithium source and the additive containing the D element.
In the present invention, the precursor containing nickel, cobalt, and manganese is preferably a precursor having a low cobalt content, and more preferably a precursor having an empirical formula (Ni)0.5Co0.1Mn0.4)(OH)2The precursor of (1).
In the present invention, more preferably has an empirical formula (Ni)0.5Co0.1Mn0.4)(OH)2The precursor of (1). On one hand, the preparation cost of the anode material is effectively reduced due to low cobalt content, and on the other hand, the manganese content is higher, and the manganese is a framework material in the prepared anode material and plays a role in stabilizing the structure, so that the manganese content is high, the volume expansion rate of the prepared battery is smaller in the charge-discharge cycle process, and the prepared battery is safer and more beneficial to use under high voltage.
According to the invention, the lithium source is selected from lithium-containing compounds, the additive being an additive containing the element D.
In the invention, in order to reduce the cost, the precursor with lower cobalt content is adopted for preparation, but the reduction of the cobalt content can reduce the stability of the crystal structure of the material, increase the mixed discharge, cause the irreversible migration of lithium ions and further reduce the rate capability and the capacity of the material. In order to increase the stability of the material structure, additives containing other elements are added in the preparation process to improve the stability of the material crystal structure, so that the rate capability of the material is increased.
The lithium source is selected from lithium-containing compounds, preferably, the lithium source is selected from one or more of lithium-containing carbonate, organic salt, oxide and hydroxide; more preferably, the lithium source is selected from one or more of lithium-containing carbonates and oxides.
The additive containing the D element is selected from one or more of D-containing oxide, carbonate, organic salt or hydroxide; preferably one or more of D-containing oxide and carbonate; more preferably an oxide containing D.
The positive electrode material is prepared by adding the additive containing the D element, and mainly aims to improve the rate performance deterioration caused by the reduction of the cobalt content, and specifically, on one hand, the additive can enter a transition metal layer in the synthesis process, stabilize the structure of the transition metal layer and inhibit the dissolution of transition metal atoms Ni, Co and Mn, so that the structural collapse of the material in the charge-discharge cycle process is inhibited, the capacity fading speed is slowed down, and the cycle performance of a battery prepared from the positive electrode material is effectively improved; in the second aspect, the addition of other elements inhibits the Jahn-Teller effect, so that the dissolution and loss of manganese are reduced, the reduction of manganese serving as a framework material is avoided, the volume expansion rate of the prepared anode material is small in the charge-discharge cycle process, and the anode material is more favorable for being used under high voltage; in the third aspect, because oxygen vacancies on the surface of the material are increased in high-voltage charge-discharge cycles, a stronger bond needs to be formed between an element with larger electronegativity and oxygen to inhibit the increase of the oxygen vacancies, so that the stability of the surface structure of the material is ensured, meanwhile, the mixed-row is effectively reduced, the multiplying power performance of the material is improved, and the positive electrode material capable of being used under high voltage is prepared; in the fourth aspect, due to the addition of other elements, lithium ions can be more favorably diffused into the material, so that the capacitance of the material is improved.
The D is selected from one or more of elements in the subgroup, preferably, the D is one or more of rare earth elements, Y, W and Mo, and more preferably, the D is one or more of Nd, Y, W and Mo.
In the invention, a codoping additive containing Nd element is selected, a codoping mode of multiple elements is adopted, other elements are added to mutually promote with Nd, and more lithium ions are diffused to the interior of the material, so that the capacitance of the prepared battery is improved.
When the co-doping element is selected, the element with the same radius and electronegativity as Nd is preferably selected, so that the co-doping element and Nd form a mutual synergistic promotion effect, the lattice stability of the prepared positive pole material sheet is improved, the mixed arrangement is reduced, the charge transfer and ion transport characteristics are improved, and the multiplying power performance of the material is improved.
In the invention, the molar ratio of lithium in the nickel, cobalt and manganese-containing precursor and the lithium source to D in the additive is 1: (1.0-1.1): (0.00005 to 0.001); preferably 1: (1.02-1.08): (0.00008 to 0.0008); more preferably 1: (1.03-1.07): (0.0001 to 0.0005);
when more than one doping element is present, the other elements are also added in the above molar ratios.
In the invention, the using amount of the precursor is fixed, the adding amount of the lithium source is calculated according to the mass of the precursor and the lithium proportion, the adding amount of the lithium source is controlled within a reasonable range, if the adding amount of the lithium is insufficient, the lithium diffused into the material is insufficient, and the electric capacity of the finally prepared battery is reduced; if the amount of lithium added is too large, the cycle retention of the positive electrode material may decrease.
