CN110391407B - Power battery positive electrode material with core-shell structure and preparation method and application thereof - Google Patents
Power battery positive electrode material with core-shell structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a core-shell structured positive electrode material of a power battery, a preparation method and application thereof 0.5 Mn 1.45 Zr 0.05 O 3.95 F 0.05 And coating a layer of electrochemical active prussian blue analogue MHCF on the nickel lithium manganate single crystal by using a wet in-situ coating method to form a unique core-shell structure. The lithium nickel manganese oxide positive electrode material modified by anion and cation co-doping has high discharge specific capacity and a stable single crystal structure, and meanwhile, an in-situ coating layer of MHCF has good circulation stability and a large lithium ion diffusion channel, so that direct contact between lithium nickel manganese oxide crystals and electrolyte can be effectively isolated, and the circulation stability and the rate capability of the composite material are improved.
Description
Technical Field
The invention belongs to the field of new energy batteries, and particularly relates to a power battery positive electrode material with a core-shell structure, and a preparation method and application thereof.
Background
With the gradual exhaustion of fossil energy and the global warming problem caused by the combustion of the fossil energy, countries in the world publish the time for forbidding fuel vehicles, and China sets up an electric vehicle subsidy policy for dealing with the trend, so that power batteries of the most key parts of new energy power vehicles attract great attention of people.
At present, power batteries commonly used in the market are lithium iron phosphate batteries, lithium manganate batteries, lithium cobaltate batteries, ternary batteries and the like, and the main factor for determining whether the power batteries can effectively improve the endurance capacity is the energy density of the positive electrode material of the power battery.
The ternary positive electrode material series is a high energy density material generally seen by researchers, is the mainstream direction of the market at present, and is mainly divided into 111, 523, 622 and 811 series according to the content of transition metals of nickel, cobalt and manganese/aluminum. The 111 and 523 series of the battery cells have good circulation stability and high safety, but the series of the battery cells have high cobalt content, so that the cost is greatly increased, and the energy density cannot meet the requirements of people at the present stage (the energy density of the battery cell monomer is more than 300 Wh/Kg). The high nickel series 622 and 811 have reduced cost by increasing nickel content and reducing cobalt content, and have improved energy density and specific discharge capacity, but have correspondingly reduced service life and safety. Therefore, the current research trend is mainly to develop a high-nickel ternary positive electrode for reducing cobalt and extracting nickel, a high-capacity lithium-rich manganese-based positive electrode material and a solid electrolyte to improve the energy density and the safety coefficient.
The spinel lithium nickel manganese oxide serving as a binary anode material without transition metal cobalt has the cost about 1/3 of that of a ternary material, and has the advantages of a 4.74V voltage platform, 147mAh/g theoretical specific capacity, high energy density and power density, wide raw material source, mature preparation process and the like. However, the spinel lithium nickel manganese oxide cathode material with the upper limit cut-off voltage as high as 5V is easy to cause the corrosion action between the surface of the active material and the electrolyte, so that the active material is lost, and Ni generated in the charging process 4+ The electrolyte with strong oxidizing property and easy oxidation decomposition can further intensify the decomposition and gas production of the electrolyte, the side reaction product is deposited on the surface of the electrode, the interface impedance of the battery is increased, and meanwhile, the positive electrode material is caused by Mn 3+ If too much, the electrolyte will dissolve. Therefore, the electrochemical performance of the nickel lithium manganate is modified by surface coating.
Chinese patent application CN 107946551A discloses a doped lithium nickel manganese oxide material, a modified lithium nickel manganese oxide positive electrode and a preparation method thereof, wherein the positive electrode is doped with positive ion yttrium and Li 2 SnO 3 Surface coating is carried out to improve the structural stability of the lithium nickel manganese oxide positive electrode material and inhibit side reaction of a contact interface, but Li 2 SnO 3 Not electrochemically active itself, and can reduce the energy density of the active material.
