CN114455642B - Method for preparing nano pore precursor - Google Patents

Method for preparing nano pore precursor Download PDF

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CN114455642B
CN114455642B CN202111658811.7A CN202111658811A CN114455642B CN 114455642 B CN114455642 B CN 114455642B CN 202111658811 A CN202111658811 A CN 202111658811A CN 114455642 B CN114455642 B CN 114455642B
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precursor
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CN114455642A (en
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张燕辉
王承乔
邢王燕
阳锐
杜先锋
王政强
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Yibin Guangyuan Lithium Battery Co ltd
Yibin Libao New Materials Co Ltd
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Yibin Guangyuan Lithium Battery Co ltd
Yibin Libao New Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/11—Powder tap density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a preparation method of a nano-pore precursor, which is characterized by comprising the following steps: s1, preparing a ternary salt solution of nickel, cobalt and manganese, alkali liquor and an ammonia water solution; s2, preparing a surfactant, wherein the surfactant comprises tetradecyl trimethyl ammonium bromide and cetyl pyridine bromide; s3, introducing the ternary salt solution, alkali liquor, ammonia water solution and surfactant into a reaction kettle to perform precursor synthesis reaction to obtain precursor slurry; s4, performing post-treatment on the precursor slurry to obtain the nanopore precursor. The advantages are that: 1. the specific surface area of the precursor can be increased while the tap density of the precursor is not affected; 2. the morphology of the particles can be effectively regulated and controlled.

Description

Method for preparing nano pore precursor
Technical Field
The invention relates to a lithium battery production technology, in particular to a lithium ion battery anode material precursor production technology.
Background
Along with the gradual consumption of traditional energy sources and the improvement of environmental protection requirements, the development of new energy systems and the perfection of storage and application systems, the lithium ion battery gradually replaces the application of traditional power batteries such as lead-acid batteries and nickel-hydrogen batteries on electric vehicles due to the characteristics of high energy density, good cycle performance, environmental friendliness and the like, and the research and development and application of the lithium ion battery become key technologies for the competition of new energy automobiles worldwide.
The lithium ion battery consists of a positive electrode material, a negative electrode material, a diaphragm, electrolyte and other main parts, wherein the positive electrode material is a key factor for determining the performance quality of the lithium ion battery, the ternary material is a preferred material of the lithium battery due to low price and stable performance, and the ternary precursor is a standard product for highly customizing the ternary positive electrode material and is a key material for producing the ternary positive electrode. The properties of the ternary precursor directly determine the main physicochemical properties of the ternary cathode material, such as particle size, element proportion, impurity content and the like, so that the consistency, rate capability, energy density, cycle life and other core electrochemical properties of the lithium battery are affected.
High nickel materials have been touted for their higher energy density and lower cost advantages compared to low nickel materials. However, the high nickel material also has high activity due to Ni, so that the precipitation speed of transition metal ions in coprecipitation process is too high, precursor primary particles are closely accumulated, pores in particles are less, primary particles of the sintered positive electrode material are compact, lithium ion transmission is hindered, and the power performance of the material is affected.
Disclosure of Invention
The invention provides a preparation method of a nano-pore precursor, which aims at improving the specific surface area of the precursor without affecting the tap density of the precursor.
The technical scheme adopted by the invention is as follows: a method of preparing a nanoporous precursor comprising the step of using a surfactant in the precursor synthesis, said surfactant comprising tetradecyltrimethylammonium bromide and cetylpyridinium bromide.
The invention can be implemented according to the following steps:
s1, preparing a ternary salt solution of nickel, cobalt and manganese, alkali liquor and an ammonia water solution;
s2, preparing a surfactant, wherein the surfactant comprises tetradecyl trimethyl ammonium bromide and cetyl pyridine bromide;
s3, introducing the ternary salt solution, alkali liquor, ammonia water solution and surfactant into a reaction kettle to perform precursor synthesis reaction to obtain precursor slurry;
s4, performing post-treatment on the precursor slurry to obtain the nanopore precursor.
