CN110518221B - Method for preparing lithium silicate coated lithium nickel cobalt manganese oxide positive electrode material by anti-solvent method - Google Patents
Method for preparing lithium silicate coated lithium nickel cobalt manganese oxide positive electrode material by anti-solvent method Download PDFInfo
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Abstract
A method for preparing a lithium silicate-coated lithium nickel cobalt manganese oxide positive electrode material by an anti-solvent method comprises the following steps: (1) dispersing nickel cobalt manganese hydroxide into a silicon source-containing aqueous solution, adding a lithium source, and stirring to obtain a suspension; (2) adding an anhydrous organic solvent into the suspension, stirring to deposit lithium silicate on the surface of the nickel, cobalt and manganese hydroxide, stirring, and evaporating to dryness to obtain powder; (3) and mixing the powder with a lithium source, and sintering to obtain the lithium silicate-coated nickel cobalt lithium manganate positive electrode material. According to the invention, the lithium silicate coated lithium nickel cobalt manganese oxide cathode material is synthesized by an anti-solvent method, so that the gaps among primary particles in the lithium nickel cobalt manganese oxide cathode material are effectively reduced, the spatial structure layout is more reasonable, the stability is stronger, the preparation process is simple, the cost is low, and the lithium nickel cobalt manganese oxide coated lithium nickel manganese oxide cathode material is suitable for industrial production.
Description
Technical Field
The invention relates to a preparation method of a lithium ion battery positive electrode material, in particular to a method for preparing a lithium silicate coated nickel cobalt lithium manganate positive electrode material by an anti-solvent method.
Background
The continuous consumption of fossil energy and the increasingly prominent environmental problems restrict the sustainable development of economy, and the acceleration of the development of new energy industry is the inevitable requirements of adjusting energy structure, improving ecological environment, changing development mode and energy utilization mode, and is also the strategic choice of cultivating new economic growth points, improving overall competitiveness and driving the development of related industries. The state starts from energy conservation and emission reduction, the development of new energy electric vehicles is greatly promoted, and the lithium ion battery is used as an important part of the new energy electric vehicles, and the performance of the lithium ion battery plays a decisive role in the safety, the endurance mileage and the like of the electric vehicles. The nickel cobalt lithium manganate anode material is one of the most concerned materials in the current lithium ion battery research, the theoretical discharge specific capacity of the nickel cobalt lithium manganate anode material is up to 278mAh/g, the voltage platform is 3.6V, and the nickel cobalt lithium manganate anode material has extremely high energy density and power density and is considered as an ideal choice for the next generation of power battery anode materials. However, the nickel cobalt lithium manganate positive electrode material is generally a secondary sphere composed of nanoscale primary particles, and is very easy to collapse in structure in a circulation process, so that the electrochemical performance of the nickel cobalt lithium manganate positive electrode material is seriously influenced. The surface coating is a common method for solving the problem of the nickel cobalt lithium manganate positive electrode material, and is to find a suitable material for coating the nickel cobalt lithium manganate positive electrode material.
CN106910881A discloses a preparation method of lithium metatitanate coated lithium nickel cobalt aluminate cathode material, but due to the defects in the preparation method, the coating layer is not uniform, thereby affecting the electrochemical performance.
CN107910539A discloses a preparation method of a lithium silicate coated lithium nickel cobalt aluminate anode material, wherein the mass percentage of lithium silicate in the material is 1-10 wt%, and the lithium silicate forms a coating layer with the thickness of 2-20 nm and is coated on the lithium nickel cobalt aluminate; the positive electrode material is spherical particles with the particle size of 5-15 mu m. The method comprises the following steps: (1) adding a silicon source into an organic solvent, uniformly stirring, adding water, adding nickel cobalt aluminum hydroxide, heating, stirring, reacting, and evaporating to dryness to obtain silicon dioxide coated nickel cobalt aluminum hydroxide precursor powder; (2) and grinding and uniformly mixing the nickel hydroxide, cobalt and aluminum precursor powder coated with the silicon dioxide and the lithium salt, placing the mixture in a tubular furnace, and sintering the mixture in two sections under an oxidizing atmosphere to obtain the nickel-cobalt-aluminum hydroxide lithium-cobalt alloy material. Although the method can effectively reduce the problem of residual lithium on the surface during conventional coating, the clearance between primary particles of the product nickel cobalt lithium manganate positive electrode material is larger, and the stability is still to be improved.
