CN111816877A - High-nickel cobalt-free quaternary anode material and preparation method thereof - Google Patents
High-nickel cobalt-free quaternary anode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-nickel cobalt-free quaternary anode material and a preparation method thereof, wherein the chemical formula of the anode material is LiNixMnyMzN(1‑x‑y‑z)O2Wherein x is more than or equal to 0.8<1，0<y<0.2，0<z<0.2, M and N are the combination of any two of Al, Mg, Zr, Ti, Cr, W, V, Ce, Fe, Cu, Zn and Nb. The main advantages of the invention are: expensive cobalt element is not used, an ammonia water complexing agent is not used in the preparation process of the precursor, the surface alkali content of the high-nickel cobalt-free quaternary anode material obtained by primary sintering is low, and the washing and secondary sintering processes of the material are not involved, so that the preparation cost is greatly reduced; in addition, the high-nickel cobalt-free quaternary cathode material hasThe specific capacity of the material reaches more than 200mAh/g under 1C multiplying power, the cycling stability is excellent, and the capacity retention rate exceeds 95% after 500 cycles.
Description
Technical Field
The invention relates to the technical field of lithium battery materials, in particular to a high-nickel cobalt-free ternary cathode material and a preparation method thereof.
Background
Lithium ion batteries have high energy density and long life and are therefore ideal energy sources for electric vehicles and other power tools. In the layered transition metal oxide positive electrode material, the nickel cobalt lithium manganate has higher specific capacity, so the research of many people is attracted.
In the nickel cobalt lithium manganate cathode material, nickel mainly plays a role in participating in oxidation-reduction reaction and providing capacity, cobalt has the functions of stabilizing the structure and inhibiting lithium-nickel mixing and phase change, and manganese mainly has the functions of improving thermal stability and safety. The nickel-cobalt-lithium manganate ternary material has good electrochemical performance due to the synergistic effect of nickel, cobalt and manganese.
With the improvement of the endurance requirement of the lithium ion battery, the development of the anode material with higher specific capacity is required. Therefore, in recent years, a high nickel ternary positive electrode material has received much attention. Compared with the common ternary cathode material, the high-nickel ternary cathode material has higher nickel content, so that the specific capacity is higher. However, the increase of the nickel content effectively increases the specific capacity of the ternary cathode material, and brings many disadvantages, such as serious mixed cation discharge, high surface alkali, unstable material structure and easy phase change, which all cause the reduction of the structural stability and the electrochemical cycle performance of the ternary cathode material. Therefore, development of a high nickel ternary positive electrode material with high stability is required. In order to improve the electrochemical performance of the high-nickel ternary cathode material, the high-nickel ternary cathode material needs to be modified, and currently, common modes comprise ion doping, surface coating, gradient material preparation and the like, and the modification processes all make the preparation process more complicated and further improve the preparation cost.
In various ternary cathode materials researched at present, cobalt is indispensable, but due to the scarcity and concentrated distribution of global cobalt resources, the price of cobalt-containing raw materials is higher and higher, the cost of the cathode materials is greatly increased, and further the industrial development of the lithium ion battery technology is hindered. Therefore, it is a current development trend of the cathode material to reduce the cobalt content in the ternary cathode material and even develop cobalt-free materials. For example, researchers have studied binary positive electrode materials such as lithium nickel manganese oxide, lithium nickel magnesium oxide, and lithium nickel aluminum oxide, but the specific capacity and the cycle performance of the binary positive electrode materials are reduced to different degrees compared with those of ternary positive electrode materials, and thus industrialization is difficult to achieve.
Disclosure of Invention
In order to solve the technical problems, the invention provides a high-nickel cobalt-free ternary cathode material and a preparation method thereof, wherein a relatively cheap transition metal element is used for replacing a cobalt element in the ternary material, so that the development cost of the ternary cathode material is greatly reduced.