The weighed precursor, lithium source and D-element-containing additive are thoroughly mixed, preferably mechanically, more preferably in a small high-speed mixer.
The stirring speed is 500-900 r/min, preferably 600-800 r/min, more preferably 700r/min, and the stirring time is 5-60 min, preferably 10-50 min, more preferably 15-40 min, for example 20 min. The stirring speed is low, and the stirring is not uniform in a short time; to achieve the same mixing effect, it takes a long stirring time, resulting in inefficiency. Too fast a stirring rate may break up precursor particles, affecting the cycle performance of the sintered material. The short stirring time can cause the mixture to be uneven, and the product performance is influenced; too long a stirring time will reduce the actual production efficiency.
And 3, sintering the mixture obtained in the step 2.
According to the invention, the mixed materials are sintered in a muffle furnace, preferably, the mixed materials are sintered after no white spot or white line is found, and the sintering is carried out in three sections, namely low temperature, medium temperature and high temperature;
the low-temperature sintering section mainly decomposes hydroxide ions and is a water removal stage. The low-temperature sintering temperature is 300-700 ℃, and the sintering time is 1-10 h; preferably, the sintering temperature is 400-600 ℃, and the sintering time is 2-8 h; preferably, the sintering temperature is 450-550 ℃, and the sintering time is 4-6 h; for example, sintering at 500 ℃ for 5 h.
The middle-high temperature sintering process is mainly a lithium carbonate decomposition process, the decomposed lithium oxide diffuses into the material, and the nickel, cobalt and manganese are fused by breaking bonds. If the sintering time in the medium-high temperature range is too short and lithium carbonate is not sufficiently decomposed to lithium oxide, too little lithium is diffused into the material, resulting in a decrease in the capacity of the material.
The medium-high temperature sintering temperature is 750-900 ℃, and the sintering time is 5-20 h; preferably, the sintering temperature is 800-850 ℃, and the sintering time is 10-15 h; for example, sintering at 850 deg.C for 12 h.
The high-temperature sintering section is mainly a crystallization stage of the material and is also a key for controlling the grain size of the finally prepared material. If the temperature is too low and the reaction is incomplete, the stable growth of a crystal structure is not facilitated, the crystal structure is incomplete, and a heterogeneous phase is easily contained, so that the structural stability of the battery is poor in the charging and discharging processes, and the electrochemical performance of the battery is poor; if the sintering temperature is too high (for example, higher than 1000 ℃), oxygen-deficient compounds are easily formed and secondary recrystallization is promoted, which causes the material to have large crystal grains and a small specific surface area, which is not favorable for deintercalation of the lithium ion material.
The size of the particle size of the anode material can influence the capacitance of the prepared battery, the larger the particle size is, the smaller the specific surface area of the anode material is, and the contact area of the material in an electrolyte is reduced, so that the dissolution of Ni, Co and Mn is reduced, the capacity decay speed is correspondingly slowed down, and the cycle performance of the material is improved; if the particle size is too small, the specific surface area of the resulting material increases, the contact area with the electrolyte increases, and the conductivity increases, and the capacitance increases accordingly.
The high-temperature sintering temperature is 850-1000 ℃, and the sintering time is 5-20 h; preferably, the sintering temperature is 900-950 ℃, and the sintering temperature is 10-15 h; for example, 930 deg.C for 12 h.
And 4, post-treatment.
According to the invention, after the sintering product in the step 3 is cooled to room temperature, post-treatment is carried out, preferably, the cooling is natural cooling;
in the invention, the post-treatment comprises crushing and sieving, and the sintered product is crushed to obtain the high-pressure-resistant low-cobalt ternary cathode material with uniform particle size, wherein the crushing is carried out by adopting a crushing mode commonly used in the field, preferably mechanical crushing, and more preferably a crusher.
The particle size of the anode material is a key factor influencing the capacitance of the finally prepared battery, the larger the particle size is, the smaller the specific surface area of the anode material is, the smaller the contact area of the anode material and the electrolyte is, the dissolution of Ni, Co and Mn is reduced, and the prepared material has high structural stability, so that the attenuation speed of the capacitance is slowed down, and the rate capability is improved; the smaller the particle size of the positive electrode material is, the larger the specific surface area is, the larger the effective contact area with the electrolyte increases, the conductivity of the material increases, the amount of effective lithium ions for reaction increases, and the capacity of the material increases accordingly. Therefore, the final positive electrode material is crushed and sieved to control the particle size within a proper range, and the electrochemical performance of the final battery is remarkably improved.
