CN113258059A - Multi-modified lithium ion battery positive electrode material and preparation method thereof - Google Patents
Multi-modified lithium ion battery positive electrode material and preparation method thereof Download PDFInfo
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Abstract
The chemical formula of the multiple modified lithium ion battery anode material is LiNixCoyMnzCeqO2. nCeO2& LiCoO 2. The preparation method comprises the following steps: (1) adding NiSO4.6H2O, CoSO4.7H2O, MnSO4.H2O and CeO2 into a first reaction kettle, uniformly mixing, then adding an ammonia water solution, and uniformly stirring to obtain a mixed solution; (2) adding hot ammonia water into the second reaction kettle, and then adding the mixed solution for reaction to obtain precursor slurry; (4) carrying out solid-liquid separation on the precursor slurry to obtain a precursor; (3) and mixing the precursor with a lithium source and a cerium source, grinding uniformly, and calcining to obtain the catalyst. The anode material has low production cost, the lithium ion battery assembled by the anode material has good cycle performance and rate capability, and the preparation method has simple and convenient operation.
Description
Technical Field
The invention relates to a lithium ion battery anode material and a preparation method thereof, in particular to a multiple modified lithium ion battery anode material and a preparation method thereof.
Background
With the rapid development of electric vehicles (ev), hybrid vehicles (hev), and plug-in hybrid vehicles (phev), lithium ion batteries with higher energy density and longer cycle life have been widely studied. Ternary materials (NCM type materials) have also attracted considerable attention because of their higher energy density and lower cost. Wherein LiNi0.83Co0.11Mn0.06O2The positive electrode material is considered to be a promising positive electrode material due to high operating voltage. However, at high operating voltages, LiNi0.83Co0.11Mn0.06O2The drastic side reaction between the positive electrode and the electrolyte may cause capacity degradation, and in addition, the structure of the positive electrode material tends to be unstable due to the release of oxygen when it is charged to a high voltage.
In recent years, many researchers have improved electrochemical properties of ternary materials by modification methods, such as ion doping and surface coating. However, studies have shown that the above problems cannot be effectively solved by a single modification method. The coated oxide can reduce side reactions between the positive electrode material and the electrolyte, but the oxide does not have electrochemical activity and generally reduces the specific discharge capacity and energy density of the battery. Although the rate performance of the cathode material can be improved by doping the metal element, the cycle stability of the cathode material is not improved too much.
CN110931738A discloses a complex phase high voltage anode material which is composed of LiNi with hexagonal layered structurex-aCoy-aMnz- aMbO2Rock salt phase (Li + N) O and coating agent A, and its chemical general formula is LiNix-aCoy-aMnz-aMbO2A (Li + N) O.cA; wherein a is more than 0 and less than 0.01, x is more than or equal to 0.33 and less than 1.0, y is more than or equal to 0 and less than or equal to 0.33, z is more than 0.01 and less than 0.5, b is more than 0 and less than 0.02, c is more than 0.001 and less than 0.01, and x + y + z is 1; m is one or more of Mg, Al, Ti, Zr, Sr, Y, Ce, B, W, La, Sn, Zn and Mo; n is one or more of Ni, Co and Mn; the coating agent A is TiO2、ZrO2、Al2O3、SnO2、Li3PO4、Li2B4O7、Li4TiO4And Li2SiO3One kind of (1). The preparation method comprises the following steps: (1) according to the general chemical formula LiNix-aCoy-aMnz-aMbO2·aWeighing nickel-cobalt-manganese hydroxide, a lithium source, a doped M element source and a coating agent A by (Li + N) O & cA; (2) mixing nickel cobalt manganese hydroxide, a lithium source and an M-doped element source, and sintering for the first time to obtain bulk LiNix-aCoy-aMnz-aMbO2·a(Li + N) O; (3) reacting LiNix-aCoy- aMnz-aMbO2·aCrushing (Li + N) O, adding a coating agent A, mixing, sintering for the second time, crushing and sieving to obtain the complex phase high-voltage positive electrode material LiNix-aCoy-aMnz-aMbO2·a(Li + N) O.cA. The complex phase high-voltage anode material has a complex preparation method, the doping element source and the cladding agent are sintered twice, the energy consumption is high, and the production cost is high.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing a multi-modified lithium ion battery anode material with low production cost and good cycle performance and rate capability.