As a further improvement of the invention, the molar ratio of the tetradecyl trimethyl ammonium bromide to the hexadecyl pyridine bromide in the surfactant is 5:1-2.
As a further improvement of the invention, the concentration of metal ions in the ternary salt solution is 0.1-2 mol/L, the concentration of sodium hydroxide in the alkaline solution is 3-15 mol/L, and the concentration of ammonia in the ammonia water solution is 5-10 mol/L.
As a further improvement of the present invention, step S3 is specifically: and (3) preparing a required base solution by using a mother solution in a reaction kettle, introducing nitrogen to perform air replacement, opening stirring and heating, keeping the stirring rate and the temperature in the kettle stably controlled at a certain value, adjusting the pH value and the ammonia concentration of the base solution to required values, continuously adding a ternary salt solution, an alkali solution, an ammonia solution and a surfactant into the reaction kettle at a certain flow rate according to the required proportion of the product, and according to the test condition, adjusting the flow rates of the alkali solution and the ammonia solution to stabilize the reaction atmosphere, and continuously reacting until the product with the required particle size is obtained, thereby obtaining the precursor slurry.
As a further improvement of the present invention, the post-treatment of step S4 is specifically: the precursor slurry enters a filtering device, the obtained filter cake is pulped and washed by alkali solution with the weight of 1-10 times, and is washed by deionized water with the weight of 1-10 times for several times, and after the impurity content reaches the standard, the filter cake is obtained by filtering; drying the filter cake at 100-150 ℃ for 2-24 h to obtain the nano-pore precursor.
The invention also discloses a nano-pore precursor which is prepared by the nano-pore precursor preparation method.
The invention also discloses a production method of the lithium ion battery anode material, which is characterized in that the production raw material comprises the nano-pore precursor.
The invention also discloses a lithium ion battery anode material which is prepared by the lithium ion battery anode material production method.
The invention also discloses a lithium battery comprising the positive electrode material of the lithium ion battery.
The beneficial effects of the invention are as follows: 1. the specific surface area of the precursor can be increased while the tap density of the precursor is not affected; 2. the morphology of the particles can be effectively regulated and controlled.
Detailed Description
The invention is further illustrated below with reference to examples.
Embodiment one:
the ternary precursor is prepared according to the following steps:
(1) Preparing nickel sulfate, cobalt sulfate and manganese sulfate into a ternary salt solution with the metal ion concentration of 2mol/L according to the proportion of Ni to Co to Mn=80 to 10; preparing NaOH precipitant into alkali liquor with the concentration of 9mol/L by deionized water; diluting ammonia water into ammonia water solution with ammonia concentration of 6mol/L by deionized water;
(2) Dissolving tetradecyltrimethylammonium bromide and cetylpyridinium bromide into 0.05mol/L surfactant with deionized water according to a mass ratio of 5:2;
(3) Preparing a base solution with mother solution in a reaction kettle, wherein the pH control range of the base solution is 11.80-12.00, and the ammonia concentration control range of the base solution is 0.30-0.35 mol/L; then nitrogen is introduced to perform air replacement, stirring and heating are opened, the stirring speed is kept at 900rpm, the temperature in the kettle is stably controlled at 65 ℃, the pH value of the base solution is regulated to 11.60+/-0.1, the ammonia concentration is regulated to 0.30-0.35 mol/L, and the ternary salt solution, the alkali solution, the ammonia solution and the surfactant are continuously added into the reaction kettle according to the product requirement ratio of 50:19:2:1, and continuously react until the particle size D50 of the product is obtained: 3.8-4.3 mu m to obtain precursor slurry.