CN 105280912A discloses a preparation method of oxide-coated lithium ion battery cathode material lithium nickel manganese oxide, which coats the surface of lithium nickel manganese oxide by a wet process, so as to improve the cycling stability and high temperature performance of lithium nickel manganese oxide material, but the metal oxide has poor conductivity, which is not favorable for the electronic conductivity of active material.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a spinel lithium nickel manganese oxide positive electrode material of a power battery with a core-shell structure, which is mainly characterized in that an anion-cation co-doped LiNi is synthesized by a spray drying method 0.5 Mn 1.45 Zr 0.05 O 3.95 F 0.05 And coating a layer of electrochemically active Prussian blue analogue MHCF on the nickel lithium manganate single crystal by using a wet in-situ coating method to form a unique core-shell structure.
The invention also aims to provide the cathode material prepared by the method, the lithium nickel manganese oxide cathode material modified by the anion and cation co-doping has high discharge specific capacity and a stable single crystal structure, and meanwhile, the in-situ coating layer of the MHCF has good circulation stability and a large lithium ion diffusion channel, so that the lithium nickel manganese oxide crystal can be effectively isolated from being directly contacted with the electrolyte, and the circulation stability and the rate capability of the composite material are improved.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a power battery anode material with a core-shell structure comprises the following steps:
(1) Preparation of single crystal lithium nickel manganese oxide
Weighing and mixing nickel oxide, manganese oxide and lithium carbonate according to a molar ratio of Li to Ni to Mn to Zr to F = (2.12-2.24) to 1.00 2 And an anionic additive LiF, and premixing; adding the mixture into pure water, and sanding for 1-3h; performing spray drying on the mixed slurry A after sanding to obtain a yellow-black powdery precursor B; sintering the precursor B at 800-950 ℃ in the air atmosphere for 8-16h, annealing at 650 ℃ for 5-12h, naturally cooling, and performing jet milling to obtain cathode-anode doped LiNi 0.5 Mn 1.45 Zr 0.05 O 3.95 F 0.05 Black single crystal powder C;
in the step (1), 0 < x is less than or equal to 0.1, and 0 < y is less than or equal to 0.2;
in the step (1), the lithium carbonate can be excessive by 3-6%; the lithium carbonate is in proper excess because the lithium source is partially lost during the high-temperature reaction, and in addition, the excess lithium source can reduce cation mixing and play a role in stabilizing the crystal structure.
Sanding in the step (1) at the rotating speed of 1000-2000r/min;
the spray drying of the step (1) is carried out at 190-210 ℃;
(2) Preparation of core-shell structure power battery anode material
Preparation of Na 4 Fe(CN) 6 Aqueous solution, denoted as solution D; preparing a solution containing M ions, and marking as a solution E;
premixing the single crystal powder C with sodium citrate and polyvinylpyrrolidone, adding the solution E, stirring, adding the solution D, stirring for several hours, standing at room temperature until the supernatant is clear, alternately cleaning with anhydrous ethanol and pure water for several times, and drying to obtain MHCF in-situ coated LiNi 0.5 Mn 1.5-x Zr x O 4-0.5y F y @ MHCF composite positive electrode material;
in the step (2), M can be more than one of Ni, zn, fe, co or Cu;
the core-shell structure LiNi 0.5 Mn 1.5-x Zr x O 4-0.5y F y The grain size of the @ MHCF crystal is 1-4 mu m, the thickness of the coating layer is 10-200nm, and the coating content is 1% -10%.
The material prepared by the method can be used as a lithium ion battery anode material, and the cycle stability and the rate capability of the material are obviously improved.
Compared with the prior art, the invention has the following advantages and effects:
1. the invention synthesizes Zr by a spray drying method 4+ And F - Co-doped LiNi 0.5 Mn 1.5-x Zr x O 4-0.5y F y The single crystal structure has uniform appearance, can reduce the ion mixed discharge in the material and reduce Mn 3+ Content, effectively improves the discharge specific capacity and the structural stability of the material.
2. Compared with the common metal oxide or phosphate coating, the MHCF layer coated in situ by the wet method has the advantages that the MHCF layer has lithium storage capacity, can provide partial capacity, and has good circulation stability.