The invention further aims to solve the technical problem of providing a preparation method of the multiple modified lithium ion battery anode material, which is simple and convenient to operate and low in energy consumption.
The invention solves the problemThe technical scheme adopted by the technical problem is that the multiple modified lithium ion battery anode material has a chemical formula of LiNixCoyMnzCeqO2·nCeO2&LiCeO2Wherein x, y, z, q and n are mole numbers, x is more than or equal to 0.6<1，0<y≤0.2，0<z≤0.2，0<q≤0.05，x+y+z＝1，0<n≤0.05。
The invention further solves the technical problem by adopting the technical scheme that the preparation method of the multiple modified lithium ion battery anode material comprises the following steps:
(1) mixing NiSO4·6H2O、CoSO4·7H2O、MnSO4·H2O and CeO2Adding into a first reaction kettle, mixing evenly, and then adding NH3·H2Stirring the solution O uniformly to obtain a mixed solution;
(2) adding hot ammonia water into a second reaction kettle, then adding the mixed solution obtained in the step (1), and reacting to obtain precursor slurry;
(3) carrying out solid-liquid separation on the precursor slurry obtained in the step (2), washing, drying, sieving and demagnetizing the obtained solid to obtain a precursor NixCoyMnzCeq(OH)2；
(4) The precursor Ni obtained in the step (3) is addedxCoyMnzCeq(OH)2Mixing with lithium source and cerium source, grinding uniformly, calcining to obtain multiple modified lithium ion battery anode material LiNixCoyMnzCeqO2·nCeO2&LiCeO2。
Further, in the step (1), the NH3·H2The concentration of the O solution is 4-7 mol/L, preferably 5-6 mol/L; the NH3·H2The addition amount of the O solution is 0.5-7L, preferably 5-6L.
Further, in the step (1), the temperature of the mixed solution is adjusted to be 50-70 ℃, preferably 52-60 ℃; adjusting the pH value of the mixed solution to 10.00-12.00, preferably 11.00-11.50.
Further, in the step (2), the temperature of the hot ammonia water is 40-50 ℃; the concentration of the hot ammonia water is 0.15-0.3 mol/L; the adding amount of the hot ammonia water is 0.5-10L.
Further, in the step (2), the reaction temperature is 40-55 ℃, preferably 45-50 ℃; the pH value of the reaction system is 10.00-11.50, preferably 10.50-11.00; the concentration of free ammonia in the reaction system is 4-8 g/L, preferably 5-7 g/L.
Further, in the step (4), the lithium source is one or more selected from lithium hydroxide, lithium carbonate and lithium nitrate; the cerium source is cerium nitrate.
Further, in the step (4), the molar amount of the lithium source is NiSO4·6H2O、CoSO4·7H2O and MnSO4·H2The total molar weight of the three substances O is 1 to 1.2 times.
Further, in the step (4), the calcining is performed for 5-8 hours at 400-600 ℃, and then the temperature is raised to 700-1000 ℃ for calcining for 10-16 hours.
Further, in the step (3), the calcination is preferably performed for 6-8 hours at 450-550 ℃, and then the temperature is raised to 800-1000 ℃ for calcination for 12-14 hours.
Research shows that compared with the prior art, the invention has the following beneficial effects:
(1) the invention relates to a multiple modified lithium ion battery anode material LiNixCoyMnzCeqO2·nCeO2&LiCeO2By uniformly doping Ce element and CeO in precursor material2&LiCeO2For coating, double coatingOuter layerCeO2Can resist the corrosion of HF and has the advantages of high corrosion resistance,inner layerLiCeO2Lithium impurities on the surface of the high-nickel material can be captured, the lithium ion transmission rate on the surface of the material can be improved, the cycling stability of the material is improved, the multiplying power performance of the material is improved by doping of the metal element Ce, and the multiplying power performance and the cycling performance of the material are greatly improved;
(2) the invention relates to a multiple modified lithium ion battery anode material LiNixCoyMnzCeqO2·nCeO2&LiCeO2Is a single-crystal particle, and is,the thickness of the coating layer is uniform. The lithium ion battery assembled by the anode prepared by the lithium ion battery has a discharge capacity of 198.6mAh/g under 1C multiplying power within a voltage range of 2.75-4.3V, the discharge capacity after 100 cycles of circulation under 1C is 167.8mAh/g, and the capacity retention rate reaches 84.49%;
(3) the preparation method has the advantages of simple operation, low energy consumption and low production cost, and is suitable for industrial production.