In order to achieve the technical effect, the invention adopts the following technical scheme:
the invention provides a high-nickel cobalt-free quaternary positive electrode material, which has a chemical formula of LiNixMnyMzN(1-x-y-z)O2Wherein x is more than or equal to 0.8<1，0<y<0.2，0<z<0.2, M and N are the combination of any two metals of Al, Mg, Zr, Ti, Cr, W, V, Ce, Fe, Cu, Zn and Nb.
The invention also provides a preparation method of the high-nickel cobalt-free quaternary anode material, which comprises the following steps:
(1) mixing soluble nickel salt and manganese salt according to a stoichiometric ratio of a chemical formula, and adding deionized water to prepare a mixed salt solution A1; or mixing soluble nickel salt, manganese salt and soluble salt containing M according to the stoichiometric ratio of the chemical formula, and adding deionized water to prepare a mixed salt solution A2; or mixing soluble nickel salt, manganese salt and soluble salt containing M, N according to stoichiometric ratio of chemical formula, adding deionized water to obtain mixed salt solution A3;
(2) adding sodium hydroxide or potassium hydroxide into deionized water to prepare a precipitant solution B;
(3) adding a base solution containing sodium hydroxide or potassium hydroxide into a reactor, and keeping heating and stirring; simultaneously, injecting two solutions A1 and B or A2 and B or A3 and B into the reactor at the same time while introducing inert gas into the bottom liquid of the reactor; after the reaction is finished, filtering, washing the precipitate with deionized water for several times, and drying to obtain a high-nickel binary or ternary or quaternary positive electrode material precursor;
(4) and (3) uniformly mixing the high-nickel binary anode material precursor prepared in the step (3) with a compound containing M and N and a lithium source, or uniformly mixing the high-nickel ternary anode material precursor prepared in the step (3) with a compound containing N and a lithium source, or uniformly mixing the high-nickel quaternary anode material precursor prepared in the step (3) with a lithium source, calcining in an oxygen atmosphere, grinding and sieving the calcined material to obtain the high-nickel cobalt-free quaternary anode material.
The further technical scheme is that the total concentration of metal cations in the mixed salt solution in the step (1) is 0.1-5 mol/L.
The further technical scheme is that the concentration of the precipitant solution in the step (2) is 0.2-10 mol/L.
The further technical scheme is that the volume of the base solution in the step (3) is 10-30% of the total volume of the reactor, the reaction temperature is 40-80 ℃, the inert gas is nitrogen or argon, the pH value of the reaction system is 11-13, and the reaction time is 1-40 h.
The further technical scheme is that the lithium source in the step (4) is lithium carbonate, lithium hydroxide, lithium acetate or lithium nitrate, the molar ratio of the added Li element to the total amount of Ni, Mn, M and N is Li (Ni + Mn + M + N) (1-1.1): 1, the calcining temperature is 600-1000 ℃, and the calcining time is 5-20 hours.
Because expensive cobalt elements are not used in the high-nickel cobalt-free quaternary anode material, an ammonia water complexing agent is not used in the preparation process of the precursor, the high-nickel cobalt-free quaternary anode material obtained by primary sintering has low surface alkali content, and does not relate to the washing and secondary sintering processes of the material, so the preparation cost is greatly reduced; in addition, due to the synergistic effect among various metal ions, the high-nickel cobalt-free quaternary anode material not only has excellent rate performance, but also has good cycle stability.
Compared with the prior art, the invention has the following beneficial effects:
(1) the positive electrode material does not contain cobalt element, an ammonia water complexing agent is not used in the precursor preparation process, the surface alkali content of the high-nickel cobalt-free quaternary positive electrode material obtained by primary sintering is low, and the processes of washing and secondary sintering of the material are not involved, so that the preparation cost is greatly reduced.
(2) By controlling the preparation conditions, the obtained high-nickel cobalt-free quaternary anode material has excellent rate performance and high stability.