(4) And (3) enabling the precipitate generated by the reaction to enter a filtering device, recycling the obtained mother solution, pulping and washing the obtained filter cake by using alkali solution with the weight being 6 times that of the filter cake, washing the filter cake by using deionized water with the weight being 8 times that of the filter cake for several times, filtering the filter cake after the impurity content reaches the standard, and drying the filter cake at 120 ℃ for 12 hours to obtain a ternary precursor product.
(5) The specific surface area and tap density of the resulting ternary precursor product were measured and the results are shown in table 1.
Comparative example one:
this comparative example is a control experiment of example one, which was performed in the same procedure and conditions as example one, except that: no surfactant was used. The method comprises the following specific steps:
(1) Preparing nickel sulfate, cobalt sulfate and manganese sulfate into a ternary salt solution with the metal ion concentration of 2mol/L according to the proportion of Ni to Co to Mn=80 to 10; preparing NaOH precipitant into alkali liquor with the concentration of 9mol/L by deionized water; diluting ammonia water into ammonia water solution with ammonia concentration of 6mol/L by deionized water;
(2) Preparing a base solution with mother solution in a reaction kettle, wherein the pH control range of the base solution is 11.80-12.00, and the ammonia concentration control range of the base solution is 0.30-0.35 mol/L; then nitrogen is introduced to perform air replacement, stirring and heating are opened, the stirring speed is kept at 900rpm, the temperature in the kettle is stably controlled at 65 ℃, the pH value of the base solution is regulated to 11.60+/-0.1, the ammonia concentration is regulated to 0.30-0.35 mol/L, and a ternary salt solution, an alkali solution and an ammonia solution are continuously added into the reaction kettle according to the product requirement ratio in a ratio of 50:19:2, and the reaction is continued until the product particle diameter D50: 3.8-4.3 mu m to obtain precursor slurry.
(3) And (3) enabling the precipitate generated by the reaction to enter a filtering device, recycling the obtained mother solution, pulping and washing the obtained filter cake by using alkali solution with the weight being 6 times that of the filter cake, washing the filter cake by using deionized water with the weight being 8 times that of the filter cake for several times, filtering the filter cake after the impurity content reaches the standard, and drying the filter cake at 120 ℃ for 12 hours to obtain a ternary precursor product.
(4) The specific surface area and tap density of the resulting ternary precursor product were measured and the results are shown in table 1.
Comparative example two:
this comparative example is a control experiment of example one, which was performed in the same procedure and conditions as example one, except that: the surfactant used was only tetradecyltrimethylammonium bromide. The method comprises the following specific steps:
the ternary precursor is prepared according to the following steps:
(1) Preparing nickel sulfate, cobalt sulfate and manganese sulfate into a ternary salt solution with the metal ion concentration of 2mol/L according to the proportion of Ni to Co to Mn=80 to 10; preparing NaOH precipitant into alkali liquor with the concentration of 9mol/L by deionized water; diluting ammonia water into ammonia water solution with ammonia concentration of 6mol/L by deionized water;
(2) Dissolving tetradecyl trimethyl ammonium bromide into deionized water to obtain 0.05mol/L surfactant;
(3) Preparing a base solution with mother solution in a reaction kettle, wherein the pH control range of the base solution is 11.80-12.00, and the ammonia concentration control range of the base solution is 0.30-0.35 mol/L; then nitrogen is introduced to perform air replacement, stirring and heating are opened, the stirring speed is kept at 900rpm, the temperature in the kettle is stably controlled at 65 ℃, the pH value of the base solution is regulated to 11.60+/-0.1, the ammonia concentration is regulated to 0.30-0.35 mol/L, and the ternary salt solution, the alkali solution, the ammonia solution and the surfactant are continuously added into the reaction kettle according to the product requirement ratio of 50:19:2:1, and continuously react until the particle size D50 of the product is obtained: 3.8-4.3 mu m to obtain precursor slurry.