Drawings
FIG. 1 shows a precursor Ni of a multiple modified lithium ion battery cathode material obtained in example 1 of the present invention0.83Co0.11Mn0.06Ce0.001(OH)2SEM image of (d).
FIG. 2 is a lithium ion battery cathode material LiNi which is modified by multiple times in embodiment 2 of the invention0.83Co0.11Mn0.06Ce0.002O2·0.02CeO2&LiCeO2SEM image of (d).
FIG. 3 is LiNi which is a lithium ion battery cathode material modified by multiple times in embodiment 2 of the invention0.83Co0.11Mn0.06Ce0.002O2·0.02CeO2&LiCeO2And the cycle performance curve of the cathode material obtained in comparative example 1.
Detailed Description
The invention is further described with reference to the following figures and specific examples. It should be noted that the described embodiments illustrate only some of the embodiments of the invention, and should not be construed as limiting the scope of the claims. All other changes and modifications which can be made by one skilled in the art based on the embodiments of the present invention without inventive faculty are within the scope of the claims of the present application.
Example 1
The chemical formula of the multiple modified lithium ion battery anode material of the embodiment is LiNi0.83Co0.11Mn0.06Ce0.001O2·0.01CeO2&LiCeO2
The multiple modified lithium ion battery cathode material LiNi of the embodiment0.83Co0.11Mn0.06Ce0.001O2·0.01CeO2&LiCeO2The preparation method comprises the following steps:
(1) adding 0.83moL of NiSO4·6H2O、0.11moL CoSO4·7H2O、0.06moL MnSO4·H2O and 0.001moL CeO2Adding the mixture into a first reaction kettle, uniformly mixing, and then adding 5L of 5mol/L NH3·H2Stirring the solution O uniformly, adjusting the temperature of a reaction system to be 50 ℃ and the pH value to be 11.00 to obtain a mixed solution;
(2) adding 4L of 0.15mol/L hot ammonia water with the temperature of 50 ℃ into a second reaction kettle, then adding the mixed solution obtained in the step (1), controlling the temperature of the reaction solution to be 50 ℃, the pH value to be 10.50 and the concentration of free ammonia to be 5g/L, and reacting for 30 hours to obtain precursor slurry; conveying the precursor slurry to a centrifuge for filtering, washing, drying, sieving and demagnetizing the obtained solid to obtain precursor Ni0.83Co0.11Mn0.06Ce0.001(OH)2；
(3) In terms of mole ratios, as per Li: weighing 1.2mol of lithium nitrate and 0.01mol of cerium nitrate according to the proportion of (Ni + Co + Mn) ═ 1.2:1, and mixing with 1mol of precursor Ni obtained in the step (2)0.83Co0.11Mn0.06Ce0.001(OH)2Mixing, grinding uniformly, pre-calcining for 6h at 450 ℃, and then heating to 820 ℃ for calcining for 14h to obtain the multiple modified lithium ion battery cathode material LiNi0.83Co0.11Mn0.06Ce0.001O2·0.01CeO2&LiCeO2。
The precursor Ni of the multiple modified lithium ion battery anode material of the embodiment0.83Co0.11Mn0.06Ce0.001(OH)2The particle size of the particles is 2 to 4 μm as shown in FIG. 1. LiNi which is a lithium ion battery anode material and is subjected to multiple modification by adopting the embodiment0.83Co0.11Mn0.06Ce0.001O2·0.01CeO2&LiCeO2Assembled by the finished positive electrodeThe electrochemical performance test of the CR2025 button cell shows that the discharge capacity under 1C multiplying power reaches 195.6mAh/g, the discharge capacity after 100 cycles under 1C reaches 157.3mAh/g, and the capacity retention rate reaches 80.4 percent in the voltage range of 2.75-4.3V.