Currently, no method for preparing the lithium silicate coated lithium nickel cobalt manganese oxide cathode material by an anti-solvent method is disclosed.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a method for preparing a lithium silicate coated lithium nickel cobalt manganese oxide cathode material by using a desolvation method, wherein the method can improve the structural stability of the lithium nickel cobalt manganese oxide cathode material.
The technical scheme adopted by the invention for solving the technical problem is that the method for preparing the lithium silicate coated lithium nickel cobalt manganese oxide positive electrode material by the anti-solvent method comprises the following steps:
(1) dispersing nickel cobalt manganese hydroxide into a silicon source-containing aqueous solution, adding a lithium source, and stirring to obtain a suspension;
(2) adding an anhydrous organic solvent into the suspension, stirring to deposit lithium silicate on the surface of the nickel, cobalt and manganese hydroxide, stirring, and evaporating to dryness to obtain powder;
(3) and mixing the powder with a lithium source, and sintering to obtain the lithium silicate-coated nickel cobalt lithium manganate positive electrode material.
Further, in the step (1), the silicon source is one or more of lithium pentasilicate, tetraethyl silicate, methyl orthosilicate, polysiloxane or methyltriethoxysilane; the lithium source is one or more of lithium hydroxide, lithium acetate or lithium carbonate.
Further, in the step (1), the molar ratio of the lithium source to the silicon source is Li/Si =1 (Li)2Si2O5)、Li/Si=2(Li2SiO3)、Li/Si=3(Li6Si2O7)、Li/Si=4(Li4SiO4) Or Li/Si =8 (Li)8SiO6)。
Further, in the step (1), the molar concentration of the aqueous solution containing the silicon source is 0.001-0.01M.
Further, in the step (1), the stirring time is 10-30 min, and the stirring speed is 80-900 r/min.
Further, in the step (2), the volume ratio of the suspension to the anhydrous organic solvent is 1-5: 5; the anhydrous organic solvent is one or more of anhydrous methanol, anhydrous ethanol, glycol or anhydrous propanol.
Further, in the step (2), the stirring time is 1-3 h, and the stirring speed is 80-900 r/min.
Further, in the step (3), the temperature for evaporating to dryness is 60-80 ℃, and the stirring speed is 80-900 r/min.
Further, in the step (3), the lithium source is one or more of lithium hydroxide, lithium acetate and lithium carbonate; the number of moles of the lithium source is such that the number of moles of lithium = (1.01 to 1.10) × the number of moles of nickel cobalt manganese hydroxide.
Further, in the step (3), the sintering temperature is 850-950 ℃, the sintering time is 10-15 hours, and the sintering atmosphere is oxygen.
The lithium silicate-coated lithium nickel cobalt manganese oxide cathode material has the lithium silicate content of 1-10 mol%.
Compared with the prior art, the invention has the following beneficial effects: (1) according to the invention, the lithium silicate-coated lithium nickel cobalt manganese oxide positive electrode material is synthesized by a reverse solution method for the first time, and the lithium silicate can effectively reduce the gaps among primary particles of the lithium nickel cobalt manganese oxide positive electrode material and has a space structure advantage; (2) li of the invention2SiO3Coated LiNi0.8Co0.1Mn0.1O2The positive electrode material is assembled into a battery, the first discharge gram capacity is 213.1 mAh/g within the voltage range of 2.7-4.3V and under 0.1C, and the capacity retention rate reaches 96.1% after 50 cycles of circulation under the multiplying power of 1C, which shows that the lithium silicate coated nickel cobalt lithium manganate positive electrode material provided by the invention has better circulation stability and multiplying power performance; (3) the method has simple preparation process and low cost, and is suitable for industrial production.
