CN115863613A - Lithium manganese iron phosphate coated modified high-nickel positive electrode material, and preparation method and application thereof - Google Patents
Lithium manganese iron phosphate coated modified high-nickel positive electrode material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a manganese lithium iron phosphate coated modified high-nickel cathode material, a preparation method and application thereof, belonging to the technical field of lithium ion battery preparation. The preparation method comprises the following two steps: firstly, LMFP, boric acid and NCM are mechanically mixed in a certain ratio, and then heat treatment is carried out at 220-300 ℃ under inert gas atmosphere. The method can form dense LMFP/LiBO on the NMC surface 2 The composite coating layer does not affect the charge transfer resistance, namely the rate performance of the material.
Description
Technical Field
The invention relates to a manganese lithium iron phosphate coated modified high-nickel cathode material, a preparation method and application thereof, belonging to the technical field of lithium ion battery preparation.
Background
Layered oxide LiNixCoyMn1-x-yO 2 (NCM) due to its higher theoretical specific capacity (about 280 mAh g −1 ) And high operating voltages, are a major family of battery positive electrode materials for electric vehicle applications. The properties of the material are closely related to the Ni content. It is reported that the higher the Ni content, the larger the specific capacity, but at the same time the safety performance is seriously deteriorated. In addition, increasing the charge cut-off voltage may increase the specific capacity, but this also sacrifices the safety of the battery. It is therefore of great importance to improve the safety properties of nickel-rich NCM materials without affecting their electrochemical properties, in particular the energy density of the battery.
During thermal runaway of an NCM battery, a series of exothermic reactions occur in the components inside the battery, wherein the release of oxygen from the NCM caused by phase change is a key step, and oxygen is used as a necessary promoter to initiate further chain reaction. Studies have shown that NCM positive electrode materials are susceptible to phase transition from a layered structure to a spinel structure at high temperatures and eventually to a rock-salt phase. Since Ni is in MO 2 The activation barrier for migration in the framework (M stands for Ni, co, mn) is much lower than that of Co and Mn, and the high-nickel NCM is easy to have phase change at a lower threshold temperature. Furthermore, delithiation (charging process) of NCM promotes the layer-to-spinel transition, since the unoccupied octahedral sites in the Li layer promote the transition metal ions to migrate from the transition metal layer to the lithium layer, which is a necessary step for the phase transition.
The electrolyte is in direct contact with the surface of the material, and the phase change of the NCM is accelerated by the existence of the electrolyte in the charge and discharge processes, because the electrolyte is reported to react with the high-oxidation-state NCM material to cause lithium ions and oxygen in crystal lattices to be extracted, so that the migration barrier of transition metal ions is reduced. Thus, the electrolyte significantly lowers the onset temperature of the phase transition, accelerating thermal runaway of the NCM material.
Various strategies have been devised to prevent or retard thermal runaway and improve the charge-discharge cycle stability of NCM batteries, including the use of flame-retardant electrolytes, oxide coatings, and/or temperature-responsive electrical (or ionic) barrier additives. In addition, the active NCM material is modified with a different coating to prevent its reaction with the electrolyte. The success of these approaches is often accompanied by the price of the electrochemical performance of the cell. Inorganic oxide (Al) using a coating method as an example 2 O 3 , ZrO 2 , Y 2 O 3 Etc.), fluoride (AlF) 3 , ZrFx, MgF 2 Etc.) and phosphates (FePO) 4 , MnPO 4 Etc.) have been widely studied for their high thermal and electrochemical stability. However, these coatings have significantly limited rate capability of coating modified NCM cathode materials because of limited ionic and electronic conductivity. The inactive coating material also reduces the energy density of the overall battery. Therefore, it is a challenge how to balance safety and performance by adjusting the coating thickness.
Lithium iron manganese phosphate (LMFP) has an olivine structure similar to that of lithium iron phosphate (LFP), and has high safety and stability. LMFP material Li under 2.75-4.35V voltage window + The storage capacity can reach 150 mAh g −1 . Meanwhile, the LMFP contains manganese element, so that the LMFP has a higher discharge platform (4.1V)vsLi + /Li), the overall energy density is about 20% higher than that of the conventional LFP. Thus, the energy density of the resulting battery using the LMFP blended with the NCM can be maintained at a level substantially comparable to that of the NCM battery. CN 109761210A relates to a method for preparing lithium iron manganese phosphate, which adopts a solution low-temperature hydrothermal synthesis method, and lithium iron manganese phosphate (LMFP) is coated on a ternary material, so that the circulation capacity retention rate and the safety performance of the ternary material are improved. The safety of a soft package battery manufactured by electrode slurry mixed with a small amount of LMFP and single crystal type NCM is also obviously improved. Concretely, a small amount of NCM pole slurry type 622 is addedMixed slurry was prepared with Limn0.3fe0.7po4 (LMFP), and the fabricated cathode exhibited a structure in which the surfaces of micron-sized NCM particles were surrounded by nanoscale LMFP particles. In this structure, the NCM/electrolyte contact is replaced by a NCM/LMFP/electrolyte contact. The phosphate anode material does not show oxygen precipitation phase change, so that the phosphate anode material has higher thermal stability than a nickel-rich layered anode material, thermal runaway is remarkably delayed, and the safety of the battery is improved. The LMFP and the NCM are matched for use, which is beneficial to realizing a high voltage platform, high energy density and high safety performance, and the subsequent large-scale application of the LMFP and the NCM is expected.