Example 2
The chemical formula of the multiple modified lithium ion battery anode material of the embodiment is LiNi0.83Co0.11Mn0.06Ce0.002O2·0.02CeO2&LiCeO2
The multiple modified lithium ion battery cathode material LiNi of the embodiment0.83Co0.11Mn0.06Ce0.002O2·0.02CeO2&LiCeO2The preparation method comprises the following steps:
(1) adding 0.83moL of NiSO4·6H2O、0.11moL CoSO4·7H2O、0.06moL MnSO4·H2O and 0.002moL CeO2Adding the mixture into a first reaction kettle, uniformly mixing, and then adding 5.5L of 6mol/L NH3·H2Stirring the solution O uniformly, adjusting the temperature of a reaction system to 55 ℃ and the pH value to 11.20 to obtain a mixed solution;
(2) adding 4L of 0.2mol/L hot ammonia water with the temperature of 48 ℃ into a second reaction kettle, then adding the mixed solution obtained in the step (1), controlling the temperature of the reaction solution to be 48 ℃, the pH value to be 10.80 and the concentration of free ammonia to be 8g/L, and reacting for 35 hours to obtain precursor slurry; conveying the precursor slurry to a centrifuge for filtering, washing, drying, sieving and demagnetizing the obtained solid to obtain precursor Ni0.83Co0.11Mn0.06Ce0.002(OH)2；
(3) In terms of mole ratios, as per Li: weighing 1.05mol of lithium nitrate and 0.02mol of cerium nitrate according to the proportion of (Ni + Co + Mn) ═ 1.05:1, and mixing with 1mol of precursor Ni obtained in the step (2)0.83Co0.11Mn0.06Ce0.002(OH)2Mixing, grinding uniformly, pre-calcining at 550 ℃ for 5h, heating to 840 ℃ and calcining for 14h to obtain the multiple modified lithium ion battery cathode material LiNi0.83Co0.11Mn0.06Ce0.002O2·0.02CeO2&LiCeO2。
The precursor Ni of the multiple modified lithium ion battery anode material of the embodiment0.83Co0.11Mn0.06Ce0.002(OH)2Has a particle diameter of 2 to 4 μm, and is a positive electrode material LiNi0.83Co0.11Mn0.06Ce0.002O2·0.02CeO2&LiCeO2The SEM image of (A) is shown in FIG. 2, and the particle size is 2 to 4 μm. LiNi which is a lithium ion battery anode material and is subjected to multiple modification by adopting the embodiment0.83Co0.11Mn0.06Ce0.002O2·0.02CeO2&LiCeO2The prepared positive electrode is assembled into a CR2025 button cell for electrochemical performance test. The electrochemical performance detection result is shown in fig. 3, and in the voltage range of 2.75-4.3V, the discharge capacity under the rate of 1C reaches 198.6mAh/g, the discharge capacity after 100 cycles of 1C circulation is 167.8mAh/g, and the capacity retention rate reaches 84.49%.
Example 3
The chemical formula of the multiple modified lithium ion battery anode material of the embodiment is LiNi0.83Co0.11Mn0.06Ce0.003O2·0.03CeO2&LiCeO2The preparation method comprises the following steps:
the multiple modified lithium ion battery cathode material LiNi of the embodiment0.83Co0.11Mn0.06Ce0.003O2·0.03CeO2&LiCeO2The preparation method comprises the following steps:
(1) adding 0.83moL of NiSO4·6H2O、0.11moL CoSO4·7H2O、0.06moL MnSO4·H2O and 0.003moL CeO2Adding the mixture into a first reaction kettle, uniformly mixing, and then adding 6L of 6mol/L NH3·H2Stirring the solution O uniformly, and adjusting the temperature of a reaction system to 52 ℃ and the pH value to 11.50 to obtain a mixed solution;
(2) 4.5L of 0.3 mol/L48 ℃ hot ammonia water is added into a second reaction kettle, then the mixed solution obtained in the step (1) is introduced, and the temperature of the reaction solution is controlled at 50 DEG CReacting for 35 hours to obtain precursor slurry, wherein the pH value is 11.00 and the concentration of free ammonia is 8 g/L; conveying the precursor slurry to a centrifuge for filtering, washing, drying, sieving and demagnetizing the obtained solid to obtain precursor Ni0.83Co0.11Mn0.06Ce0.003(OH)2；
(3) In terms of mole ratios, as per Li: weighing 1.1mol of lithium hydroxide, 0.03mol of cerium nitrate and 1mol of precursor Ni obtained in the step (2) according to the proportion of (Ni + Co + Mn) ═ 1.1:10.83Co0.11Mn0.06Ce0.002(OH)2Mixing, grinding uniformly, pre-calcining for 8h at 460 ℃, then heating to 810 ℃ and calcining for 14h to obtain the multiple modified lithium ion battery cathode material LiNi0.83Co0.11Mn0.06Ce0.003O2·0.03CeO2&LiCeO2。
