CN114655990A - Use of composite materials - Google Patents

Use of composite materials Download PDF

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CN114655990A
CN114655990A CN202210529179.4A CN202210529179A CN114655990A CN 114655990 A CN114655990 A CN 114655990A CN 202210529179 A CN202210529179 A CN 202210529179A CN 114655990 A CN114655990 A CN 114655990A
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lithium
manganese hydroxide
precursor
composite material
nickel
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CN114655990B (en
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张宝
程磊
丁瑶
邓鹏�
林可博
周亚楠
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Zhejiang Power New Energy Co Ltd
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Abstract

The invention belongs to the field of lithium ion battery materials, and discloses an application of a composite material in a lithium ion battery material. According to the invention, the porous composite material of aluminum fluoride coated with nano manganese hydroxide is formed by etching nano aluminum powder. And then, in the wet preparation stage of the precursor material, the composite material slowly releases the nano manganese hydroxide, so that the precursor grows on the manganese hydroxide and gradually wraps the manganese hydroxide. The precursor material is dried at a higher temperature, hydrogen fluoride gas is slowly released, aluminum fluoride is converted into aluminum oxide, and the precursor becomes loose and porous. And then sintering through lithium mixing to obtain the cathode material. Due to the existence of the three-dimensional channel in the anode material, lithium ions are more thoroughly deintercalated in the charge and discharge processes, and the material has better reversibility and stability. The existence of lithium manganate and lithium aluminate also provides more pillars for the material, and reduces the structural collapse of the anode material in the long-cycle process.

Description

Use of composite materials
The application is a divisional application of a patent with the application number of 2022102671804 and the name of 'precursor material, cathode material, preparation method, composite material and application', and the application date of 2022, 3 months and 18 days.
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to an application of a composite material in a lithium ion battery material.
Background
Lithium ion batteries have become the main power source for electric vehicles due to their high energy density and long service life. To meet the market demand for long driving mileage and short charging time of electric vehicles, research is currently focused on developing a positive electrode material having high energy and high power density. Because LiNi0.8Co0.1Mn0.1O2(NCM811) high Capacity (about 200 mAh. g)-1) High working voltage (-3.8V vs Li)+/Li) and low cost, is the most promising material to meet this market demand. However, the rate performance of NCM811 is poor, mainly due to two reasons: (1) NCM811 having alpha-NaFeO2A layered structure (space group R-3 m) having lithium layers and transition metal layers alternately arranged. Due to the fact thatThe energy barrier of lithium ions in the lithium layer is low, and it tends to be transported in two dimensions. (2) Lithium ions and divalent nickel ions have similar radii and nickel ions tend to occupy octahedral sites in the lithium layer during material synthesis and electrochemical cycling, thereby blocking the two-dimensional path for lithium ion diffusion within the lithium layer. In addition, since the nickel-oxygen bond energy is higher than that of the lithium-oxygen bond, the lattice spacing of the lithium plate is reduced by the inversion defect of the divalent nickel ion, which leads to higher activation barrier diffusion of the lithium ion and finally reduces the macroscopic diffusivity of the lithium ion.
In order to further improve the cycling stability and rate capability of the high nickel material, many scholars make efforts. Patent document No. CN113479944A discloses a preparation method of a modified high-nickel ternary cathode material: uniformly mixing the nickel-cobalt-manganese hydroxide precursor with a lithium source and a magnesium source, and then performing two-stage sintering to obtain a magnesium-doped ternary high-nickel positive electrode material; dispersing the magnesium-doped ternary high-nickel positive electrode material in an organic solvent, adding a vanadium source and a lithium source, uniformly stirring, heating to evaporate, drying, and sintering at high temperature to obtain the lithium vanadate-coated magnesium-doped high-nickel ternary positive electrode material. The high-nickel ternary cathode material subjected to double modification treatment by magnesium ion doping and fast ion conductor coating can synergistically improve the cycle performance and rate capability of the material. Patent document No. CN112750991A discloses a double-modified high-nickel ternary material and a preparation method thereof, the method comprising: (1) performing first roasting on a mixture containing a high-nickel ternary precursor and a lithium salt to obtain a high-nickel ternary base material; (2) mixing the high-nickel ternary base material with nano ZrO2Are mixed to obtain ZrO2A coated high nickel ternary material; (3) subjecting the ZrO to2Carrying out secondary roasting on the coated high-nickel ternary material to obtain Li2NiZrO4Cladding and subsurface layer doping Zr double modified high nickel ternary material. The method provided by the invention effectively reduces the surface activity of the ternary material, thereby reducing the residual alkali content on the surface of the material and improving the cycle performance of the ternary material. However, the above doping and coating methods cannot change the situation that lithium ions can only conduct in a two-dimensional channel.