Drawings
FIG. 1 is Li in example 12SiO3Coated LiNi0.8Co0.1Mn0.1O2SEM images of the cathode material after 100 cycles at 1C magnification;
FIG. 2 is a pairLiNi in proportion 10.8Co0.1Mn0.1O2SEM images of the cathode material after 100 cycles at 1C magnification;
FIG. 3 is Li in example 12SiO3Coated LiNi0.8Co0.1Mn0.1O2Positive electrode Material and LiNi in comparative example 10.8Co0.1Mn0.1O2And (3) comparing the cycle curves of the cathode material at the discharge rate of 1C.
Detailed Description
The invention is further illustrated by the following examples and figures.
The chemical reagents used in the examples of the present invention, unless otherwise specified, are commercially available in a conventional manner.
Example 1
Li2SiO3Coated LiNi0.8Co0.1Mn0.1O2A positive electrode material:
the Li2SiO3In a molar percentage of 1%, Li2SiO3In LiNi0.8Co0.1Mn0.1O2Forming a uniform coating layer on the surface of the anode material by in-situ growth; the positive electrode material is spherical particles with the particle size of 10-12 mu m.
The embodiment comprises the following steps:
(1) 3.694 g (40 mmol) of Ni0.8Co0.1Mn0.1(OH)2Dispersed in 10 mL of 0.008M Li2Si5O11To the aqueous solution, 0.027 g (0.64 mmol) of LiOH. H was added2O and stirring to obtain a suspension;
(2) adding 50 mL of absolute ethyl alcohol into the suspension, stirring for 1 h, and evaporating to dryness at 80 ℃ to obtain powder;
(3) the resulting powder was mixed with 1.779 g (42.4 mmol) of LiOH. H2Mixing O and sintering at 780 ℃ for 12 h to obtain Li2SiO3Coated LiNi0.8Co0.1Mn0.1O2And (3) a positive electrode material.
Weigh 0.400g of this exampleExample obtained Li2SiO3Coated LiNi0.8Co0.1Mn0.1O2Adding 0.050g of conductive carbon black as a conductive agent and 0.050g of PVDF (polyvinylidene fluoride) as a binder into a positive electrode material, uniformly mixing, coating on an aluminum foil to prepare a positive electrode plate, and taking a metal lithium plate as a negative electrode, Celgard 2300 as a diaphragm and 1mol/L LiPF in a vacuum glove box6DMC (volume ratio 1: 1) as electrolyte, and assembling into a CR2025 button cell.
As shown in FIG. 1, Li obtained in this example2SiO3Coated LiNi0.8Co0.1Mn0.1O2The positive electrode material can still keep a complete spherical shape after being circulated for 100 circles under the multiplying power of 1C.
As shown in FIG. 3, Li obtained in this example2SiO3Coated LiNi0.8Co0.1Mn0.1O2The first discharge gram capacity of the anode material is 213.1 mAh/g within the voltage range of 2.7-4.3V and at 0.1C, and the capacity retention rate of 50 cycles of the anode material is up to 96.1% under the multiplying power of 1C.
Example 2
Li4SiO4Coated LiNi0.8Co0.1Mn0.1O2A positive electrode material:
the Li4SiO4In a molar percentage of 1%, Li4SiO4In LiNi0.8Co0.1Mn0.1O2Forming a uniform coating layer on the surface of the anode material by in-situ growth; the positive electrode material is spherical particles with the particle size of 10-12 mu m.