The precursor Ni of the multiple modified lithium ion battery anode material of the embodiment0.83Co0.11Mn0.06Ce0.003(OH)2The particle size of the positive electrode material is 2-4 mu m, and the multiple modified lithium ion battery positive electrode material LiNi is adopted0.83Co0.11Mn0.06Ce0.003O2·0.03CeO2&LiCeO2The prepared positive electrode is assembled into a CR2025 button cell for electrochemical performance test. In the voltage range of 2.75-4.3V, the discharge capacity under the 1C multiplying power reaches 192.6mAh/g, the discharge capacity after 100 cycles under the 1C multiplying power is 158.7mAh/g, and the capacity retention rate reaches 82.4%.
Comparative example 1
(1) 0.83moL of NiSO4·6H2O, 0.11moL of CoSO4·7H2O and 0.06moL of MnSO4·H2O (Ni: Co: Mn: 83:11:6) is added into the first reaction kettle and mixed evenly, and simultaneously 7L NH is added3·H2Feeding an O solution (5mol/L) into a first reaction kettle at a constant speed through a metering pump, controlling the temperature of a reaction system at 50 ℃ and the pH value at 11.00; adding 10L of hot dilute ammonia water with the temperature of 50 ℃ and the ammonia concentration of 0.15mol/L into a second reaction kettle according to the volume ratio of 6: 1;
(2) then will beAdding the mixed liquid in the first reaction kettle into the second reaction kettle for reaction, controlling the temperature of a reaction system at 50 ℃, the pH value at 10.50 and the concentration of free ammonia in the system at 5g/L, after precursor slurry is uniformly mixed, conveying the mixture to a centrifugal machine for filtration, washing, drying, sieving and demagnetizing the obtained solid to obtain a precursor Ni0.83Co0.11Mn0.06(OH)2；
(3) In terms of mole ratios, as per Li: weighing lithium nitrate according to the proportion of (Ni + Co + Mn) 1.2:1, and mixing 1mol of precursor material Ni prepared in the step (2)0.83Co0.11Mn0.06(OH)2Mixing with 1.2mol of lithium nitrate evenly, burning for 6h at 450 ℃, and burning for 14h at 820 ℃ to obtain the ternary cathode material LiNi0.83Co0.11Mn0.06O2. And (3) assembling the CR2025 button cell by adopting the positive electrode made of the positive electrode material obtained in the comparative example, and carrying out electrochemical performance test. As shown in FIG. 3, in the voltage range of 2.75-4.3V, the discharge capacity at 1C rate is 190.5mAh/g, the capacity after 100 cycles at 1C is 137.1mAh/g, and the capacity retention rate is 71.9%.
Claims (9)
1. The multiple modified lithium ion battery cathode material is characterized in that the chemical formula of the multiple modified lithium ion battery cathode material is LiNixCoyMnzCeqO2·nCeO2&LiCeO2Wherein x, y, z, q and n are mole numbers, x is more than or equal to 0.6<1，0<y≤0.2，0<z≤0.2，0<q≤0.05，x+y+z＝1，0<n≤0.05。
2. The preparation method of the multiple modified lithium ion battery positive electrode material according to claim 1, characterized by comprising the following steps:
(1) mixing NiSO4·6H2O、CoSO4·7H2O、MnSO4·H2O and CeO2Adding into a first reaction kettle, mixing evenly, and then adding NH3·H2Stirring the solution O uniformly to obtain a mixed solution;
(2) adding hot ammonia water into a second reaction kettle, then adding the mixed solution obtained in the step (1), and reacting to obtain precursor slurry;
(3) carrying out solid-liquid separation on the precursor slurry, washing, drying, sieving and demagnetizing the obtained solid to obtain precursor NixCoyMnzCeq(OH)2；
(4) The precursor Ni obtained in the step (3) is addedxCoyMnzCeq(OH)2Mixing with lithium source and cerium source, grinding uniformly, calcining to obtain multiple modified lithium ion battery anode material LiNixCoyMnzCeqO2·nCeO2&LiCeO2。
3. The method for preparing the multiple modified lithium ion battery cathode material according to claim 2, wherein in the step (1), the NH is added3·H2The concentration of the O solution is 4-7 mol/L; the NH3·H2The addition amount of the O solution is 0.5-7L.