Sieving the crushed product, preferably sieving the crushed product by a sieve of 100-500 meshes, more preferably sieving the crushed product by a sieve of 200-300 meshes, for example, 300 meshes.
The third aspect of the invention provides a high-pressure-resistant low-cobalt ternary cathode material prepared by the preparation method of the second aspect of the invention, wherein the particles are in a sphere-like shape, and the particle size is between 3 and 6 mu m. The button cell has excellent electrochemical performance under high pressure, such as small internal resistance change and good high-temperature cycle performance, and the capacity retention rate of the button cell is more than or equal to 95%, preferably more than or equal to 97% after 50 cycles of a cycle performance test of the button cell prepared from the high-pressure-resistant low-nickel cathode material under the conditions of 3.0-4.5V and 55 ℃ and 1C; the button cell prepared from the high-voltage-resistant low-nickel ternary cathode material is subjected to internal resistance test under the conditions of 3.0-4.6V and 25 ℃ at 1C, and the internal resistance of the button cell changes slightly along with the increase of cycle times.
The invention has the following beneficial effects:
(1) the high-pressure-resistant low-cobalt ternary cathode material is prepared by adopting a precursor containing nickel, cobalt and manganese, a lithium source and an additive containing a D element as raw materials through a one-step solid-phase sintering method, the raw materials are wide in source and low in price, and particularly, the cobalt content in the precursor is only 10%, so that the cost of the material is greatly reduced;
(2) according to the invention, trace doping elements are added, so that the finally prepared button cell has good electrochemical performance under high voltage, the high-voltage performance of the cell is improved, and the preparation cost is reduced;
(3) the preparation method disclosed by the invention is used for preparing the high-pressure-resistant low-cobalt ternary cathode material by a one-time solid-phase sintering method, the preparation process is simple, the prepared product is stable in quality, the complex preparation process in the prior art is omitted, the waste of resources and energy is avoided, the production efficiency is improved, the development and preparation costs are reduced, and the large-scale industrial production is easy to realize;
(4) the high-pressure-resistant low-cobalt ternary cathode material prepared by the invention has the advantages that the particle size is between 3 and 6 microns, the boundaries among particles are clear, the particle surfaces are smooth, the particles can be well contacted with a conductive agent, the diffusion of lithium ions is further facilitated, the internal resistance of a battery is effectively reduced, the internal resistance change is small along with the increase of cycle times, and the electrochemical performance of the cathode material is improved;
(5) the high-pressure-resistant low-cobalt ternary cathode material prepared by the method has a spherical-like particle shape, so that the specific surface area of the material is effectively reduced, the contact of the material with an electrolyte is reduced, the dissolution of nickel, cobalt and manganese is reduced, the structural stability is improved, and the rate capability and high-temperature cycle performance of the prepared material are improved;
(6) the button cell prepared from the high-pressure-resistant low-cobalt ternary cathode material has lower internal resistance at 3.0-4.6V and 25 ℃ and 1C, and the internal resistance changes less with the increase of cycle times; the button cell has excellent cycling performance at 3.0-4.5V and 1C at 55 ℃, and the capacity retention rate of the button cell is more than 97% after 50 cycles.
Examples
The invention is further illustrated by the following specific examples, which are intended to be illustrative only and not limiting to the scope of the invention.
Example 1
First, weighing (Ni)0.5Co0.1Mn0.4)(OH)2100g of precursor, 42.30g of lithium carbonate was weighed out in a molar excess of 6% Li, and neodymium oxide (Nd) was weighed out2O3) 0.06g of additive, tungsten oxide (WO)3) 0.038g of additive;
respectively adding the precursor, lithium carbonate and neodymium oxide additives into a small-sized high-speed mixer for mixing, ensuring uniform mixing, and ensuring that white spots and white lines are not found in the mixed material;
the mixture is synthesized for one time in a muffle furnace at the synthesis temperature of 500 ℃/5h +850 ℃/12h +930 ℃/12 h;
and (4) after the muffle furnace is naturally cooled, taking out the material and sieving the material by a 300 molybdenum sieve to obtain a final product.