The embodiment comprises the following steps:
(1) 3.694 g (40 mmol) of Ni0.8Co0.1Mn0.1(OH)2Dispersed in 40 mL of 0.01M C16H36O40.067 g (1.6 mmol) of LiOH. H was added to the Si aqueous solution2O and stirring to obtain a suspension;
(2) adding 60 mL of absolute ethyl alcohol into the suspension, stirring for 2h, and evaporating to dryness at 70 ℃ to obtain powder;
(3) will be describedThe powder was obtained together with 1.779 g (42.4 mmol) of LiOH. H2Mixing O and sintering for 10 h at 800 ℃ to obtain Li4SiO4Coated LiNi0.8Co0.1Mn0.1O2And (3) a positive electrode material.
0.400g of Li obtained in the example was weighed4SiO4Coated LiNi0.8Co0.1Mn0.1O2Adding 0.050g of conductive carbon black as a conductive agent and 0.050g of PVDF (polyvinylidene fluoride) as a binder into a positive electrode material, uniformly mixing, coating on an aluminum foil to prepare a positive electrode plate, and taking a metal lithium plate as a negative electrode, Celgard 2300 as a diaphragm and 1mol/L LiPF in a vacuum glove box6DMC (volume ratio 1: 1) as electrolyte, and assembling into a CR2025 button cell.
By detection, Li obtained in this example4SiO4Coated LiNi0.8Co0.1Mn0.1O2The positive electrode material can still keep a complete spherical shape after being circulated for 100 circles under the multiplying power of 1C.
By detection, Li obtained in this example4SiO4Coated LiNi0.8Co0.1Mn0.1O2The first discharge gram capacity of the anode material is 210.7mAh/g within the voltage range of 2.7-4.3V and at 0.1C, and the capacity retention rate of 50 cycles of the anode material is up to 95.4% under the multiplying power of 1C.
Example 3
Li4SiO4Coated LiNi0.8Co0.15Al0.05O2A positive electrode material:
the Li4SiO4In a molar percentage of 1%, Li4SiO4In LiNi0.8Co0.15Al0.05O2Forming a uniform coating layer on the surface of the anode material by in-situ growth; the positive electrode material is spherical particles with the particle size of 10-12 mu m.
The embodiment comprises the following steps:
(1) 3.671 g (40 mmol) of Ni0.8Co0.15Al0.05(OH)2Dispersed in 40 mL of 0.01M C16H36O4To the aqueous Si solution, add0.067 g (1.6 mmol) of LiOH. H2O and stirring to obtain a suspension;
(2) adding 80 mL of absolute ethyl alcohol into the suspension, stirring for 2h, and evaporating to dryness at 75 ℃ to obtain powder;
(3) the resulting powder was mixed with 1.813 g (43.2 mmol) of LiOH. H2Mixing O and sintering for 10 h at 850 ℃ to obtain Li4SiO4Coated LiNi0.8Co0.15Al0.05O2And (3) a positive electrode material.
0.400g of Li obtained in the example was weighed4SiO4Coated LiNi0.8Co0.15Al0.05O2Adding 0.050g of conductive carbon black as a conductive agent and 0.050g of PVDF (polyvinylidene fluoride) as a binder into a positive electrode material, uniformly mixing, coating on an aluminum foil to prepare a positive electrode plate, and taking a metal lithium plate as a negative electrode, Celgard 2300 as a diaphragm and 1mol/L LiPF in a vacuum glove box6DMC (volume ratio 1: 1) as electrolyte, and assembling into a CR2025 button cell.
By detection, Li obtained in this example4SiO4Coated LiNi0.8Co0.15Al0.05O2The positive electrode material can still keep a complete spherical shape after being circulated for 100 circles under the multiplying power of 1C.
By detection, Li obtained in this example4SiO4Coated LiNi0.8Co0.15Al0.05O2The first discharge gram capacity of the anode material is 208.9 mAh/g within the voltage range of 2.7-4.3V and at 0.1C, and the capacity retention rate of 50 cycles is up to 91.4% under the multiplying power of 1C.