Disclosure of Invention
In order to change the situation that lithium ions in the cathode material can only be conducted in a two-dimensional channel, the invention mainly aims to provide a three-dimensional lithium ion-releasing cathode material, a precursor material and a preparation method.
In order to achieve the above object, the present invention provides the following technical solutions.
Firstly, the invention provides a precursor material, wherein aluminum fluoride coated by porous manganese hydroxide is distributed in secondary particles of the precursor material.
The invention also provides a precursor material, which is loose and porous, and alumina coated by porous manganese hydroxide is distributed in the secondary particles.
Secondly, the invention provides a preparation method of the high nickel precursor material, which comprises the following steps:
step S1, preparing the porous manganese hydroxide coated aluminum fluoride composite material: ultrasonically dispersing nano aluminum powder in water, then adding manganese fluoride powder in a stirring and heating state, reacting for a period of time, and centrifugally filtering reaction slurry to obtain a solid phase, namely the porous manganese hydroxide coated aluminum fluoride composite material;
step S2, introducing a nickel-cobalt-manganese mixed salt solution, a precipitator solution, a complexing agent solution and a suspension of a porous manganese hydroxide coated aluminum fluoride composite material into the bottom liquid of the reaction kettle in a parallel flow manner, and carrying out a coprecipitation reaction;
and step S3, after the coprecipitation reaction is finished, centrifugally washing reaction slurry, wherein a solid phase is a precursor material of aluminum fluoride coated by porous manganese hydroxide and distributed in the secondary particles.
Further, the aluminum powder preferably has a size of 100 to 800nm, and more preferably 100 to 600 nm.
Further, in step S1, the heating temperature is 40 to 60 ℃, preferably 45 to 55 ℃.
Further, in step S1, the molar ratio of the manganese fluoride to the aluminum powder is 1: 1-1: 10, preferably 1: 5-1: 8.
further, in step S1, the reaction time is 10 to 40min, preferably 20 to 30 min.
Further, in step S2, a nickel-cobalt-manganese mixed salt solution is prepared according to the element content of the precursor material, and the total concentration of metal ions in the nickel-cobalt-manganese mixed salt solution is 0.1 to 3mol/L, preferably 1.5 to 2.5 mol/L.
Further, in step S2, the solid content of the suspension of the porous manganese hydroxide-coated aluminum fluoride composite material is 1-2.5 g/L;
further, in step S2, the feeding mol ratio of the nickel-cobalt-manganese mixed salt to the porous manganese hydroxide coated aluminum fluoride composite material per hour is 1000: 1-200: 1.
further, in step S2, the complexing agent solution is an ammonia solution, and the precipitant solution is a sodium hydroxide solution.
Further, in the step S2, the pH value of the reaction kettle bottom liquid is 11-13, and the ammonia concentration is 3-10 g/L; the volume of the reaction kettle bottom liquid accounts for 1/4-1/2 of the volume of the reaction kettle. Further preferably, the ammonia concentration of the bottom liquid of the reaction kettle is 4-8 g/L.
Further, in step S2, the temperature of the coprecipitation reaction is 50-70 ℃, preferably 55-65 ℃; the stirring speed of the coprecipitation reaction is 300-800 rpm, preferably 400-750 rpm; the pH value of the coprecipitation reaction is 10-13, and preferably 10.4-12.2; in the coprecipitation reaction process, the concentration of ammonia in the system is 2-12 g/L, preferably 4-8 g/L; the time of the coprecipitation reaction is 40-100 h, preferably 55-85 h.