Disclosure of Invention
The invention aims to provide a manganese lithium iron phosphate coated modified high-nickel positive electrode material, a preparation method and application thereof, aiming at the problems in the prior art. The positive electrode material prepared by the method can solve the problems of poor cycle performance and low safety of the positive electrode material in the prior art.
In order to achieve the purpose of the invention, the technical scheme of the application is as follows:
a preparation method of a manganese lithium iron phosphate coated modified high-nickel cathode material comprises the following steps: adding LMFP (lithium manganese iron phosphate material) and NCM into an ethanol solution containing a small amount of fluorine-containing surfactant, mixing, and then carrying out vacuum drying to obtain an LMFP-NCM mixture; then mechanically fusing the LMFP-NCM mixture with a certain amount of boric acid according to the proportion, and then performing heat treatment in inert gas to form a denser LMFP/LiBO on the NCM surface 2 The composite coating layer of (1).
As a preferred embodiment of the present application, the fluorosurfactant is at least one of FS-104 and/or Kemu FS-3100.
In a preferred embodiment of the present invention, the mass ratio of the fluorosurfactant to ethanol is from 0.001 to 0.005; the mass ratio of ethanol to solid material (NCM + LMFP) is 0.2 to 0.6.
In a preferred embodiment of the present invention, the ratio of NCM, LMFP and boric acid is 1.
As a preferred embodiment of the present invention, the mass ratio of NCM, LMFP, fluorosurfactant and boric acid is 1:0.2:0.005:0.002.
as a better embodiment in the application, the mechanical mixing means that the materials are placed in a high-speed mixer for mixing, and the rotating speed is 500 to 900rpm; more preferably 500rpm; the time for mechanical mixing is 5 to 10min, more preferably 10min.
In a preferred embodiment of the present application, the inert gas is argon (high purity, 99.99%).
As a better embodiment in the application, the low-temperature heat treatment temperature is 220-300 ℃ and the time is 4-8h; more preferably, the temperature is 250 ℃ and the time is 8 hours.
Another object of the present invention is to protect the lithium iron manganese phosphate coated modified high nickel positive electrode material obtained by any one or a combination of the above method steps.
Further, the prepared manganese lithium iron phosphate coated modified high-nickel cathode material comprises an NCM (non-volatile memory) substrate and a composite layer, wherein the composite layer is coated on the surface of the NCM substrate; the NCM base material is a high-nickel cobalt-free NiMn binary material or a high-nickel ternary material; the general formula of the high-nickel cobalt-free NiMn binary material is LiNizMn 1-z O 2 Wherein 0.20<z<0.50; the general formula of the high-nickel ternary material is LiNixCoyMn 1-x-y O 2 Wherein, 0.7<x is less than or equal to 0.98, y is less than or equal to 0.02 and less than or equal to 0.3, and x + y is less than 1; the composite layer comprises lithium iron manganese phosphate (LiMn) x Fe 1-x PO 4 (wherein x is more than or equal to 0.4 and less than or equal to 0.8) and lithium borate LiBO 2 。
In the present application, if the two (LMFP, NCM) are directly subjected to physical mixing, such as mechanical stirring or mechanical fusion, the metal oxide coating agent is coated by a solid phase or physically mixed. The direct physical mixing of the micron-sized secondary spherical particles and LMFP nanoparticles does not avoid a solid-solid interface, which may affect the transmission of lithium ions or electrons, and the interface contact of the two is only physical adsorption, the binding force is not strong enough, local nanoparticle agglomeration may occur, partial region of the surface of the NCM cannot be completely coated, and meanwhile, partial NCM and nano LMFP may be separated during the subsequent homogenizing, coating, rolling and the like, so that the coating layer on the surface of the NCM is lost, thereby affecting the cycle performance and the thermal stability of the NCM.
Boric acid is white powdery crystal, the melting temperature is 169 ℃, namely the boric acid forms a molten state with fluidity above the temperature, a compact protective layer is easily formed on the surface of a base material, and a small amount of residual lithium LiOH and Li on the surface are reacted under the condition of heat treatment 2 CO 3 The reaction can produce LiBO 2 . The substance is firmly bonded with the ternary cathode material due to B-O bond connection, and has good compatibility. Meanwhile, due to good lithium ion conductivity, when the ternary material is used as a surface modification additive of a high ternary material, the lithium ion conductivity is not influenced. The LMFP and the boric acid are jointly used as the NCM surface coating agent, namely the LMFP, the boric acid and the NCM are mechanically fused according to a certain proportion and then are subjected to low-temperature (220 to 300 ℃) heat treatment for 4 to 8 hours in inert gas, so that the relatively compact LMFP/LiBO is formed on the NMC surface 2 The composite coating layer of (1).
The third invention aims to protect the application of the lithium iron manganese phosphate coated modified high-nickel cathode material prepared by the method, and the material is used for preparing a lithium ion battery.
The application provides a battery, and a battery preparation material of the battery comprises a finished product of the manganese lithium iron phosphate coated modified high-nickel cathode material.