3. The composite cathode material with the core-shell structure can effectively isolate the direct contact between the high-voltage electrolyte and the lithium nickel manganese oxide crystal through the MHCF coating layer, and avoids Ni with strong oxidizing property 4+ Side reaction with electrolyte and Mn 2+ So as to ensure the excellent circulation stability of the lithium nickel manganese oxide material.
Drawings
Fig. 1 is XRD patterns of composite cathode materials prepared in examples and comparative examples.
FIG. 2 is a LiNi synthesized in example 1 0.5 Mn 1.4 Zr 0.1 O 3.975 F 0.05 SEM image of @ NiHCF composite cathode material.
FIG. 3 is a view showing a composite LiNi synthesized in comparative example 1 0.5 Mn 1.4 Zr 0.1 O 3.95 F 0.05 SEM image of the cathode material.
Fig. 4 is a graph showing discharge curves of the positive electrode materials obtained in example 1 and comparative example 1 at 1C for cycles 1, 100, and 500.
Fig. 5 is a graph showing rate performance of the positive electrode materials obtained in example 1 and comparative example 3.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Example 1
A preparation method of a power battery anode material with a core-shell structure comprises the following steps:
(1) Preparation of lithium nickel manganese oxide
Nickel oxide, trimanganese tetroxide and lithium carbonate are weighed in a molar ratio of Li to Ni to Mn to Zr to F =2.2 2 And anion additive LiF, and premixing, wherein the lithium carbonate is excessive by 5%, adding the mixture into a sand mill using pure water as a solvent, and sanding for 1.5h at the speed of 1500r/min, wherein solid and liquid phases are mixedThe mass ratio of the mixed material is 15 percent (the mixed material accounts for 15 percent of the mass of pure water), the mixed slurry A after sanding is continuously transferred into a spray dryer through a peristaltic pump for spray drying at 200 ℃ to obtain yellow black powdery precursor B, then the precursor B is put into a high-temperature furnace at 850 ℃, sintered for 12h in the air atmosphere and annealed for 8h at 650 ℃, and after natural cooling, airflow crushing is carried out to obtain LiNi after doping of the positive and negative plasma 0.5 Mn 1.4 Zr 0.1 O 3.975 F 0.05 Black single crystal powder C.
(2) Preparing a core-shell structure composite material:
taking a proper amount of Na 4 Fe(CN) 6 ·10H 2 Preparing solution of O and pure water, recording as solution D, and taking appropriate amount of NiCl 2 ·6H 2 Preparing a solution from O and pure water, and marking as a solution E;
premixing the single crystal powder C with sodium citrate serving as a complexing agent and PVP serving as a reducing agent, placing the premixed solution into a 500mL empty beaker, pouring the solution E into the beaker, stirring the solution at room temperature for 30min, finally adding the solution D into the 500mL beaker, continuing stirring the solution D for 3h, stopping standing the solution at room temperature for 48h until the supernatant is clear, alternately cleaning the solution for 5 times by using a large amount of absolute ethyl alcohol and pure water, and drying the solution by blowing air at 80 ℃ for 12h to obtain the LiNi with the core-shell structure 0.5 Mn 1.4 Zr 0.1 O 3.975 F 0.05 @ NiHCF composite cathode material.
Example 2
A preparation method of a power battery anode material with a core-shell structure comprises the following steps:
(1) Preparation of single crystal lithium nickel manganese oxide
Nickel oxide, manganomanganic oxide and lithium carbonate were weighed into a mixer in a molar ratio Li: ni: mn: zr: F =2.12 2 And anion additive LiF, premixing, wherein the lithium carbonate is excessive by 3%, adding the mixture into a sand mill using pure water as a solvent, sanding for 3 hours at the speed of 1000r/min, wherein the mass ratio of solid to liquid is 20%, continuously transferring the sanded mixed slurry A into a spray dryer through a peristaltic pump, and performing spray drying at 190 ℃ to obtain yellow and black powderAnd putting the precursor B into a high-temperature furnace at 900 ℃, sintering for 10h in the air atmosphere, annealing for 12h at 650 ℃, naturally cooling, and performing jet milling to obtain cathode-anode doped LiNi 0.5 Mn 1.45 Zr 0.05 O 3.95 F 0.1 Black single crystal powder C.