Further, in step S3, the washing times of the centrifugal washing are 3-6, and the Na content and the S content in the solid phase are less than 200ppm and 1300ppm respectively.
And (3) drying the precursor material of the aluminum fluoride coated by the porous manganese hydroxide in the secondary particles at a high temperature to obtain the loose and porous precursor material of the aluminum oxide coated by the porous manganese hydroxide in the secondary particles.
Further, the drying is tubular furnace drying, the drying temperature is 200-280 ℃, and preferably 220-260 ℃; the drying time is 6-24 h, preferably 8-16 h. The gas generated in the drying process is introduced into water.
Based on the same inventive concept, the invention provides the positive electrode material which is loose and porous, and lithium aluminate coated by lithium manganate is distributed in the positive electrode material.
And (3) mixing and sintering the precursor material of the alumina coated by the porous manganese hydroxide and the lithium source which are loose and porous and distributed in the secondary particles to obtain the cathode material.
Further, sintering is carried out twice, the sintering temperature for the first time is 400-600 ℃, and the sintering time is 3-8 hours; the sintering temperature of the second time is 600-900 ℃, and the sintering time is 10-20 h; and introducing nitrogen in the sintering process.
Based on the same inventive concept, the invention provides a composite material which is porous manganese hydroxide coated aluminum fluoride.
The invention also provides the application of the composite material in the preparation process of precursor materials and anode materials.
The inventor forms the porous composite material of aluminum fluoride coated with the nano manganese hydroxide by etching the nano aluminum powder. And then compounding the precursor material in a wet preparation stage of the precursor material, slowly releasing the nano manganese hydroxide to enable the precursor to grow on the manganese hydroxide and gradually wrap the manganese hydroxide, and finally forming a watermelon structure: the precursor material is melon pulp, the melon seeds are formed by manganese hydroxide and aluminum fluoride, the manganese hydroxide is shells of the melon seeds, and the aluminum fluoride is melon seed kernels. The precursor material is dried at a higher temperature, hydrogen fluoride gas is slowly released, aluminum fluoride is converted into aluminum oxide, and the watermelon also becomes loose and porous. And then, through lithium mixing and sintering, the melon pulp becomes a positive electrode material, the shell of the melon seed becomes lithium manganate, and the kernel of the melon seed becomes lithium aluminate.
During charging and discharging, the c-axis of the high-nickel cathode material shrinks and expands, and the c-axis of lithium manganate is basically unchanged, so that lattice mismatch occurs at a crystal boundary. The lattice mismatch can increase the free volume at the crystal boundary, so that lithium ions can have a new migration channel, namely, the lithium ion migration channel in the [001] crystal axis direction is additionally added besides the [010] and [100] crystal axes, and a 3D migration channel is formed.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention develops the application of the porous manganese hydroxide coated aluminum fluoride composite material in the lithium ion battery material, and the three-dimensional lithium ion-deintercalated anode material is prepared by the application of the material.
(2) The process for preparing the porous manganese hydroxide coated aluminum fluoride composite material is simple, and the composite material can be produced in large batch.
(3) In the preparation process of the precursor, the composite material is introduced in the main coprecipitation method process to obtain the precursor material with a special structure. And sintering the precursor material to obtain the three-dimensional lithium ion-deintercalated anode material. The process does not increase the equipment burden and the personnel burden of the prior coprecipitation process and sintering process, and has wide industrialized application prospect.
(4) Because lithium ions can migrate through the three-dimensional channel, the migration rate of the lithium ions is improved, and the loose and porous structure further promotes the migration rate of the lithium ions, so that the rate capability of the material is greatly improved. And due to the existence of the three-dimensional channel, lithium ions are more thoroughly deintercalated and embedded in the charge and discharge process, the reversibility of the material is better, and the stability of the material is better finally. The existence of lithium manganate and lithium aluminate also provides more pillars for the material, and reduces the structural collapse of the material in the long-term circulation process.
Drawings
Fig. 1 is a cross-sectional SEM image of a precursor material of aluminum fluoride coated with porous manganese hydroxide distributed in the secondary particles prepared in example 1 of the present invention.
Fig. 2 is a graph comparing the capacity retention of the positive electrode material obtained in example 1 of the present invention with that of conventional NCM 811.