Referring to this, the method for preparing the battery may include:
mixing the NCM electrode material obtained by coating modification with polyvinylidene fluoride (PVDF) serving as an active substance and acetylene black serving as a conductive agent according to the mass ratio of 85 to 10, fully and uniformly grinding, then adding N-methyl pyrrolidone (NMP) serving as a dispersing agent to disperse the mixture, grinding the mixture into uniform slurry (with the solid content of 65-69%) again, and coating the uniform slurry on an aluminum foil. Subsequently, the coated slurry was transferred to a vacuum oven at 110 ℃ for drying for 6 hours, and then the dried electrode material was rolled by a roll mill and dried in the vacuum oven at 120 ℃ for 12 hours. Taking out the dried electrode film, punching the sheet, weighing,and transferring the standard pole piece into a glove box for assembling the battery. Wherein, the electrolyte component that the equipment battery used is: 1M LiPF 6 Lithium salt and DMC + EC solvent. The electrode plate and the lithium plate of the ternary material modified by NCM and B/LMFP @ F-NCM are respectively used as a positive electrode and a negative electrode to be assembled into a button type half cell in a glove box. And (3) carrying out alternating current impedance test, constant current charge and discharge test under different multiplying powers and cycle performance stability test under 1C multiplying power on the assembled battery. Wherein, 1C =200mA · g -1 。
Compared with the prior art, the invention has the following beneficial effects:
and (I) because the boric acid in a molten state has certain fluidity and is similar to glue, the nano-scale LMFP particles are adhered on the surface of the micron-scale NCM secondary sphere more tightly. Small amount of residual fluorine surfactant on surface and LMFP/LiBO 2 The formed dense coating layer prevents the electrolyte from directly contacting with the NCM surface, and inhibits the surface interface performance from deteriorating. In addition, liBO formed by reaction of boric acid and residual lithium on the surface 2 Not only reduces the residual alkali on the surface of NCM, but also reduces the residual alkali on the surface of the NCM due to LiBO 2 Good lithium ion conductivity, so that a denser LMFP/LiBO is formed on the surface of the NMC 2 The composite coating layer does not affect the charge transfer resistance, namely the rate performance of the material.
And (II) the capacity retention rate of the battery obtained by the composite modified material after 100 cycles is improved by more than 20% compared with the performance of the battery prepared by an unmodified blank NCM sample.
Drawings
FIG. 1 is a blank LiNi 0.92 Co 0.055 Mn 0.025 O 2 SEM images of the sample and B/LMFP @ F-NCM composite; wherein a is an SEM image of a blank sample, and the magnification is 3000 times; b is an SEM image of a blank sample, and the magnification is 10000 times; c is an SEM image of the B/LMFP @ F-NCM composite material, and the magnification is 3000 times; d is SEM image of B/LMFP @ F-NCM composite material with magnification of 10000 times.
FIG. 2 is an XRD spectrum of a blank sample (NCM), an LFMP/NCM composite sample, an LFMP and fluorosurfactant composite coating sample B/LMFP @ F-NCM;
FIG. 3 is a graph of the cycling performance of blank NCM samples, LMFP/NCM, B/LMFP/NCM and B/LMFP @ F-NCM;
FIG. 4 is a DSC thermal runaway curve comparison graph of blank NCM-like, B/LMFP @ F-NCM composite coated samples.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. The specific embodiments described herein are merely illustrative of the invention and are not intended to be limiting.
In the present application, lithium manganese iron phosphate is a commercially available product, and in the following examples, lithium manganese iron phosphate produced by tianjinston energy technology ltd (model SLMFP-64) is used.
In the present application, the ratios that are not specified are mass ratios, and% are mass percentages.
Example 1:
the embodiment provides a manganese lithium iron phosphate coated modified high-nickel cathode material, which is prepared by the following method:
step (1): mechanically fusing an NCM92 calcined material and a lithium iron manganese phosphate material in an ethanol solvent containing a fluorine surfactant;
0.5g of FS-3100 was weighed out and added to 50mL of ethanol solvent, and stirred at 300rpm for 30min to sufficiently disperse the mixture to prepare an ethanol solution containing a small amount of FS-3100 fluorosurfactant. 80g of LiNi was weighed 0.92 Co 0.055 Mn0. 025 O 2 (NCM) the positive electrode material was added to an ethanol solution containing FS-3100 fluorosurfactant and stirred (250 rpm) for 15min to mix well. And then, weighing 20g of lithium manganese iron phosphate, adding the 20g of lithium manganese iron phosphate into the solution, ensuring that the mass ratio of the lithium manganese iron phosphate to the NCM material is 2, wherein the weight ratio of FS-3100: (NCM + LFMP) mass ratio =0.005, and stirring and mixing were continued for 30min, followed by rapidly pouring the mixture solution into a vacuum filtration apparatus for filtration. And then immediately transferring the filter cake into a vacuum drying oven, and drying at 150 ℃ for 2h to obtain the dried fluorosurfactant and lithium manganese iron phosphate coated NCM material, which is marked as LMFP @ F-NCM.