(2) Preparing a core-shell structure composite material:
taking a proper amount of Na 4 Fe(CN) 6 ·10H 2 Preparing solution D from O and pure water, and taking appropriate amount of FeSO 4 ·7H 2 Preparing a solution from the O and pure water, and marking as a solution E;
premixing the single crystal powder C with sodium citrate serving as a complexing agent and PVP serving as a reducing agent, placing the premixed solution into a 500mL empty beaker, pouring the solution E into the beaker, stirring the solution at room temperature for 20min, finally adding the solution D into the 500mL beaker, continuing stirring the solution D for 1h, stopping standing the solution at room temperature for 8h until the supernatant is clear, alternately cleaning the solution for 5 times by using a large amount of absolute ethyl alcohol and pure water, and drying the solution by blowing air at 80 ℃ for 12h to obtain the LiNi with the core-shell structure 0.5 Mn 1.4 Zr 0.1 O 3.95 F 0.05 @ FeHCF composite positive electrode material.
Example 3
A preparation method of a power battery anode material with a core-shell structure comprises the following steps:
(1) Preparation of single crystal lithium nickel manganese oxide
Nickel oxide, manganous manganic oxide and lithium carbonate are weighed in a molar ratio of Li to Ni to Mn to Zr to F =2.24 2 And anion additive LiF, premixing, wherein the lithium carbonate is 6% in excess, adding the mixture into a sand mill using pure water as a solvent, sanding for 3 hours at a speed of 2000r/min, wherein the mass ratio of solid to liquid is 30%, continuously transferring the sanded mixed slurry A into a spray dryer through a peristaltic pump, performing spray drying at 210 ℃ to obtain a yellow-black powdery precursor B, then placing the precursor B into a 950 ℃ high-temperature furnace, sintering for 8 hours in the air atmosphere, annealing for 12 hours at 650 ℃, naturally cooling, and performing air flow crushing to obtain an anion and cation phase doped precursor BHybridized LiNi 0.5 Mn 1.45 Zr 0.05 O 3.975 F 0.05 Black single crystal powder C.
(2) Preparation of core-shell structure composite material
Taking a proper amount of Na 4 Fe(CN) 6 ·10H 2 Preparing solution D from O and pure water, and taking appropriate amount of CoSO 4 ·7H 2 Preparing a solution from O and pure water, and marking as a solution E;
premixing the single crystal powder C with sodium citrate serving as a complexing agent and PVP serving as a reducing agent, placing the premixed solution into a 500mL empty beaker, pouring the solution E into the beaker, stirring the solution at room temperature for 40min, finally adding the solution D into the 500mL beaker, continuing stirring the solution D for 5h, stopping standing the solution at room temperature for 36h until the supernatant is clear, alternately cleaning the solution for 5 times by using a large amount of absolute ethyl alcohol and pure water, and drying the solution by blowing air at 80 ℃ for 12h to obtain the LiNi with the core-shell structure 0.5 Mn 1.45 Zr 0.05 O 3.975 F 0.05 @ CoHCF composite positive electrode material.
Comparative example 1
Preparation of single crystal lithium nickel manganese oxide:
nickel oxide, manganomanganic oxide and lithium carbonate were weighed into a mixer in a molar ratio Li: ni: mn: zr: F =2.2 = 1 2 And anion additive LiF, premixing, wherein the lithium carbonate is excessive by 5%, adding the mixture into a sand mill using pure water as a solvent, sanding at the speed of 1500r/min for 1.5h, wherein the mass ratio of solid to liquid is 15%, continuously transferring the sanded mixed slurry A into a spray dryer through a peristaltic pump, performing spray drying at 200 ℃ to obtain a yellow-black powdery precursor B, then putting the precursor B into a high-temperature furnace at 850 ℃, sintering for 12h in the air atmosphere, annealing at 650 ℃ for 8h, naturally cooling, and performing jet milling to obtain LiNi doped with the anion and cation plasma 0.5 Mn 1.4 Zr 0.1 O 3.975 F 0.05 Black single crystal powder C.