4. The preparation method of the multiple modified lithium ion battery positive electrode material according to claim 2 or 3, wherein in the step (1), the temperature of the mixed solution is adjusted to 50-70 ℃; and adjusting the pH value of the mixed solution to 10.00-12.00.
5. The preparation method of the multiple modified lithium ion battery cathode material according to any one of claims 2 to 4, wherein in the step (2), the temperature of the hot ammonia water is 40 to 50 ℃; the concentration of the hot ammonia water is 0.15-0.3 mol/L; the adding amount of the hot ammonia water is 0.5-10L.
6. The preparation method of the multiple modified lithium ion battery cathode material according to any one of claims 2 to 5, wherein in the step (2), the reaction temperature is 40 to 55 ℃; the pH value of the reaction system is 10.00-11.50; the concentration of free ammonia in the reaction system is 4-8 g/L.
7. The preparation method of the multiple modified lithium ion battery positive electrode material according to any one of claims 2 to 6, wherein in the step (4), the lithium source is one or more selected from lithium hydroxide, lithium carbonate and lithium nitrate; the cerium source is cerium nitrate.
8. The preparation method of the multiple modified lithium ion battery cathode material according to any one of claims 2 to 7, wherein in the step (4), the molar amount of the lithium source is NiSO4·6H2O、CoSO4·7H2O and MnSO4·H2The total molar weight of the three substances O is 1 to 1.2 times.
9. The preparation method of the multiple modified lithium ion battery positive electrode material according to any one of claims 2 to 8, wherein in the step (4), the calcination is performed by calcining at 400 to 600 ℃ for 5 to 8 hours, and then heating to 700 to 1000 ℃ for 10 to 16 hours.
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| CN106328908A (en) * | 2016-11-16 | 2017-01-11 | 吉林化工学院 | Lithium-rich anode material for lithium ion battery and preparation method thereof |
| CN106654237A (en) * | 2017-02-17 | 2017-05-10 | 中国科学院过程工程研究所 | Nickel-cobalt-aluminum-lithium ion battery positive material as well as preparation method and application thereof |
| CN108711615A (en) * | 2018-05-30 | 2018-10-26 | 广州朝锂新能源科技有限公司 | Metal-doped ceria surface modifies the nickelic positive electrode of lithium ion battery |
| CN109301207A (en) * | 2018-09-27 | 2019-02-01 | 北京理工大学 | A kind of surface layer doping Ce3+And surface layer coats CeO2NCM tertiary cathode material and preparation method thereof |
| CN112002901A (en) * | 2020-08-12 | 2020-11-27 | 中南大学 | Metal compound coated ternary cathode material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106328908A (en) * | 2016-11-16 | 2017-01-11 | 吉林化工学院 | Lithium-rich anode material for lithium ion battery and preparation method thereof |
| CN106654237A (en) * | 2017-02-17 | 2017-05-10 | 中国科学院过程工程研究所 | Nickel-cobalt-aluminum-lithium ion battery positive material as well as preparation method and application thereof |
| CN108711615A (en) * | 2018-05-30 | 2018-10-26 | 广州朝锂新能源科技有限公司 | Metal-doped ceria surface modifies the nickelic positive electrode of lithium ion battery |
| CN109301207A (en) * | 2018-09-27 | 2019-02-01 | 北京理工大学 | A kind of surface layer doping Ce3+And surface layer coats CeO2NCM tertiary cathode material and preparation method thereof |
| CN112002901A (en) * | 2020-08-12 | 2020-11-27 | 中南大学 | Metal compound coated ternary cathode material and preparation method thereof |
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