Detailed Description
The present invention will now be described in detail with reference to the drawings, which are given by way of illustration and explanation only and should not be construed to limit the scope of the present invention in any way. Furthermore, those skilled in the art can combine features from the embodiments in this document and from different embodiments accordingly, based on the description in this document.
The chemical reagents used in the examples of the present invention, unless otherwise specified, are commercially available in a conventional manner.
Example 1
Step (1): adding nanoscale aluminum powder with the size of about 200nm into water, and performing ultrasonic dispersion to obtain an aluminum powder suspension with the solid content of 2.5 g/L. Transferring the aluminum powder suspension into a round-bottom flask, stirring at 300rpm, heating to 45 ℃, adding manganese fluoride powder (the molar ratio of manganese fluoride to aluminum powder is 1: 5), reacting for 20min, and centrifuging and washing a product to obtain the porous manganese hydroxide coated aluminum fluoride composite material. Water is added into the composite material to obtain suspension with solid content of 1 g/L.
Step (2): according to the proportion of Ni: co: and (2) preparing a nickel-cobalt-manganese sulfate solution according to the molar ratio of Mn =8:1:1, wherein the total concentration of metal ions in the sulfate solution is 2 mol/L. And preparing a reaction kettle bottom solution, wherein the pH value of the bottom solution is 11.6, and the ammonia concentration is 4 g/L. The volume of the base solution was 1/2 times the volume of the autoclave. And then pumping the nickel-cobalt-manganese sulfate solution, the ammonia water solution, the sodium hydroxide solution and the composite material suspension of aluminum fluoride coated by manganese hydroxide into the bottom liquid of the reaction kettle at the same time, controlling the temperature of the reaction system to be 60 ℃, the stirring speed to be 600rpm, the pH value to be 10.6-11.6 and the ammonia concentration to be 4-8 g/L. The flow rate of the nickel cobalt manganese sulfate solution is 1.5L/h, and the molar ratio of the nickel cobalt manganese sulfate fed per hour to the manganese hydroxide coated aluminum fluoride composite material is 800: 1. After reacting for 60h, the granularity reaches the standard, and the reaction is stopped.
And (3): and (3) centrifugally washing and drying the material obtained in the step (2). The washing mode is that the washing is carried out after alkaline washing, the number of times of alkaline washing is 2, and the number of times of water washing is 4. The final sodium content was 196ppm and the sulfur content was 1199 ppm. The drying temperature is 220 ℃ and the drying time is 12 h.
And (4): and (4) mixing and sintering the material obtained in the step (3) and a lithium source. Controlling the atmosphere in the tubular furnace to be nitrogen in the sintering process, wherein the first sintering temperature is 400 ℃, and the sintering time is 5 hours; the sintering temperature of the second time is 700 ℃, and the sintering time is 10 h. And after sintering, naturally cooling to room temperature to obtain the cathode material.
FIG. 1 is a sectional SEM image of a precursor material obtained in example 1, wherein manganese hydroxide is in a porous structure and coated on the surface of aluminum fluoride; the porous manganese hydroxide coated aluminum fluoride composite material is dispersed in the precursor secondary particles.
The cathode material obtained in example 1 was further analyzed for comparison in terms of electrochemical properties.
The NCM811 precursor produced and sold by the company (New energy GmbH, Pa Wa, Zhejiang) is mixed with lithium and sintered, and the sintering process is completely the same as the step (4) described in the example 1. And after sintering, naturally cooling to room temperature to obtain the NCM811 cathode material.
The positive electrode material obtained in example 1 and the NCM811 positive electrode material were assembled into a button cell according to a conventional method in the art, and the capacity retention rate of the cell was tested, with the results shown in fig. 2. As can be seen from fig. 2, the capacity retention rate of the cathode material obtained in example 1 is significantly higher than that of the NCM811 cathode material, and the capacity retention rate advantage of the cathode material obtained in example 1 is more and more significant as the cycle number increases.