Comparative example 1:
with LiNi0.8Co0.1Mn0.1O2Preparing the positive electrode material into a positive electrode for battery assembly:
0.400g LiNi was weighed0.8Co0.1Mn0.1O2Adding 0.050g of conductive carbon black as a conductive agent and 0.050g of PVDF (polyvinylidene fluoride) as a binder into the positive electrode material, coating the mixture on an aluminum foil to prepare a positive electrode plate, and taking a metal lithium plate as a negative electrode and a Celgard 2300 as a separator in a vacuum glove boxMembrane, 1mol/L LiPF6DMC (volume ratio 1: 1) as electrolyte, and assembling into a CR2025 button cell. The first discharge gram capacity of the assembled battery is 205.0 mAh/g within the voltage range of 2.7-4.3V and under the multiplying power of 0.1C.
Li in example 12SiO3Coated LiNi0.8Co0.1Mn0.1O2Positive electrode Material and LiNi in comparative example 10.8Co0.1Mn0.1O2The cyclic curve ratio of the positive electrode material under the discharge rate of 1C is shown in figure 3, wherein the first 3 circles are the process of activating the material under the discharge rate of 0.1C, the assembled battery is in the voltage range of 2.7-4.3V, and Li2SiO3Coated LiNi0.8Co0.1Mn0.1O2The first discharge specific capacities of the anode material and the uncoated material are 213.1 mAh/g and 205.0 mAh/g respectively. After 50 cycles, Li2SiO3Coated LiNi0.8Co0.1Mn0.1O2The capacity retention ratio of the positive electrode material was 96.1%, while that of uncoated LiNi0.8Co0.1Mn0.1O2The capacity retention of the material was only 84.7%, indicating that the LiNi was present after coating0.8Co0.1Mn0.1O2The electrochemical performance of the material is obviously improved.
Comparative example 2:
with LiNi0.8Co0.15Al0.05O2And the positive electrode material is made into a positive electrode for battery assembly.
And (3) electrochemical performance testing:
0.400g LiNi was weighed0.8Co0.15Al0.05O2Adding 0.050g of conductive carbon black serving as a conductive agent and 0.050g of PVDF (polyvinylidene fluoride) serving as a binder into a high-nickel ternary positive electrode material, coating the high-nickel ternary positive electrode material on aluminum foil to prepare a positive electrode plate, and taking a metal lithium plate as a negative electrode, Celgard 2300 as a diaphragm and 1mol/L LiPF in a vacuum glove box6DMC (volume ratio 1: 1) as electrolyte, and assembling into a CR2025 button cell.
The first discharge gram capacity of the assembled battery is 202.1 mAh/g within the voltage range of 2.7-4.3V and under the multiplying power of 0.1C. After 50 cycles, Li2SiO3Coated LiNi0.8Co0.1Mn0.1O2The capacity retention ratio of the positive electrode material was 91.4%, while that of uncoated LiNi0.8Co0.1Mn0.1O2The capacity retention of the material was only 59.6%.
Claims (12)
1. A method for preparing a lithium silicate coated lithium nickel cobalt manganese oxide positive electrode material by an anti-solvent method is characterized by comprising the following steps:
(1) dispersing nickel cobalt manganese hydroxide into a silicon source-containing aqueous solution, adding a lithium source, and stirring to obtain a suspension;
(2) adding an anhydrous organic solvent into the suspension, stirring to deposit lithium silicate on the surface of the nickel, cobalt and manganese hydroxide, stirring, and evaporating to dryness to obtain powder;
(3) mixing the powder with a lithium source, and sintering to obtain the lithium silicate-coated nickel cobalt lithium manganate positive electrode material;
in the step (1), the silicon source is one or more of lithium pentasilicate, tetraethyl silicate, methyl orthosilicate, polysiloxane or methyltriethoxysilane; the lithium source is one or more of lithium hydroxide, lithium acetate or lithium carbonate;
in the step (1), the molar concentration of the aqueous solution containing the silicon source is 0.001-0.01M;
in the step (2), the volume ratio of the suspension to the anhydrous organic solvent is 1-5: 5; the anhydrous organic solvent is one or more of anhydrous methanol, anhydrous ethanol, glycol or anhydrous propanol;
in the step (2), the stirring time is 1-3 h, and the stirring speed is 80-900 r/min.