Drawings
FIG. 1 is a scanning electron microscope image of a high-nickel cobalt-free quaternary cathode material prepared in example 1 of the present invention;
FIG. 2 is a first-turn charge-discharge curve diagram of the high-nickel cobalt-free quaternary anode material prepared in example 1 of the present invention;
FIG. 3 is a diagram of the cycle performance of the high-nickel cobalt-free quaternary cathode material prepared in example 1 of the present invention.
Detailed Description
The following further describes embodiments of the present invention with reference to the drawings and specific examples.
Example 1
Adding nickel sulfate and manganese sulfate into deionized water according to the molar ratio of metal ions Ni to Mn of 0.95 to 0.03 to obtain a mixed salt solution, wherein the total concentration of the metal ions is 2.0 mol/L; preparing 4.0mol/L NaOH solution. Adding the mixed salt solution into a reaction kettle containing 30% of base solution while stirring, adjusting the dropping speed of the NaOH solution to ensure that the pH of the solution in the reaction kettle is stabilized at 11.3, setting the reaction temperature to be 50 ℃, and continuously introducing N into the solution in the whole reaction process to avoid the oxidation of metal ions2. After reacting for 20h, centrifuging the solution, washing the precipitate for multiple times by using deionized water, and drying to obtain Ni0.95Mn0.03(OH)1.96And (3) precursor. Weighing appropriate amount of the precursor, Al (OH)3、Mg(OH)2And LiOH, wherein the molar ratio of metal elements is Ni, Mn, Al, Mg and Li is 0.95:0.03:0.01:0.01:1.05, the four are uniformly mixed and sintered in a high-temperature furnace, the sintering temperature is 670 ℃, the sintering time is 15 hours, and the sintering atmosphere is O2. After sintering, grinding and sieving the obtained material to obtain the high-nickel cobalt-free quaternary materialPositive electrode material LiNi0.95Mn0.03Al0.01Mg0.01O2. FIG. 1 is a scanning electron microscope image of the high-nickel cobalt-free quaternary cathode material prepared in the present embodiment; FIG. 2 is a first-turn charge-discharge curve diagram of the high-nickel cobalt-free quaternary positive electrode material prepared in this example; FIG. 3 is a diagram of the cycle performance of the high-Ni cobalt-free quaternary cathode material prepared in this example.
Example 2
Adding nickel sulfate, manganese sulfate and magnesium sulfate into deionized water according to the molar ratio of metal ions Ni to Mn to Mg of 0.9 to 0.08 to 0.01 to obtain a mixed salt solution, wherein the total concentration of the metal ions is 5.0 mol/L; 10.0mol/L KOH solution was prepared. Adding the mixed salt solution into a reaction kettle containing 10% of base solution while stirring, and adjusting the dripping speed of the KOH solution to ensure that the pH value of the solution in the reaction kettle is stabilized at 12.0, the reaction temperature is set to be 40 ℃, and in order to avoid the oxidation of metal ions, Ar is continuously introduced into the solution in the whole reaction process. After reacting for 40h, centrifuging the solution, washing the precipitate for multiple times by using deionized water, and drying to obtain Ni0.9Mn0.08Mg0.01(OH)1.98And (3) precursor. Weighing appropriate amount of the precursor and ZrO2And LiNO3Wherein the molar ratio of the metal elements is Ni, Mn, Mg, Zr and Li is 0.9:0.08:0.01:0.01:1.08, the three are uniformly mixed and sintered in a high-temperature furnace, the sintering temperature is 720 ℃, the sintering time is 20h, and the sintering atmosphere is O2. After sintering, grinding and sieving the obtained material to obtain the high-nickel cobalt-free quaternary anode material LiNi0.9Mn0.08Mg0.01Zr0.01O2。
Example 3