Step (2): blending and sintering an LMFP @ F-NCM material and boric acid:
the 100gLMFP @ F-NCM material after mechanical fusion was blended with 0.2g boric acid (guaranteed mass ratio of 100.2) in a high speed mixer at a rotation speed of 600r/min for 15min, and then the mixture was loaded in a sagger and transferred into a box furnace. In an argon atmosphere (furnace pressure controlled at 10Pa, gas flow rate at 3 m) 3 H) heating to 220 ℃ at the speed of 3 ℃/min, sintering for 8h, then naturally cooling to 120 ℃, and taking out to obtain LiBO 2 The fast ion conductor layer coating material B/LMFP @ F-NCM (manganese iron phosphate coated modified high nickel anode material).
The NCM92 calcined material is prepared by the following steps:
(1) preparation of Ni by coprecipitation 0.92 Co 0.05 Mn 0.03 (OH) 2 Precursor: mixing the raw materials NiSO 4 ·6H 2 O、CoSO 4 ·7H 2 O and MnSO 4 ·H 2 Weighing O according to a certain molar ratio (the molar ratio is x: y:1-x-y, the total amount of Ni, co and Mn is =0.2 mol/L), adding into deionized water, stirring at a constant speed of 600rpm to completely dissolve to obtain a transition metal ion solution, then inputting into a tank reactor by a flow pump, and adding into a reactor N 2 Stirring was continued under an atmosphere. Simultaneously, 0.2mol/L NaOH solution and a proper amount of NH are added 3 ·H 2 After mixing, the mixture is input into the transition metal ion solution through a flow pump. The stirring speed was maintained at 700rpm, and the pH =11.0 was maintained under control. Then, the mixture is precipitated, vacuum filtered and separated, washed by deionized water, to remove impurity ions and sulfate ions, and then the collected precipitate is fully dried in a vacuum oven at 120 ℃ for 12 hours; obtained Ni 0.92 Co 0.055 Mn 0.025 (OH) 2 And (3) precursor products.
(2) The obtained Ni 0.92 Co 0.055 Mn 0.025 (OH) 2 Precursor product and LiOH H 2 And O is uniformly mixed, wherein the mass ratio of Ni + Co + Mn metal ions to lithium salt is ensured to be 1. Placing the mixture in a box furnace, O 2 Raising the temperature at a speed of 3 ℃/min under the atmosphere, and firstly pre-lithium at 500 DEG CSintering for 6h, heating to 750 ℃ at the speed of 3 ℃/min, preserving heat for 12h, naturally cooling to 120 ℃, and taking out sintered LiNi 0.92 Co 0.055 Mn 0.025 O 2 And is referred to as the NCM92 positive electrode material.
Example 2:
the embodiment provides a manganese lithium iron phosphate coated modified high-nickel cathode material, which is prepared by the following method:
step (1): mechanically fusing an NCM92 calcined material and a lithium iron manganese phosphate material in an ethanol solvent containing a fluorine surfactant;
0.25g of FS-3100 and 0.25g of FS-104 fluorine surfactant are weighed and added into 50mL of ethanol solvent, stirred for 30min at 300rpm, and fully dispersed to prepare ethanol solution containing the composite fluorine surfactant with a certain concentration. 80g of LiNi was weighed 0.92 Co 0.055 Mn0. 025 O 2 (NCM) the positive electrode material was added to an ethanol solution containing FS-3100 fluorosurfactant and stirred (250 rpm) for 15min to mix well. Subsequently, 20g of lithium manganese iron phosphate is weighed and added into the solution, the mass ratio of the lithium manganese iron phosphate to the NCM material is ensured to be 2, the mass ratio of the fluorosurfactant to (NCM + LFMP) is =0.005, the mixture is continuously stirred and mixed for 30min, and then the mixture solution is quickly poured into a vacuum filtration device for filtration. And then immediately transferring the filter cake to a vacuum drying oven for drying for 2h at the temperature of 150 ℃, thus obtaining the dried fluorosurfactant and lithium manganese iron phosphate coated NCM material which is marked as LMFP @ F-NCM.
Step (2): blending and sintering an LMFP @ F-NCM material and boric acid:
the mechanically fused 100gLMFP @ F-NCM material was blended with 0.8g boric acid in a high speed mixer at 600r/min for 15min, and the mixture was loaded into a sagger and transferred into a box furnace. In an argon atmosphere (furnace pressure controlled at 10Pa, gas flow rate at 3 m) 3 H) heating to 280 ℃ at the speed of 3 ℃/min, sintering for 5h, then naturally cooling to 120 ℃, and taking out to obtain LiBO 2 The fast ion conductor layer coating material B/LMFP @ F-NCM (manganese iron phosphate coated modified high nickel anode material).
The NCM92 fired material described above was prepared in accordance with the procedure of example 1.