The scanning electron microscope test is carried out on the prepared final product, the obtained result is shown in figure 1, and as can be seen from figure 1, the prepared particles are in a sphere-like shape, the boundaries of the particles are clear, the particle size is uniform, the small particles do not agglomerate, the particle size is between 3 and 6 microns, and the morphology regularity of the particles is high.
Example 2
First, weighing (Ni)0.5Co0.1Mn0.4)(OH)2100g of precursor, 42.30g of lithium carbonate was weighed out in a molar excess of 6% Li, and neodymium oxide (Nd) was weighed out2O3) 0.06g of additive;
respectively adding the precursor, lithium carbonate and neodymium oxide additives into a small-sized high-speed mixer for mixing, ensuring uniform mixing, and ensuring that white spots and white lines are not found in the mixed material;
the mixture is synthesized for one time in a muffle furnace, and the synthesis temperature refers to 500 ℃/5h +850 ℃/12h +930 ℃/12 h;
after the muffle furnace is naturally cooled, taking out the material and sieving the material by a 300 molybdenum sieve to obtain a final product, and carrying out test analysis;
comparative example
First, weighing (Ni)0.5Co0.1Mn0.4)(OH)2100g of precursor, and 42.30g of lithium carbonate is weighed according to the molar weight of excess 6% Li;
respectively adding the precursor and lithium carbonate into a small-sized high-speed mixer for mixing, so as to ensure uniform mixing, wherein white spots and white lines are not found in the mixed material;
the mixture is synthesized for one time in a muffle furnace, and the synthesis temperature refers to 500 ℃/5h +850 ℃/12h +930 ℃/12 h;
and (4) after the muffle furnace is naturally cooled, taking out the material and sieving the material by a 300 molybdenum sieve to obtain a final product.
The scanning electron microscope test is carried out on the prepared final product, the obtained result is shown in fig. 2, and as can be seen from fig. 2, the prepared final product is roughly spherical, the particle sizes are different, the material without the Nd-based additive has relatively poor morphology regularity, small particle agglomeration phenomenon exists locally, the particle size is about 4um, and compared with the scanning electron microscope photo of the anode material prepared in the embodiment 1, the addition of the additive containing Nd element is beneficial to improving the morphology regularity of the material particles.
Examples of the experiments
Experimental example 1
The plateau voltage drop is obtained by a power-off test, the test voltage is 3.0-4.6V, and the temperature is 25 ℃. The battery is charged and discharged through the first circle of 0.1C/0.1C, the first circle of 0.2C/0.2C, the first circle of 0.5C/1C and the first circle of 0.2C/1C, and the voltage platform is counted to change from the first circle of 0.5C/1C to the voltage platform of 50 circles.
As can be seen from fig. 3, the addition of the Nd-based additive is beneficial to reduce the plateau pressure drop of the material during the circulation process, indicating that the Nd-based additive is beneficial to stabilizing the internal structural stability of the material.
Experimental example 2
The aluminum foil coated on the final products obtained in example 1 and the comparative example were used as a positive plate, a lithium metal plate was used as a negative plate to prepare a button cell, and the button cell was subjected to internal resistance measurement at a voltage of 3.0 to 4.6V and a temperature of 25 ℃. The battery is charged and discharged through the first circle of 0.1C/0.1C, charged and discharged through the first circle of 0.2C/0.2C and circulated for 50 circles through 0.5C/1C, and the internal resistance is counted from the first circle of 0.5C/1C to the voltage internal resistance of 50 circles. The results are shown in FIG. 4.
As can be seen from fig. 4, after the Nd-based additive is added, the internal resistance of the battery is lower than that of the battery without the Nd-based additive, and as the cycle number increases, the internal resistance of the battery prepared after the Nd-based additive is added increases at a very slow speed as the cycle number increases, and the internal resistance after 50 cycles is lower than that of the battery without the Nd-based additive, which indicates that the incorporation of the Nd element is beneficial to reducing the ionic charge transfer resistance of the material during the charge-discharge cycle.
Experimental example 3
The aluminum foils coated on the final products obtained in example 1 and the comparative example were used as positive plates, the lithium metal plate was used as a negative plate to prepare button cells, electrochemical performance of the button cells was tested, and the batteries obtained in example 1 and the comparative example were subjected to cycle performance testing at 3.0 to 4.5V, 55 ℃, 1C rate using a blue bond system, and the results are shown in fig. 5.