Adding nickel sulfate and manganese sulfate into deionized water according to the molar ratio of metal ions Ni to Mn of 0.8 to 0.18 to obtain a mixed salt solution, wherein the total concentration of the metal ions is 1 mol/L; 2.0mol/L NaOH solution is prepared. Adding the mixed salt solution into a reaction kettle containing 20% of base solution while stirring, adjusting the dropping speed of the NaOH solution to ensure that the pH of the solution in the reaction kettle is stabilized at 11, setting the reaction temperature to be 60 ℃, and continuously introducing N into the solution in the whole reaction process to avoid the oxidation of metal ions2. After reaction for 10h, the solution is centrifuged, and the precipitate is washed with deionized water for multiple times and dried to obtain Ni0.8Mn0.18(OH)1.96And (3) precursor. Weighing appropriate amount of the precursor and TiO2、WO3And Li2CO3Wherein the molar ratio of the metal elements is Ni, Mn, Ti, W and Li is 0.8:0.18:0.01:0.01:1.1, the four are uniformly mixed and sintered in a high-temperature furnace, the sintering temperature is 1000 ℃, the sintering time is 5h, and the sintering atmosphere is O2. After sintering, grinding and sieving the obtained material to obtain the high-nickel cobalt-free quaternary anode material LiNi0.8Mn0.18Ti0.01W0.01O2。
Example 4
Adding nickel sulfate, manganese sulfate, magnesium sulfate and chromium sulfate into deionized water according to the molar ratio of metal ions Ni, Mn, Mg and Cr of 0.92:0.05:0.02:0.01 to obtain a mixed salt solution, wherein the total concentration of the metal ions is 0.1 mol/L; 0.2mol/L KOH solution is prepared. Adding the mixed salt solution into a reaction kettle containing 30% of base solution while stirring, adjusting the dripping speed of the KOH solution to ensure that the pH of the solution in the reaction kettle is stabilized at 12.5, setting the reaction temperature to 80 ℃, and continuously introducing N into the solution in the whole reaction process to avoid the oxidation of metal ions2. After reacting for 1h, centrifuging the solution, washing the precipitate for multiple times by using deionized water, and drying to obtain Ni0.92Mn0.05Mg0.02Cr0.01(OH)2.01And (3) precursor. Weighing a proper amount of the precursor and LiOH, wherein the molar ratio of metal elements is Ni, Mn, Mg, Cr and Li is 0.92:0.05:0.02:0.01:1.03, uniformly mixing the metal elements and the LiOH, placing the mixture into a high-temperature furnace for sintering, wherein the sintering temperature is 700 ℃, the sintering time is 15h, and the sintering atmosphere is O2. After sintering, grinding and sieving the obtained material to obtain the high-nickel cobalt-free quaternary anode material LiNi0.92Mn0.05Mg0.02Cr0.01O2。
Example 5
Adding nickel sulfate and manganese sulfate into deionized water according to the molar ratio of metal ions Ni to Mn of 0.93 to 0.04 to obtain a mixed salt solution, wherein the metal ionsThe total concentration of (a) is 2 mol/L; preparing 4.0mol/L NaOH solution. Adding the mixed salt solution into a reaction kettle containing 30% of base solution while stirring, adjusting the dropping speed of the NaOH solution to stabilize the pH of the solution in the reaction kettle at 12.8, setting the reaction temperature at 50 ℃, and continuously introducing N into the solution in the whole reaction process to avoid the oxidation of metal ions2. After reacting for 15h, centrifuging the solution, washing the precipitate for multiple times by using deionized water, and drying to obtain Ni0.93Mn0.04(OH)1.94And (3) precursor. Weighing appropriate amount of the precursor and V2O5、CeO2And LiOH, wherein the molar ratio of metal elements is Ni, Mn, V, Ce and Li is 0.93, 0.04, 0.02, 0.01, 1.01, the four are uniformly mixed and sintered in a high-temperature furnace, the sintering temperature is 650 ℃, the sintering time is 15 hours, and the sintering atmosphere is O2. After sintering, grinding and sieving the obtained material to obtain the high-nickel cobalt-free quaternary anode material LiNi0.93Mn0.04V0.02Ce0.01O2。