(4) And (3) enabling the precipitate generated by the reaction to enter a filtering device, recycling the obtained mother solution, pulping and washing the obtained filter cake by using alkali solution with the weight being 6 times that of the filter cake, washing the filter cake by using deionized water with the weight being 8 times that of the filter cake for several times, filtering the filter cake after the impurity content reaches the standard, and drying the filter cake at 120 ℃ for 12 hours to obtain a ternary precursor product.
(5) The specific surface area and tap density of the resulting ternary precursor product were measured and the results are shown in table 1.
Comparative example three:
this comparative example is a control experiment of example one, which was performed in the same procedure and conditions as example one, except that: cetyl pyridinium bromide alone was used as the surfactant. The method comprises the following specific steps:
the ternary precursor is prepared according to the following steps:
(1) Preparing nickel sulfate, cobalt sulfate and manganese sulfate into a ternary salt solution with the metal ion concentration of 2mol/L according to the proportion of Ni to Co to Mn=80 to 10; preparing NaOH precipitant into alkali liquor with the concentration of 9mol/L by deionized water; diluting ammonia water into ammonia water solution with ammonia concentration of 6mol/L by deionized water;
(2) Dissolving cetyl pyridine bromide into deionized water to obtain 0.05mol/L surfactant;
(3) Preparing a base solution with mother solution in a reaction kettle, wherein the pH control range of the base solution is 11.80-12.00, and the ammonia concentration control range of the base solution is 0.30-0.35 mol/L; then nitrogen is introduced to perform air replacement, stirring and heating are opened, the stirring speed is kept at 900rpm, the temperature in the kettle is stably controlled at 65 ℃, the pH value of the base solution is regulated to 11.60+/-0.1, the ammonia concentration is regulated to 0.30-0.35 mol/L, and the ternary salt solution, the alkali solution, the ammonia solution and the surfactant are continuously added into the reaction kettle according to the product requirement ratio of 50:19:2:1, and continuously react until the particle size D50 of the product is obtained: 3.8-4.3 mu m to obtain precursor slurry.
(4) And (3) enabling the precipitate generated by the reaction to enter a filtering device, recycling the obtained mother solution, pulping and washing the obtained filter cake by using alkali solution with the weight being 6 times that of the filter cake, washing the filter cake by using deionized water with the weight being 8 times that of the filter cake for several times, filtering the filter cake after the impurity content reaches the standard, and drying the filter cake at 120 ℃ for 12 hours to obtain a ternary precursor product.
(5) The specific surface area and tap density of the resulting ternary precursor product were measured and the results are shown in table 1.
Comparative example four:
this comparative example is a control experiment of example one, which was performed in the same procedure and conditions as example one, except that: the tetradecyltrimethylammonium bromide was replaced with hexadecyltrimethylammonium bromide. The method comprises the following specific steps:
the ternary precursor is prepared according to the following steps:
(1) Preparing nickel sulfate, cobalt sulfate and manganese sulfate into a ternary salt solution with the metal ion concentration of 2mol/L according to the proportion of Ni to Co to Mn=80 to 10; preparing NaOH precipitant into alkali liquor with the concentration of 9mol/L by deionized water; diluting ammonia water into ammonia water solution with ammonia concentration of 6mol/L by deionized water;
(2) Dissolving cetyl trimethyl ammonium bromide and cetyl pyridine bromide into 0.05mol/L surfactant with deionized water according to a mass ratio of 1:1;
(3) Preparing a base solution with mother solution in a reaction kettle, wherein the pH control range of the base solution is 11.80-12.00, and the ammonia concentration control range of the base solution is 0.30-0.35 mol/L; then nitrogen is introduced to perform air replacement, stirring and heating are opened, the stirring speed is kept at 900rpm, the temperature in the kettle is stably controlled at 65 ℃, the pH value of the base solution is regulated to 11.60+/-0.1, the ammonia concentration is regulated to 0.30-0.35 mol/L, and the ternary salt solution, the alkali solution, the ammonia solution and the surfactant are continuously added into the reaction kettle according to the product requirement ratio of 50:19:2:1, and continuously react until the particle size D50 of the product is obtained: 3.8-4.3 mu m to obtain precursor slurry.