2. The method for preparing the lithium silicate coated lithium nickel cobalt manganese oxide cathode material according to the claim 1, wherein in the step (1), the molar ratio of the lithium source to the silicon source is Li/Si =1, Li/Si =2, Li/Si =3, Li/Si =4 or Li/Si = 8.
3. The method for preparing the lithium silicate-coated lithium nickel cobalt manganese oxide cathode material according to the claim 1 or 2, wherein in the step (1), the stirring time is 10-30 min, and the stirring speed is 80-900 r/min.
4. The method for preparing the lithium silicate-coated lithium nickel cobalt manganese oxide cathode material by the anti-solvent method according to claim 1 or 2, wherein in the step (2), the temperature for evaporating to dryness is 60-80 ℃.
5. The method for preparing the lithium silicate coated lithium nickel cobalt manganese oxide positive electrode material according to the claim 3, wherein in the step (2), the temperature for evaporating to dryness is 60-80 ℃.
6. The method for preparing the lithium silicate-coated lithium nickel cobalt manganese oxide cathode material according to the claim 1 or 2, wherein in the step (3), the lithium source is one or more of lithium hydroxide, lithium acetate or lithium carbonate; the number of moles of the lithium source is such that the number of moles of lithium = (1.01 to 1.10) × the number of moles of nickel cobalt manganese hydroxide.
7. The method for preparing the lithium silicate coated lithium nickel cobalt manganese oxide positive electrode material according to the claim 3, wherein in the step (3), the lithium source is one or more of lithium hydroxide, lithium acetate or lithium carbonate; the number of moles of the lithium source is such that the number of moles of lithium = (1.01 to 1.10) × the number of moles of nickel cobalt manganese hydroxide.
8. The method for preparing the lithium silicate coated lithium nickel cobalt manganese oxide positive electrode material according to the claim 4, wherein in the step (3), the lithium source is one or more of lithium hydroxide, lithium acetate or lithium carbonate; the number of moles of the lithium source is such that the number of moles of lithium = (1.01 to 1.10) × the number of moles of nickel cobalt manganese hydroxide.
9. The method for preparing the lithium silicate-coated lithium nickel cobalt manganese oxide cathode material according to the claim 1 or 2, wherein in the step (3), the sintering temperature is 850-950 ℃, the sintering time is 10-15 h, and the sintering atmosphere is oxygen.
10. The method for preparing the lithium silicate coated lithium nickel cobalt manganese oxide cathode material according to claim 3, wherein in the step (3), the sintering temperature is 850-950 ℃, the sintering time is 10-15 h, and the sintering atmosphere is oxygen.
11. The method for preparing the lithium silicate coated lithium nickel cobalt manganese oxide cathode material according to the claim 4, wherein in the step (3), the sintering temperature is 850-950 ℃, the sintering time is 10-15 h, and the sintering atmosphere is oxygen.
12. The method for preparing the lithium silicate coated lithium nickel cobalt manganese oxide cathode material according to claim 6, wherein in the step (3), the sintering temperature is 850-950 ℃, the sintering time is 10-15 h, and the sintering atmosphere is oxygen.
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| CN112670482B (en) * | 2020-12-25 | 2022-04-12 | 合肥国轩高科动力能源有限公司 | Ternary cathode material and preparation method and application thereof |
| CN114150164A (en) * | 2021-12-21 | 2022-03-08 | 苏州中科百奥科技发展有限公司 | Method for separating lithium ions from mixed solution |
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