Example 6
Adding nickel sulfate, manganese sulfate, ferrous sulfate and copper sulfate into deionized water according to the molar ratio of metal ions Ni to Mn to Fe to Cu of 0.96 to 0.02 to 0.01 to obtain a mixed salt solution, wherein the total concentration of the metal ions is 2 mol/L; preparing 4.0mol/L NaOH solution. Adding the mixed salt solution into a reaction kettle containing 30% of base solution while stirring, adjusting the dropping speed of the NaOH solution to ensure that the pH of the solution in the reaction kettle is stabilized at 13, setting the reaction temperature to be 50 ℃, and continuously introducing N into the solution in the whole reaction process to avoid the oxidation of metal ions2. After reacting for 20h, centrifuging the solution, washing the precipitate for multiple times by using deionized water, and drying to obtain Ni0.96Mn0.02Fe0.01Cu0.01(OH)2And (3) precursor. Weighing a proper amount of the precursor and LiOH, wherein the molar ratio of metal elements is Ni, Mn, Fe, Cu and Li is 0.96:0.02:0.01:0.01:1, uniformly mixing the precursor and the LiOH, placing the mixture into a high-temperature furnace for sintering, wherein the sintering temperature is 600 ℃, the sintering time is 20h, and the sintering atmosphere is O2. After sintering, grinding and sieving the obtained material to obtain the high-nickel cobalt-free quaternary positive electrodeLiNi as a polar material0.96Mn0.02Fe0.01Cu0.01O2。
Example 7
Adding nickel sulfate, manganese sulfate and zinc sulfate into deionized water according to the molar ratio of metal ions Ni to Mn to Zn of 0.88 to 0.08 to 0.02 to obtain a mixed salt solution, wherein the total concentration of the metal ions is 2.0 mol/L; 4.0mol/L KOH solution is prepared. Adding the mixed salt solution into a reaction kettle containing 30% of base solution while stirring, adjusting the dripping speed of the KOH solution, stabilizing the pH of the solution in the reaction kettle at 11.8, setting the reaction temperature to 70 ℃, and continuously introducing N into the solution in the whole reaction process to avoid the oxidation of metal ions2. After reacting for 30h, centrifuging the solution, washing the precipitate for multiple times by using deionized water, and drying to obtain Ni0.88Mn0.08Zn0.02(OH)2And (3) precursor. Weighing appropriate amount of the precursor and Nb2O5And CH3COOLi, wherein the molar ratio of metal elements is Ni, Mn, Zn, Nb and Li is 0.88:0.08:0.02:0.02:1.05, the three are uniformly mixed and placed in a high-temperature furnace for sintering, the sintering temperature is 730 ℃, the sintering time is 15 hours, and the sintering atmosphere is O2. After sintering, grinding and sieving the obtained material to obtain the high-nickel cobalt-free quaternary anode material LiNi0.88Mn0.08Zn0.02Nb0.02O2。
Performance testing
Weighing 10g of the cathode material prepared in examples 1 to 7, adding 100mL of deionized water, stirring for 10min, standing, and measuring the pH of the material by a pH meter as shown in Table 1:
TABLE 1 pH values of examples 1 to 7
| Sample (I) | pH |
| Example 1 | 11.62 |
| Example 2 | 11.57 |
| Example 3 | 11.55 |
| Example 4 | 11.61 |
| Example 5 | 11.59 |
| Example 6 | 11.61 |
| Example 7 | 11.58 |
The positive electrode materials prepared in examples 1 to 7 were made into button half cells, and electrochemical performance tests were performed, and the obtained data are shown in table 2:
TABLE 2 electrochemical performance of button half-cells prepared in examples 1-7
Although the present invention has been described herein with reference to the illustrated embodiments thereof, which are intended to be preferred embodiments of the present invention, it is to be understood that the invention is not limited thereto, and that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure.