Example 3:
the embodiment provides a method for efficiently compounding lithium iron manganese phosphate and a high-nickel ternary cathode material, which is prepared by the following steps:
step (1): mechanically fusing an NCM92 calcined material and a lithium iron manganese phosphate material in an ethanol solvent containing a fluorine surfactant;
0.8g of FS-3100 is weighed and added into 50mL of ethanol solvent, stirred for 30min at 300rpm, and fully dispersed to prepare ethanol solution containing FS-3100 fluorine surfactant with certain concentration. 80g of NCM positive electrode material was weighed into an ethanol solution containing FS-3100 fluorosurfactant and stirred (250 rpm) for 15min to mix well. And then, weighing 20g of lithium manganese iron phosphate, adding the 20g of lithium manganese iron phosphate into the solution, ensuring that the mass ratio of the lithium manganese iron phosphate to the NCM material is 2, wherein the weight ratio of FS-3100: (NCM + LFMP) mass ratio =0.008, stirring and mixing was continued for 30min, and then the mixture solution was quickly poured into a vacuum filtration apparatus for filtration. And then immediately transferring the filter cake to a vacuum drying oven for drying for 2h at the temperature of 150 ℃, thus obtaining the dried fluorosurfactant and lithium manganese iron phosphate coated NCM material which is marked as LMFP @ F-NCM.
Step (2): blending and sintering an LMFP @ F-NCM material and boric acid:
the mechanically fused 100gLMFP @ F-NCM material was blended with 0.5g boric acid in a high speed mixer at 600r/min for 15min, and the mixture was loaded into a sagger and transferred into a box furnace. In an argon atmosphere (furnace pressure controlled at 10Pa, gas flow rate at 3 m) 3 H) heating to 250 ℃ at the speed of 3 ℃/min, sintering for 5h, naturally cooling to 120 ℃, and taking out to obtain LiBO 2 The fast ion conductor layer is coated with a material B/LMFP @ F-NCM (manganese iron phosphate coated modified high-nickel positive electrode material).
The NCM92 fired material described above was prepared in accordance with the procedure of example 1.
Example 4:
the embodiment provides a method for efficiently compounding lithium iron manganese phosphate and a high-nickel ternary cathode material, which is prepared by the following steps:
step (1): mechanically fusing an NCM92 calcined material and a lithium iron manganese phosphate material in an ethanol solvent containing a fluorine surfactant;
0.2g of FS-3100 is weighed and added into 50mL of ethanol solvent, stirred for 30min at 300rpm, and fully dispersed to prepare ethanol solution containing FS-3100 fluorine surfactant with certain concentration. 80g of NCM positive electrode material was weighed into an ethanol solution containing FS-3100 fluorosurfactant and stirred (250 rpm) for 15min to mix well. And then, weighing 20g of lithium manganese iron phosphate, adding the 20g of lithium manganese iron phosphate into the solution, ensuring that the mass ratio of the lithium manganese iron phosphate to the NCM material is 2, wherein the weight ratio of FS-3100: (NCM + LFMP) mass ratio =0.008, stirring and mixing was continued for 30min, and then the mixture solution was quickly poured into a vacuum filtration apparatus for filtration. And then immediately transferring the filter cake to a vacuum drying oven for drying for 2h at the temperature of 150 ℃, thus obtaining the dried fluorosurfactant and lithium manganese iron phosphate coated NCM material which is marked as LMFP @ F-NCM.
Step (2): blending and sintering an LMFP @ F-NCM material and boric acid:
the mechanically fused 100gLMFP @ F-NCM material was blended with 0.2g boric acid in a high speed mixer at 600r/min for 15min, and the mixture was loaded into a sagger and transferred into a box furnace. In an argon atmosphere (furnace pressure controlled at 10Pa, gas flow rate at 3 m) 3 H) heating to 220 ℃ at the speed of 3 ℃/min, sintering for 8h, naturally cooling to 120 ℃, and taking out to obtain LiBO 2 The fast ion conductor layer coating material B/LMFP @ F-NCM (manganese iron phosphate coated modified high nickel anode material).
The NCM92 fired material described above was prepared in accordance with the procedure of example 1.
Example 5:
the embodiment provides a method for efficiently compounding lithium iron manganese phosphate and a high-nickel ternary cathode material, which is prepared by the following steps:
step (1): mechanically fusing an NCM92 calcined material and a lithium iron manganese phosphate material in an ethanol solvent containing a fluorine surfactant;
0.8g of FS-3100 is weighed and added into 50mL of ethanol solvent, stirred for 30min at 300rpm, and fully dispersed to prepare ethanol solution containing FS-3100 fluorine surfactant with certain concentration. 80g of NCM positive electrode material was weighed into an ethanol solution containing FS-3100 fluorosurfactant and stirred (250 rpm) for 15min to mix well. And then, weighing 20g of lithium manganese iron phosphate, adding the 20g of lithium manganese iron phosphate into the solution, ensuring that the mass ratio of the lithium manganese iron phosphate to the NCM material is 2, wherein the weight ratio of FS-3100: (NCM + LFMP) mass ratio =0.008, stirring and mixing was continued for 30min, and then the mixture solution was quickly poured into a vacuum filtration apparatus for filtration. And then immediately transferring the filter cake to a vacuum drying oven for drying for 2h at the temperature of 150 ℃, thus obtaining the dried fluorosurfactant and lithium manganese iron phosphate coated NCM material which is marked as LMFP @ F-NCM.
Step (2): blending and sintering an LMFP @ F-NCM material and boric acid:
the mechanically fused 100gLMFP @ F-NCM material was blended with 0.8g boric acid in a high speed mixer at 600r/min for 15min, and the mixture was loaded into a sagger and transferred into a box furnace. In an argon atmosphere (furnace pressure controlled at 10Pa, gas flow rate at 3 m) 3 H) heating to 220 ℃ at the speed of 3 ℃/min, sintering for 5h, naturally cooling to 120 ℃, and taking out to obtain LiBO 2 The fast ion conductor layer coating material B/LMFP @ F-NCM (manganese iron phosphate coated modified high nickel anode material).