Example 2
Step (1): adding nanoscale aluminum powder with the size of about 250nm into water, and performing ultrasonic dispersion to obtain an aluminum powder suspension with the solid content of 3 g/L. Transferring the aluminum powder suspension into a round-bottom flask, stirring at a stirring speed of 400rpm, heating to 45 ℃, adding manganese fluoride powder (the molar ratio of manganese fluoride to aluminum powder is 1: 3), reacting for 25min, and centrifuging and washing a product to obtain the porous manganese hydroxide coated aluminum fluoride composite material. The composite material is added with water to prepare suspension with solid content of 1.5 g/L.
Step (2): according to the proportion of Ni: co: and (3) preparing a nickel-cobalt-manganese sulfate solution according to the proportion of Mn =8.8:0.9:0.3, wherein the total concentration of metal ions in the nickel-cobalt-manganese sulfate solution is 2.5 mol/L. Preparing ammonia water solution as complexing agent and sodium hydroxide solution as precipitant. Preparing a reaction kettle bottom solution, wherein the pH value of the reaction kettle bottom solution is 12.0, the ammonia concentration is 6g/L, and the volume of the reaction kettle bottom solution accounts for 1/3 of the volume of the reaction kettle. And simultaneously pumping the turbid liquid of the composite material of the nickel-cobalt-manganese sulfate solution, the ammonia water solution, the sodium hydroxide solution and the manganese hydroxide coated aluminum fluoride into a reaction kettle in parallel, wherein the flow rate of the nickel-cobalt-manganese sulfate solution is 2.5L/h, and carrying out coprecipitation reaction. The molar ratio of the fed nickel cobalt manganese sulfate to the manganese hydroxide coated aluminum fluoride composite material per hour was 750: 1. The temperature of the reaction system is controlled to be 55 ℃, the stirring speed is 800rpm, the pH value of the reaction system is kept in the range of 11.4-12.0, and the ammonia concentration is kept in the range of 6-8 g/L. After reacting for 65 hours, the granularity reaches the standard, and the reaction is stopped.
And (3): and (3) centrifugally washing and drying the slurry obtained in the step (2). The washing mode is that the alkali washing is carried out firstly and then the water washing is carried out, the number of the alkali washing is 2, and the number of the water washing is 5. The sodium content of the washed material was 76ppm and the sulfur content was 682 ppm. The material was further dried at 230 ℃ for 14 h.
And (4): and (4) mixing the material obtained in the step (3) with a lithium source, and performing secondary sintering. The atmosphere in the tubular furnace is controlled to be nitrogen. The primary sintering temperature is 400 ℃, and the sintering time is 6 hours. The secondary sintering temperature is 800 ℃, and the sintering time is 14 h. And then, naturally cooling to room temperature to obtain the cathode material.
Example 3
Step (1): adding the nanoscale aluminum powder with the size of about 400nm into water, and performing ultrasonic dispersion to obtain an aluminum powder suspension with the solid content of 3 g/L. Transferring the aluminum powder suspension into a round-bottom flask, stirring at a stirring speed of 300rpm, heating to 50 ℃, adding manganese fluoride powder (the molar ratio of manganese fluoride to aluminum powder is 1: 4), reacting for 30min, and centrifuging and washing a product to obtain the porous manganese hydroxide coated aluminum fluoride composite material. The composite material is added with water to prepare suspension with solid content of 2 g/L.
Step (2): according to the proportion of Ni: co: the ratio of Mn =9:0.5:0.5 was formulated into a nickel cobalt manganese sulfate solution with a total metal ion concentration of 2 mol/L. Preparing ammonia solution as complexing agent and sodium hydroxide solution as precipitant. Preparing a reaction kettle bottom solution, wherein the pH value of the reaction kettle bottom solution is 12.1, the ammonia concentration is 4g/L, and the volume of the reaction kettle bottom solution accounts for 1/2 of the volume of the reaction kettle. And simultaneously pumping the nickel-cobalt-manganese sulfate solution, the ammonia water solution, the sodium hydroxide solution and the composite material suspension of aluminum fluoride coated by manganese hydroxide into the reaction kettle in parallel, wherein the flow rate of the nickel-cobalt-manganese sulfate solution is 3.5L/h, and carrying out coprecipitation reaction. The molar ratio of the nickel-cobalt-manganese mixed salt fed per hour to the manganese hydroxide coated aluminum fluoride composite material is 800: 1. The temperature of the reaction system is controlled to be 65 ℃, the stirring speed is 800rpm, the pH value is in the range of 11.2-12.1, and the ammonia concentration is in the range of 4-8 g/L. After 80 hours of reaction, the granularity reaches the standard, and the reaction is stopped.