Claims (6)
1. The high-nickel cobalt-free quaternary positive electrode material is characterized in that the chemical formula of the high-nickel cobalt-free quaternary positive electrode material is LiNixMnyMzN(1-x-y-z)O2Wherein x is more than or equal to 0.8<1，0<y<0.2，0<z<0.2, M and N are the combination of any two metals of Al, Mg, Zr, Ti, Cr, W, V, Ce, Fe, Cu, Zn and Nb.
2. The preparation method of the high-nickel cobalt-free quaternary anode material is characterized by comprising the following steps of:
(1) mixing soluble nickel salt and manganese salt according to a stoichiometric ratio of a chemical formula, and adding deionized water to prepare a mixed salt solution A1; or mixing soluble nickel salt, manganese salt and soluble salt containing M according to the stoichiometric ratio of the chemical formula, and adding deionized water to prepare a mixed salt solution A2; or mixing soluble nickel salt, manganese salt and soluble salt containing M, N according to stoichiometric ratio of chemical formula, adding deionized water to obtain mixed salt solution A3;
(2) adding sodium hydroxide or potassium hydroxide into deionized water to prepare a precipitant solution B;
(3) adding a base solution containing sodium hydroxide or potassium hydroxide into a reactor, and keeping heating and stirring; simultaneously, injecting two solutions A1 and B or A2 and B or A3 and B into the reactor at the same time while introducing inert gas into the bottom liquid of the reactor; after the reaction is finished, filtering, washing the precipitate with deionized water for several times, and drying to obtain a high-nickel binary or ternary or quaternary positive electrode material precursor;
(4) and (3) uniformly mixing the high-nickel binary anode material precursor prepared in the step (3) with a compound containing M and N and a lithium source, or uniformly mixing the high-nickel ternary anode material precursor prepared in the step (3) with a compound containing N and a lithium source, or uniformly mixing the high-nickel quaternary anode material precursor prepared in the step (3) with a lithium source, calcining in an oxygen atmosphere, grinding and sieving the calcined material to obtain the high-nickel cobalt-free quaternary anode material.
3. The method for preparing the high-nickel cobalt-free quaternary cathode material according to claim 2, wherein the total concentration of metal cations in the mixed salt solution in the step (1) is 0.1-5 mol/L.
4. The preparation method of the high-nickel cobalt-free quaternary cathode material according to claim 2, wherein the concentration of the precipitant solution in the step (2) is 0.2-10 mol/L.
5. The preparation method of the high-nickel cobalt-free quaternary positive electrode material according to claim 2, wherein the volume of the base solution in the step (3) is 10-30% of the total volume of the reactor, the reaction temperature is 40-80 ℃, the inert gas is nitrogen or argon, the pH of the reaction system is 11-13, and the reaction time is 1-40 h.
6. The method for preparing the high-nickel cobalt-free quaternary cathode material according to claim 2, wherein the lithium source in the step (4) is lithium carbonate, lithium hydroxide, lithium acetate or lithium nitrate, the molar ratio of the added Li element to the total amount of Ni, Mn, M and N is Li (Ni + Mn + M + N): 1-1.1: 1, the calcination temperature is 600-1000 ℃, and the calcination time is 5-20 h.
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| CN112582599A (en) * | 2020-12-10 | 2021-03-30 | 万华化学(四川)有限公司 | Cobalt-free high-nickel quaternary positive electrode material, and preparation method and application thereof |
| CN113603158A (en) * | 2021-08-06 | 2021-11-05 | 湖南杉杉能源科技有限公司 | Cobalt-free anode material precursor and preparation method thereof |
| CN113675395A (en) * | 2021-08-19 | 2021-11-19 | 蜂巢能源科技有限公司 | Binary anode material, preparation method thereof and lithium ion battery |
| CN113745494A (en) * | 2021-07-30 | 2021-12-03 | 格林美股份有限公司 | Preparation method of cobalt-free cathode material |
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Application publication date: 20201023 |