The NCM92 fired material described above was prepared in accordance with the procedure of example 1.
Comparative example 1:
the embodiment provides a method for efficiently compounding lithium iron manganese phosphate and a high-nickel ternary cathode material, which is prepared by the following steps:
step (1): mechanically fusing an NCM92 calcined material, a lithium manganese iron phosphate material and a boric acid coating agent;
80g of NCM cathode material, 20g of lithium manganese iron phosphate and 0.5g of boric acid are weighed and added into a high-speed mixer, the materials are blended for 15min at the rotating speed of 600r/min, and then the mixture is contained in a sagger and is transferred into a box furnace. Heating to 220 deg.C at a rate of 3 deg.C/min under argon atmosphere (pressure in furnace is controlled at 10Pa, gas flow is 3m 3/h), sintering for 8h, and naturally cooling to 120 deg.CTaking out to obtain LiBO 2 And the fast ion conductor layer cladding material is B/LMFP @ F-NCM.
The NCM92 fired material described above was prepared in accordance with the procedure of example 1.
Comparative example 2:
the embodiment provides a method for efficiently compounding lithium iron manganese phosphate and a high-nickel ternary cathode material, which is prepared by the following steps:
step (1): mechanically fusing the NCM92 calcined material and the lithium iron manganese phosphate material in an ethanol solvent containing the fluorosurfactant, weighing 0.5g of FS-3100, adding the FS-3100 into 50mL of the ethanol solvent, stirring at 300rpm for 30min, and fully dispersing to prepare a fluorosurfactant ethanol solution with a certain concentration. 80g of NCM positive electrode material was weighed into an ethanol solution containing FS-3100 fluorosurfactant and stirred (250 rpm) for 15min to mix well. And then, weighing 20g of lithium manganese iron phosphate, adding the 20g of lithium manganese iron phosphate into the solution, and ensuring that the mass ratio of the lithium manganese iron phosphate to the NCM material is 2, FS-3100: (NCM + LFMP) mass ratio =0.005, stirring and mixing was continued for 30min, and then the mixture solution was quickly poured into a vacuum filtration apparatus for filtration. And then immediately transferring the filter cake to a vacuum drying oven for drying for 2h at the temperature of 150 ℃, thus obtaining the dried fluorosurfactant and lithium manganese iron phosphate coated NCM material which is marked as LMFP @ F-NCM.
The NCM92 fired material described above was prepared in accordance with the procedure of example 1.
Comparative example 3:
the embodiment provides a method for efficiently compounding lithium iron manganese phosphate and a high-nickel ternary cathode material, which is prepared by the following steps:
mechanically mixing an NCM92 calcined material and a lithium manganese iron phosphate material, weighing 80g of an NCM positive electrode material and 20g of lithium manganese iron phosphate, adding into a high-speed mixer, blending for 15min at the rotating speed of 600r/min, then loading the mixture into a sagger, and transferring into a box furnace. In an argon atmosphere (furnace pressure controlled at 10Pa, gas flow rate at 3 m) 3 H) heating to 220 ℃ at the speed of 3 ℃/min, sintering for 8h, and then naturally cooling to 120 ℃ and taking out to obtain the LMFP/NCM. The NCM92 fired material described above was prepared in accordance with the procedure of example 1.
Comparative example 4:
the embodiment provides a method for efficiently compounding lithium iron manganese phosphate and a high-nickel ternary cathode material, which is prepared by the following steps:
step (1): mechanically fusing an NCM92 calcined material and a lithium iron manganese phosphate material in an ethanol solvent containing a Cetyl Trimethyl Ammonium Bromide (CTAB) surfactant;
weighing 0.5g CTAB, adding into 50mL ethanol solvent, stirring at 300rpm for 30min, fully dispersing, and preparing to obtain fluorosurfactant ethanol solution with a certain concentration. 80g of NCM positive electrode material was weighed and added to an ethanol solution containing CTAB surfactant and stirred (250 rpm) for 15min to be mixed well. And then, weighing 20g of lithium manganese iron phosphate, adding the 20g of lithium manganese iron phosphate into the solution, ensuring that the mass ratio of the lithium manganese iron phosphate to the NCM material is 2: (NCM + LFMP) mass ratio =0.008, stirring and mixing was continued for 30min, and then the mixture solution was quickly poured into a vacuum filtration apparatus for filtration. And then immediately transferring the filter cake to a vacuum drying oven for drying for 2h at the temperature of 150 ℃, thus obtaining the dried CTAB surfactant and the NCM material coated by the lithium manganese iron phosphate, and marking as LMFP @ F-NCM.
Step (2): blending and sintering an LMFP @ CTAB-NCM material and boric acid:
the mechanically fused 100gLMFP @ F-NCM material was blended with 0.8g boric acid in a high speed mixer at 600r/min for 15min, and the mixture was loaded into a sagger and transferred into a box furnace. In an argon atmosphere (furnace pressure controlled at 10Pa, gas flow rate at 3 m) 3 H) heating to 220 ℃ at the speed of 3 ℃/min, sintering for 5h, then naturally cooling to 120 ℃, and taking out to obtain LiBO 2 The fast ion conductor layer is coated with a material B/LMFP @ CTAB-NCM.