(4) And (3) enabling the precipitate generated by the reaction to enter a filtering device, recycling the obtained mother solution, pulping and washing the obtained filter cake by using alkali solution with the weight being 6 times that of the filter cake, washing the filter cake by using deionized water with the weight being 8 times that of the filter cake for several times, filtering the filter cake after the impurity content reaches the standard, and drying the filter cake at 120 ℃ for 12 hours to obtain a ternary precursor product.
(5) The specific surface area and tap density of the resulting ternary precursor product were measured and the results are shown in table 1.
TABLE 1 results of specific surface area and tap Density measurements for ternary precursor products
Specific surface area (m) 2 /g) Tap density (g/cm) 3 )
Example 1 50.32 1.52
Comparative example one 18.67 1.64
Comparative example two 31.25 1.27
Comparative example three 27.68 1.42
Comparative example four 39.54 1.47
As can be seen from a comparison of example one and comparative example one of table 1, the specific surface area of the ternary precursor can be greatly increased without changing tap by adding a surfactant consisting of tetradecyltrimethylammonium bromide and cetylpyridinium bromide to the ternary precursor synthesis reaction.
As can be seen from the comparison of the first example, the first comparative example, the second comparative example and the third comparative example in Table 1, the specific surface area is increased when the tetradecyl trimethyl ammonium bromide is added alone, but the tap density is reduced more; however, when cetylpyridinium bromide is added alone, the specific surface area is not obviously increased, but the reduction degree of the tap density is also obvious. When the tetradecyl trimethyl ammonium bromide and the cetyl pyridine bromide are combined, the specific surface area is obviously improved, and the tap density is well maintained. It can be seen that tetradecyltrimethylammonium bromide and hexadecylpyridine bromide have significant synergy in increasing the specific surface area of the ternary precursor and preventing the tap density from decreasing.
As can be seen from a comparison of the first example and the fourth comparative example in Table 1, the specific surface area was increased by a smaller extent than that of the first example and the tap density maintenance was also decreased after the tetradecyltrimethylammonium bromide was replaced with hexadecyltrimethylammonium bromide.
Electrochemical performance detection:
the ternary precursors prepared in the examples and comparative examples were prepared according to Li 2 CO 3 The molar ratio of the excess of 4 to 8 percent is that the lithium source and the lithium source are respectively sintered in a sintering furnace for 2 hours at a sintering temperature of 500 ℃ (heating rate of 20 ℃/min). Taking out the mixture after cooling, grinding and dispersing, and calcining for 12 hours at 850 ℃ (the temperature rising rate is 25 ℃/min). And cooling, taking out and crushing to obtain the positive electrode material. Preparing positive electrode materials into slurry according to the positive electrode materials, namely conductive carbon and polyvinylidene fluoride (PVDF) =90:5:5, respectively, preparing positive electrode plates (the compacted density of the plates is 3.3g/cm < 2 >), and assembling 2025 button cells by using metal lithium plates as negative electrode materials;
1. cycle performance: taking 1M LiPF6 EC:DEC:DMC =1:1:1v% as electrolyte, activating for three circles at a rate of 0.2C, and then circulating for 100 times at the rate of 0.2C, respectively measuring the discharge capacity at the 1 st cycle and the discharge capacity at the 100 th cycle, and calculating the capacity retention rate for 100 times in the cycle; the calculation formula is as follows: the specific capacity and cycle retention of the material obtained by cycling 100 times the capacity retention (%) =discharge capacity at 100 th cycle/discharge capacity at 1 st cycle ×100% are detailed in table 2.