Comparative example 2
Preparation of NiHCF material:
taking a proper amount of Na 4 Fe(CN) 6 ·10H 2 Preparing solution of O and pure water, recording as solution D, and taking appropriate amount of NiCl 2 ·6H 2 Preparing solution from O and pure water, recording the solution as solution E, premixing sodium citrate serving as a complexing agent and PVP serving as a reducing agent, placing the premixed solution into a 500mL empty beaker, pouring the solution E into the beaker, stirring the solution at room temperature for 30min, finally adding the solution D into the 500mL beaker, continuing stirring the solution for 3h, stopping stirring, standing the solution at room temperature for 48h until supernatant is clear, alternately cleaning the supernatant for 5 times by using a large amount of absolute ethyl alcohol and pure water, and performing air drying at 80 ℃ for 12h to obtain the NiHCF composite anode material of the Prussian blue analogue.
Comparative example 3
A preparation method of the composite cathode material comprises the following steps:
(1) Preparation of single crystal lithium nickel manganese oxide
The transition metal oxide nickel source, manganese source and lithium carbonate were weighed into a blender mixer and then added with the cationic additive ZrO 2 And anion additive LiF, premixing, wherein the lithium carbonate is excessive by 5%, adding the mixture into a sand mill using pure water as a solvent, sanding at the speed of 1500r/min for 1.5h, wherein the mass ratio of solid to liquid is 15%, continuously transferring the sanded mixed slurry A into a spray dryer through a peristaltic pump, carrying out spray drying at 200 ℃ to obtain a yellow black powdery precursor B, then putting the precursor B into a high-temperature furnace at 850 ℃, sintering for 12h in the air atmosphere, annealing for 8h at 650 ℃, naturally cooling, and carrying out air flow crushing to obtain LiNi doped with the anion and cation plasma 0.5 Mn 1.4 Zr 0.1 O 3.975 F 0.05 Black single crystal powder C.
(2) Preparation of alumina-coated composite material
0.529g of Al is weighed 2 O 3 And 8g of single crystal powder C are ball milled for 3 hours in a ball milling tank at the speed of 500r/min, the mixed powder is put into a sintering furnace at the temperature of 550 ℃ to be sintered for 5 hours after the ball milling is finished, and the mixed powder is naturally cooled to obtain LiNi 0.5 Mn 1.4 Zr 0.1 O 3.975 F 0.05 /Al 2 O 3 And (3) compounding the positive electrode material.
The composite material prepared in the above case is used as the anode material of the lithium ion battery, and the ratio of the anode active material: conductive agent Super-P: mixing a binder PVDF (polyvinylidene fluoride) with a mass ratio of 90 6 And 0.1M lithium bis (oxalato) borate LiBOB as a high-voltage electrolyte lithium source, 10% sulfolane SL as an additive, EC and DMC as an organic solvent at a volume ratio of 1.
Fig. 1 is an XRD pattern of the composite materials prepared in example 1 and comparative example 2, in which the XRD pattern of example 1 is compared with JCPDS No: the main peaks corresponding to 80-2162 correspond to one-to-one, and a small amount of Prussian blue analogue NiHCF peaks are accompanied.
LiNi synthesized in example 1 and comparative example 1 0.5 Mn 1.4 Zr 0.1 O 3.975 F 0.05 @ NiHCF and LiNi 0.5 Mn 1.4 Zr 0.1 O 3.975 F 0.05 The SEM of the composite material is shown in fig. 2 and 3, respectively. FIG. 4 is a graph showing the trend of the discharge curves of the materials of example 1 and comparative example 1 at a rate of 0.1C for the first, 100, and 500 charge-discharge cycles, and it is apparent that LiNi which is not subjected to coating modification 0.5 Mn 1.4 Zr 0.1 O 3.95 F 0.05 Although the initial discharge specific capacity was higher, the voltage plateau was slightly lower than that of the NiHCF-coated layer, and it was found that the polarization effect was relatively large, and that after 500 cycles, liNi having the NiHCF-coated layer was present 0.5 Mn 1.4 Zr 0.1 O 3.975 F 0.05 The composite positive electrode material has better cycle stability, and the capacity retention rates are respectively 80.1% and 63.7%.