The NCM92 fired material described above was prepared in accordance with the procedure of example 1.
And (3) carrying out performance test on the lithium iron manganese phosphate coated modified high-nickel cathode material prepared in each embodiment and the material prepared in each proportion. The determination method comprises the following steps:
the prepared material is used as an active substance and polyvinylidene fluoride (PV) as a binderDF) and acetylene black, a conductive agent, were mixed in a mass ratio of 85 to 10, and sufficiently and uniformly ground, then azomethylpyrrolidone (NMP) was added as a dispersant to disperse the mixture, and it was once more ground into a uniform slurry (about 66% solid content) and coated on an aluminum foil. Subsequently, the coated slurry was transferred to a vacuum oven at 110 ℃ for drying for 6 hours, and then the dried electrode material was rolled by a roll mill and dried in the vacuum oven at 120 ℃ for 12 hours. And taking out the dried electrode film, punching, weighing, and transferring the standard pole piece into a glove box to assemble the battery. Wherein, the used electrolyte composition of equipment battery is: 1M LiPF 6 Lithium salt and DMC + EC solvent. The electrode plate and the lithium plate of the ternary material modified by NCM and B/LMFP @ F-NCM are respectively used as a positive electrode and a negative electrode to be assembled into a button type half cell in a glove box. And (3) carrying out alternating current impedance test, constant current charge and discharge test under different multiplying powers and cycle performance stability test under 1C multiplying power on the assembled battery. Wherein 1C =200mA · g -1 。
The specific data are shown in Table 1 and FIGS. 1 to 4, wherein FIG. 1 is a blank LiNi 0.92 Co 0.055 Mn 0.025 O 2 SEM of sample, B/LMFP @ F-NCM composite; FIG. 2 is XRD patterns of blank sample and composite coated sample B/LMFP @ F-NCM; FIG. 3 is a blank NCM sample, LMFP + NCM; B/LMFP @ F-NCM cycle performance curve; FIG. 4 is a comparison of thermal runaway curves for blank NCM-like, B/LMFP @ F-NCM samples:
TABLE 1 comparison of Battery Performance of assembled button cells of different modified samples
| Sample | Sample composition | 0.1 Cg capacity （mAh g-1） | First coulomb Efficiency (%) | 1C lower 100 circles container Amount holding ratio (%) | Charge transfer resistor anti-Rct (omega) |
| Example 1 | 0.5%FS+20%LMFP-80%NCM+0.2%B；250 ℃ | 205.5 | 88.9 | 91.0 | 85.35 |
| Example 2 | 0.5% FS (FS-104 to FS-3100 mass ratio =1: 1）+20%LMFP-80%NCM+0.8%B;280℃ | 201.7 | 88.3 | 89.7 | 121.9 |
| example 3 | 0.8%FS+20%LMFP-80%NCM+0.5%B；250 ℃ | 204.2 | 90.4 | 90.7 | 94.8 |
| Example 4 | 0.2%FS+20%LMFP-80%NCM+0.2%B；220 ℃ | 206.33 | 89.3 | 90.2 | 92.93 |
| Example 5 | 0.8%FS+20%LMFP-80%NCM+0.8%B；220 ℃ | 203.5 | 89.2 | 90.8 | 176 |
| Comparative example 1 | 20%LMFP-80%NCM+0.5%B；220℃ | 202.8 | 89.5 | 88.0 | 209 |
| Comparative example 2 | 0.5%FS+20%LMFP-80%NCM；220℃ | 202.05 | 88.3 | 87.2 | 376 |
| Comparative example 3 | 20%LMFP-80%NCM | 201.2 | 87.8 | 86.0 | 486 |
| Comparative example 4 | 0.5%CTAB+20%LMFP-80%NCM-0.8%B； 220℃ | 189 | 86.1 | 80.6 | 405 |
As can be seen from Table 1, when the compounding ratio of LMFP and NCM is the same (2. In addition, alternating current impedance analysis of the sample shows that the charge transfer impedance value of the sample obtained by adding the fluorine surfactant and the boric acid as auxiliary is obviously reduced compared with that of a blank group, which shows that on one hand, the LMFP is more uniformly dispersed and coated on the surface of the NCM secondary sphere, and meanwhile, after the boric acid is added, an ultrathin lithium ion conductive LiBO2 layer formed at a gap between the NCM and the LMFP is beneficial to lithium ion conduction and reduces interface charge transfer impedance.