2. The safety performance test comprises charging to 4.5V at constant current of 0.2C and constant voltage of 4.5V to 0.1C at normal temperature (25deg.C); the battery is disassembled in a glove box protected by argon, and the positive plate is taken out and then cleaned in DMC solution; scraping electrode material from the surface of the positive plate after DMC is completely volatilized, weighing 10mg of electrode material, putting into a specially-made aluminum crucible, adding 0.1uL of electrolyte, and sealing; the scanning temperature range of DSC test is 50-500 ℃, the temperature rising rate is 10 ℃/min, and the measurement result is shown in Table 2.
Table 2 results of electrochemical property measurement of cathode materials
Figure BDA0003449001380000061
As can be seen from a comparison between the first example and the first comparative example in table 2, compared with the first comparative example without the surfactant, the second and third comparative examples independently used and the fourth comparative example with cetyl trimethyl ammonium bromide, the nano microporous cathode material of the present invention has significantly improved charge and discharge cycle performance, and after 100 cycles, the capacity retention rate of the nano microporous cathode material of the present invention is higher than that of the common ternary cathode material and the cathode material independently added with the surfactant; compared with the common ternary positive electrode material, the nano microporous positive electrode material has more stable cycle performance, and compared with the fourth comparative example, the cycle capacity retention rate is also obviously improved. The comparison example and the comparison example show that the heat release amount of DSC of the lithium ion battery prepared by the nano microporous positive electrode material is lower than that of ternary positive electrode materials produced by other modes after the lithium ion battery is charged to 4.5V, and the temperature of the strongest heat release peak is higher than that of the common ternary positive electrode material, so that the positive electrode material has a stable crystal structure, good thermal stability and excellent safety performance, and the safety performance of the battery is improved.

Claims (4)

1. A method of preparing a nanoporous precursor comprising the steps of:
s1, preparing a ternary salt solution of nickel, cobalt and manganese, alkali liquor and an ammonia water solution;
s2, preparing a surfactant, wherein the surfactant consists of tetradecyl trimethyl ammonium bromide and cetyl pyridine bromide;
s3, introducing the ternary salt solution, alkali liquor, ammonia water solution and surfactant into a reaction kettle to perform precursor synthesis reaction to obtain precursor slurry;
s4, performing post-treatment on the precursor slurry to obtain the nanopore precursor.
2. The method of preparing a nanopore precursor according to claim 1, wherein: the mole ratio of the tetradecyl trimethyl ammonium bromide to the hexadecyl pyridine bromide in the surfactant is 5:1-2.
3. The method of preparing a nanopore precursor according to claim 1, wherein: the step S3 specifically comprises the following steps: and (3) preparing a required base solution by using a mother solution in a reaction kettle, introducing nitrogen to perform air replacement, opening stirring and heating, keeping the stirring rate and the temperature in the kettle stably controlled at a certain value, adjusting the pH value and the ammonia concentration of the base solution to required values, continuously adding a ternary salt solution, an alkali solution, an ammonia solution and a surfactant into the reaction kettle at a certain flow rate according to the required proportion of the product, and according to the test condition, adjusting the flow rates of the alkali solution and the ammonia solution to stabilize the reaction atmosphere, and continuously reacting until the product with the required particle size is obtained, thereby obtaining the precursor slurry.
4. The method of preparing a nanopore precursor according to claim 1, wherein: the post-processing in step S4 specifically includes: the precursor slurry enters a filtering device, the obtained filter cake is pulped and washed by alkali solution with the weight of 1-10 times, and is washed by deionized water with the weight of 1-10 times for several times, and after the impurity content reaches the standard, the filter cake is obtained by filtering; drying the filter cake at 100-150 ℃ for 2-24 h to obtain the nano-pore precursor.
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CN112758991A (en) * 2020-12-28 2021-05-07 宜宾光原锂电材料有限公司 Preparation method of core-shell structure ternary cathode material precursor
CN112758993A (en) * 2020-12-28 2021-05-07 宜宾光原锂电材料有限公司 High-safety multi-element precursor, high-safety multi-element precursor cathode material and high-safety multi-element precursor cathode material production method

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