FIG. 5 is a graph showing the rate performance of example 1 and comparative example 3 at different rates, comparing the results to find that the NiHCF coating layer is better than the Al coating layer 2 O 3 Has better rate capability, wherein LiNi 0.5 Mn 1.4 Zr 0.1 O 3.95 F 0.05 The @ NiHCF composite cathode material still can release a specific capacity of about 74.8mAh/g at a high rate of 10C.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (6)
1. A preparation method of a power battery anode material with a core-shell structure is characterized by comprising the following steps:
(1) Preparation of single crystal lithium nickel manganese oxide
Weighing and mixing nickel oxide, manganese oxide and lithium carbonate according to a molar ratio of Li to Ni to Mn to Zr to F = (2.12-2.24) to 1.00 2 And an anionic additive LiF, and premixing; adding the mixture into pure water, and sanding for 1-3h; performing spray drying on the mixed slurry A after sanding to obtain a yellow-black powdery precursor B; sintering the precursor B at 800-950 ℃ in the air atmosphere for 8-16h, annealing at 650 ℃ for 5-12h, naturally cooling, and performing jet milling to obtain cathode-anode doped LiNi 0.5 Mn 1.45 Zr 0.05 O 3.95 F 0.05 Black single crystal powder C;
in the step (1), 0 < x is less than or equal to 0.1, and 0 < y is less than or equal to 0.2;
(2) Preparation of core-shell structure power battery anode material
Preparation of Na 4 Fe(CN) 6 Aqueous solution, denoted as solution D; preparing a solution containing M ions, and marking as a solution E;
premixing the single crystal powder C with sodium citrate and polyvinylpyrrolidone, adding the solution E, stirring, adding the solution D, stirring for several hours, standing at room temperature until the supernatant is clear, alternately cleaning with anhydrous ethanol and pure water for several times, and drying to obtain MHCF in-situ coated LiNi 0.5 Mn 1.5-x Zr x O 4-0.5y F y @ MHCF composite cathodeA pole material;
in the step (2), M is more than one of Ni, zn, fe, co or Cu;
LiNi obtained in step (2) 0.5 Mn 1.5-x Zr x O 4-0.5y F y The @ MHCF composite cathode material has the crystal grain diameter of 1-4 mu m, the thickness of a coating layer of 10-200nm and the coating content of 1-10 percent.
2. The production method according to claim 1, characterized in that: in the step (1), the lithium carbonate is excessive by 3-6%.
3. The production method according to claim 1, characterized in that: sanding in the step (1) at the rotating speed of 1000-2000r/min.
4. The method of claim 1, wherein: the spray drying of the step (1) is carried out at 190-210 ℃.
5. A power battery anode material with a core-shell structure is characterized in that: prepared by the process of any one of claims 1 to 4.
6. Use of the material of claim 5 as a positive electrode material for lithium ion batteries.
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| CN111029542A (en) * | 2019-11-28 | 2020-04-17 | 银隆新能源股份有限公司 | Prussian blue material coated lithium ion battery ternary positive electrode material and preparation method thereof |
| CN113937256A (en) * | 2020-07-14 | 2022-01-14 | 天津国安盟固利新材料科技股份有限公司 | Method for coating lithium nickel manganese oxide cathode material by spraying |
| CN112582594B (en) * | 2020-12-14 | 2022-03-15 | 格林美(湖北)新能源材料有限公司 | Cobalt-free single crystal cathode material and preparation method and application thereof |
| CN112952056B (en) * | 2021-01-27 | 2022-10-25 | 中国科学院宁波材料技术与工程研究所 | Lithium-rich manganese-based composite cathode material and preparation method and application thereof |
| CN114447290B (en) * | 2021-12-21 | 2023-04-11 | 西安理工大学 | Modification method and application of lithium-rich manganese-based positive electrode material of lithium ion battery |
| CN115745030B (en) * | 2023-01-09 | 2023-05-12 | 浙江帕瓦新能源股份有限公司 | Potassium ion battery anode material, precursor thereof and preparation method |
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