As can be seen from a and b in FIG. 1, the blank NCM secondary sphere size is about 10-12 μm, and the primary particle size is 300-600nm; as can be seen from c and d in FIG. 1, LFMP dispersed by the fluorosurfactant is uniformly coated on the NCM and the pores are LiBO 2 The thin layer of material is coated, which is beneficial to improving the conductivity of the material, resisting the corrosion of electrolyte and improving the cycling stability, and can be seen from the improvement of the subsequent electrochemical performance. Fig. 2 is an XRD spectrum of the NCM complex sample directly coated with LFMP and the NCM sample coated with fluorosurfactant and boric acid-assisted LMFP, and a comparison shows that the diffraction peak positions of the complex coated sample and the LMFP directly coated sample are substantially the same, which indicates that the addition of a small amount of fluorosurfactant and boric acid does not cause impurity generation and does not affect the peak positions of NCM and LMFP. FIG. 3 is a graph of the cycling performance of blank NCM, LFMP and fluorosurfactant, boric acid-assisted LMFP coated NCM samples, comparing to find a significant improvement in LMFP coated NCM over blank NCM samples while LFMP coated NCM dispersed with the addition of fluorosurfactant to assist inThe cycle performance of the latter stage of the boric acid treatment is obviously improved compared with that of LMFP/NCM, which probably leads LMFP to be more uniformly coated on the NCM due to the fluorine surfactant, and simultaneously leads the cycle performance to be further improved due to the electrolyte corrosion resistance of the fluorine surfactant and LiBO 2. In addition, the DSC differential thermal analysis curve in FIG. 4 shows that the thermal runaway temperature of the composite coating sample B/LMFP @ F-NCM can reach 227 ℃, which is obviously improved compared with the blank NCM sample at 220 ℃, and this shows that the composite coating sample has more excellent thermal safety performance.
The foregoing basic embodiments of the invention and their various further alternatives can be freely combined to form multiple embodiments, all of which are contemplated and claimed herein. In the scheme of the invention, each selection example can be combined with any other basic example and selection example at will. Numerous combinations will be known to those skilled in the art.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A preparation method of a manganese lithium iron phosphate coated modified high-nickel cathode material is characterized by comprising the following steps: adding LMFP and NCM into an ethanol solution containing a small amount of fluorosurfactant for mixing, and then carrying out vacuum drying on the mixture to obtain an LMFP-NCM mixture; and then mechanically fusing the LMFP-NCM mixture with a certain amount of boric acid, and then performing low-temperature heat treatment in inert gas to obtain the lithium iron manganese oxide modified anode material.
2. The method for preparing the lithium iron manganese phosphate-coated modified high-nickel cathode material according to claim 1, wherein the method comprises the following steps: the fluorine-containing surfactant is at least one or a composition of two of FS-104 and Kemu FS-3100; the mass ratio of the fluorine-containing surfactant to the ethanol is 0.001 to 0.005; the mass ratio of the ethanol to the solid material is 0.2 to 0.6, and the solid material is NCM and LMFP.
3. The method for preparing the lithium iron manganese phosphate-coated modified high-nickel cathode material according to claim 1, wherein the method comprises the following steps: the mass ratio of NCM to LMFP to boric acid is 1 to 0.1 to 0.4.
4. The method for preparing the lithium iron manganese phosphate-coated modified high-nickel cathode material according to claim 1, wherein the method comprises the following steps: the temperature of the vacuum drying is 140 +/-10 ℃, and the time is 3 +/-1 h.
5. The method for preparing the lithium iron manganese phosphate-coated modified high-nickel cathode material according to claim 1, wherein the method comprises the following steps: the mechanical fusion is to mix the materials in a high-speed mixer at the rotating speed of 500 to 900rpm; the mixing time is 5-10 min.
6. The method for preparing the lithium iron manganese phosphate-coated modified high-nickel cathode material according to claim 1, wherein the method comprises the following steps: the inert gas is pure argon.
7. The method for preparing the lithium iron manganese phosphate-coated modified high-nickel cathode material according to claim 1, wherein the method comprises the following steps: the temperature of the low-temperature heat treatment is 220-300 ℃, and the time is 4-8h.
8. The lithium iron manganese phosphate coated modified high-nickel cathode material obtained by the method according to any one of claims 1 to 7, wherein: the material comprises an NCM base material and a composite layer, wherein the composite layer is coated on the surface of the NCM base material; the NCM base material is a high-nickel cobalt-free NiMn binary material or a high-nickel ternary material.
9. The lithium iron manganese phosphate-coated modified high-nickel positive electrode material according to claim 8, wherein: the general formula of the high-nickel cobalt-free NiMn binary material is LiNizMn 1-z O2, wherein 0.20<z<0.50; the general formula of the high-nickel ternary material is LiNixCoyMn 1-x-y O 2 Wherein, 0.7<x is less than or equal to 0.98, y is less than or equal to 0.02 and less than or equal to 0.3, and x + y is less than 1; the composite layer comprises lithium iron manganese phosphate (LiMn) x Fe 1-x PO 4 And lithium borate LiBO 2 Wherein x is more than or equal to 0.4 and less than or equal to 0.8.
10. The application of the lithium iron manganese phosphate coated modified high-nickel cathode material as claimed in claim 9, wherein: the material is used for preparing a lithium ion battery.
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Inventor after: Lei Ying Inventor after: Zhang Jue Inventor after: Cao Tangzhe Inventor after: Xie Huaming Inventor after: Yuan Siqi Inventor after: Li Jianying Inventor after: Fan Hang Inventor after: Fang Yongxian Inventor after: Yang Junjie Inventor before: Lei Ying Inventor before: Zhang Jue Inventor before: Cao Tangzhe Inventor before: Xie Huaming Inventor before: Yuan Siqi Inventor before: Li Jianying Inventor before: Fan Hang Inventor before: Fang Yongxian Inventor before: Yang Junjie |