As can be seen from fig. 5, the capacity retention rates of the batteries obtained in example 1 were 97% or more, whereas the capacity retention rates of the batteries obtained in comparative example were 95% or more after 30 cycles and 94% or so after 50 cycles. Therefore, the battery capacity retention rate of the high-pressure-resistant low-cobalt ternary cathode material prepared by adding a small amount of the Nd-containing additive is greatly improved, and the Nd-based additive is beneficial to improving the capacity retention rate of the material at high temperature and high pressure and improving the high-temperature cycle performance of the material.
The Nd-O bond energy of the Nd-based additive is stronger than that of Ni-O, Co-O, Mn-O bond energy, and Nd atoms have the same atomic radius as that of Ni, Co and Mn atoms, so that the Nd-O bond energy can enter the transition metal layer in the synthesis process, stabilize the structure of the transition metal layer and inhibit the dissolution of the transition metal atoms Ni, Co and Mn, thereby inhibiting the structural collapse of the material in the charge-discharge cycle process.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. The high-voltage-resistant and low-cobalt-resistant ternary cathode material is characterized by being prepared from a precursor containing nickel, cobalt and manganese, a lithium source and an additive containing a D element, wherein the D element is selected from one or more of metal elements.
2. The high pressure resistant low cobalt ternary positive electrode material of claim 1,
the lithium source is a lithium-containing compound, preferably one or more selected from lithium-containing carbonate, organic salt, oxide and hydroxide; more preferably one or more selected from the group consisting of lithium-containing carbonates and oxides.
3. The high pressure resistant low cobalt ternary positive electrode material of claim 1,
the additive containing the D element is selected from one or more of D-containing oxide, carbonate, organic salt or hydroxide; preferably one or more of D-containing oxide and carbonate; more preferably a B-containing oxide;
the D element is selected from one or more of elements in the subgroup, preferably one or more of rare earth elements, Y, W and Mo, and more preferably one or more of Nd, Y, W and Mo;
the nickel, cobalt and manganese containing precursor is preferably a precursor with low cobalt content, more preferably a precursor with an empirical formula (Ni)0.5Co0.1Mn0.4)(OH)2The molar ratio of lithium in the lithium source to D in the additive containing the D element is 1: (1.0-1.1): (0.00005 to 0.001); preferably 1: (1.02-1.08): (0.00008 to 0.0008).
4. The high-voltage tolerant low-cobalt ternary positive electrode material according to any one of claims 1 to 3,
the high-pressure-resistant low-cobalt ternary cathode material is spherical, and the retention rate of 50-week circulation capacity of the high-pressure-resistant low-cobalt ternary cathode material is high under the conditions of 55 ℃/4.6V and 1C;
the high-voltage-resistant low-cobalt ternary cathode material can be applied to a high-voltage environment.
5. A method for preparing the high voltage tolerant low cobalt ternary positive electrode material according to any one of claims 1 to 4, comprising the steps of:
step 1, pretreating a nickel, cobalt and manganese-containing precursor;
step 2, mixing the pretreated precursor, a lithium source and an additive containing a D element;
step 3, sintering the mixture obtained in the step 2;
and 4, post-treatment.
6. The method according to claim 5, wherein, in step 1,
the pretreatment of the nickel, cobalt and manganese-containing precursor comprises crushing and sieving;
preferably, the pulverization is mechanical pulverization, more preferably, the pulverization is preferably carried out in a pulverizer;
sieving the crushed material, preferably sieving the crushed material by a sieve of 100-300 meshes, and more preferably sieving the crushed material by a sieve of 150-200 meshes.
7. The method according to claim 5 or 6, wherein, in step 2,
the weighed precursor, lithium source and D-element-containing additive are thoroughly mixed, preferably mechanically, more preferably in a small high-speed mixer.
8. The production method according to claim 1, wherein, in step 3,
sintering the mixed material in a muffle furnace, wherein the sintering is carried out in three sections, namely low temperature, medium temperature and high temperature;
the low-temperature sintering temperature is 300-700 ℃, and the sintering time is 1-10 h;
the medium-high temperature sintering temperature is 750-900 ℃;
the high-temperature sintering temperature is 850-1000 ℃.
9. The method according to one of claims 5 to 8, characterized in that, in step 4,
after the sintering product in the step 3 is cooled to room temperature, performing post-treatment, preferably, the cooling is natural cooling;
the post-treatment comprises crushing and sieving, preferably sieving by a sieve of 100-500 meshes, and more preferably sieving by a sieve of 200-300 meshes.
10. A high pressure resistant low cobalt ternary positive electrode material made according to the method of any one of claims 5 to 9.
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