And (3): and (3) centrifugally washing and drying the slurry obtained in the step (2). The washing mode is that the alkali washing is carried out firstly and then the water washing is carried out, the number of the alkali washing is 2, and the number of the water washing is 4. The sodium content of the washed material was 115ppm and the sulfur content was 965 ppm. Drying the washed material. The drying temperature is 230 ℃, and the drying time is 12 h.
And (4): and (4) mixing the material obtained in the step (3) with a lithium source, and carrying out secondary sintering. The atmosphere of the tube furnace is controlled to be nitrogen. The primary sintering temperature is 400 ℃, and the sintering time is 4 hours. The secondary sintering temperature is 750 ℃, and the sintering time is 14 h. And then naturally cooling to room temperature to obtain the cathode material.
Example 4
Step (1): adding nanoscale aluminum powder with the size of about 200nm into water, and performing ultrasonic dispersion to obtain an aluminum powder suspension with the solid content of 2 g/L. Transferring the aluminum powder suspension into a round-bottom flask, stirring at a stirring speed of 500rpm, heating to 55 ℃, adding manganese fluoride powder (the molar ratio of manganese fluoride to aluminum powder is 1: 8), reacting for 20min, and centrifuging and washing a product to obtain the porous manganese hydroxide coated aluminum fluoride composite material. The composite material is added with water to prepare suspension with solid content of 2 g/L.
Step (2): according to the proportion of Ni: co: preparing a nickel-cobalt-manganese sulfate solution with the total metal ion concentration of 1.5mol/L according to the proportion of Mn =9.2:0.5: 0.3. Preparing ammonia solution as complexing agent and sodium hydroxide solution as precipitant. Preparing reaction kettle bottom liquid, wherein the pH value of the reaction kettle bottom liquid is 12.0, the ammonia concentration is 4g/L, and the reaction kettle bottom liquid accounts for 1/2 of the volume of the reaction kettle. And pumping the nickel-cobalt-manganese sulfate solution, the ammonia water solution, the sodium hydroxide solution and the suspension of the composite material of aluminum fluoride coated by manganese hydroxide into the bottom solution of the reaction kettle at the same time, wherein the flow rate of the nickel-cobalt-manganese sulfate solution is 2.0L/h, and carrying out coprecipitation reaction. The molar ratio of the nickel-cobalt-manganese sulfate fed per hour to the manganese hydroxide-coated aluminum fluoride composite material is 800: 1. The temperature of the coprecipitation reaction system is controlled to be 60 ℃, the stirring speed is 800rpm, the pH value is 10.6-11.6, and the ammonia concentration is 4-8 g/L. After reacting for 85h, the granularity reaches the standard, and the reaction is stopped.
And (3): and (3) centrifugally washing and drying the material obtained in the step (2). The washing mode is that the washing is carried out after alkaline washing, the number of times of alkaline washing is 2, and the number of times of water washing is 4. The sodium content of the washed material was 153ppm and the sulphur content was 862 ppm. And drying the washed materials at the drying temperature of 240 ℃ for 8 h.
And (4): and (4) mixing the material obtained in the step (3) with a lithium source, and carrying out secondary sintering. The atmosphere of the tube furnace is controlled to be nitrogen. The primary sintering temperature is 400 ℃, and the sintering time is 6 hours. The secondary sintering temperature is 720 ℃, and the sintering time is 10 h. And then, naturally cooling to room temperature to obtain the cathode material.
Those not described in detail in the specification are prior art known to those skilled in the art.
The foregoing is only a preferred embodiment of the present invention. It should be noted that, for those skilled in the art, without departing from the technical principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be considered to be within the protection scope of the present invention.

Claims (1)

1. The porous manganese hydroxide coated aluminum fluoride composite material is applied to the preparation process of precursor materials and positive electrode materials.
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