CN114573047B - High-power NCM precursor and preparation method thereof - Google Patents

High-power NCM precursor and preparation method thereof Download PDF

Info

Publication number
CN114573047B
CN114573047B CN202210219808.3A CN202210219808A CN114573047B CN 114573047 B CN114573047 B CN 114573047B CN 202210219808 A CN202210219808 A CN 202210219808A CN 114573047 B CN114573047 B CN 114573047B
Authority
CN
China
Prior art keywords
solution
additive
precursor
deionized water
ncm
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210219808.3A
Other languages
Chinese (zh)
Other versions
CN114573047A (en
Inventor
张燕辉
阳锐
邢王燕
宋方亨
王承乔
王政强
左美华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yibin Guangyuan Lithium Battery Co ltd
Yibin Libao New Materials Co Ltd
Original Assignee
Yibin Guangyuan Lithium Battery Co ltd
Yibin Libao New Materials Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yibin Guangyuan Lithium Battery Co ltd, Yibin Libao New Materials Co Ltd filed Critical Yibin Guangyuan Lithium Battery Co ltd
Priority to CN202210219808.3A priority Critical patent/CN114573047B/en
Publication of CN114573047A publication Critical patent/CN114573047A/en
Application granted granted Critical
Publication of CN114573047B publication Critical patent/CN114573047B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • H01M4/36—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
    • C01P2006/40—Electric properties
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention discloses a preparation method of a high-power NCM precursor, which comprises the step of using an additive in a coprecipitation reaction, wherein the additive consists of SDBS, AES and SAS. The advantages are that: the porosity of the NCM precursor product can be obviously improved, so that the first efficiency performance, the cycle performance and the multiplying power performance of the material are improved after the synthesized precursor is sintered into the positive electrode material, and the high-power battery product is formed.

Description

High-power NCM precursor and preparation method thereof
Technical Field
The invention relates to a lithium battery production technology, in particular to a lithium ion battery anode material precursor production technology.
Background
The existing lithium ion battery has the advantages of high specific capacity, long cycle life, low self-discharge rate, no memory effect, environmental friendliness and the like, occupies a large market share in the field of wide portable electronic equipment, and is recognized as the power battery for the electric vehicle with the most development potential. The ternary nickel-cobalt-manganese/aluminum anode material is an important anode material of a lithium ion battery, has the important advantages of better performance than lithium cobaltate, far lower cost than lithium cobaltate, far higher energy density than lithium iron phosphate and the like, and is becoming a main stream anode material of an automobile power battery gradually. As the power of the new energy automobile, the cruising ability of the new energy automobile is used as a performance index which is focused at present. As a positive electrode material, which is one of key materials of lithium ion batteries, has also been put on higher demands in terms of electrical properties, so high power materials have become a current development direction. In order to better exert the excellent performance of the ternary cathode material, the preparation of the precursor is critical to the production of the ternary cathode material, and the precursor serving as the precursor of the cathode material plays a great decisive role in the performance of the cathode material.
The nickel-cobalt-manganese/aluminum ternary precursor can be prepared by a plurality of methods such as a coprecipitation method, a sol-gel method, a high temperature solid phase method and the like. In industrial production, a coprecipitation process is mostly adopted to prepare a precursor material of the positive electrode material. The internal compact supporting structure and the external high-void performance type structure NCM precursor material are prepared by using an intermittent method, so that a product with narrower particle size distribution and larger specific surface area can be obtained, and compared with a product with the same type compact structure or the high-void structure, the internal compact supporting structure and the external high-void performance type structure ternary precursor are prepared into the positive electrode material, and then the initial performance, the cycle performance and the multiplying power performance of the battery can be effectively improved, so that a high-power battery product is formed.
Disclosure of Invention
In order to improve the porosity of NCM precursor products, the synthesized precursor is sintered into a positive electrode material, and then the initial performance, the cycle performance and the multiplying power performance of the material are improved, so that high-power battery products are formed. The invention provides a high-power NCM precursor and a preparation method thereof.
The technical scheme adopted by the invention is as follows: the preparation method of the high-power NCM precursor is characterized by comprising the following steps: comprising the step of using an additive in the coprecipitation reaction, said additive consisting of SDBS, AES and SAS.
As will be readily appreciated by those skilled in the art, SDBS, AES, SAS of the present invention refers to sodium dodecylbenzenesulfonate, sodium fatty alcohol polyoxyethylene ether sulfate, and sodium secondary alkyl sulfonate, respectively.
As a further improvement of the invention, the additive consists of SDBS, AES and SAS in a mass ratio SDBS: AES: sas=1:0.01 to 1:0.01 to 1.
As a further improvement of the invention, the addition mode of the additive is as follows: and adding the additive at a certain flow rate when the coprecipitation reaction is carried out until the granularity reaches 50-80% of the process required granularity, and until the process required granularity is reached.
As a further improvement of the invention, the additive is used in an amount of not more than 5% of the dry weight of the precursor slurry produced by precipitation of the mixed salt solution fed into the reaction system in the same unit time. The flow rate of the additive solution can be specifically calculated according to the following formula: additive solution flow = mixed salt solution flow x mixed salt solution metal ion concentration x 91.7 (calculated constant, about precursor relative molecular mass) x additive mass ratio ≡338 (calculated constant, about additive average relative molecular mass) ≡additive solution concentration.
The invention can be implemented according to the following steps:
s1, preparing nickel sulfate, cobalt sulfate and manganese sulfate into mixed salt solution with metal ion concentration of 0.1-2 mol/L by using deionized water;
s2, preparing a sodium hydroxide precipitant into an alkali solution with the concentration of 3-15 mol/L by using deionized water;
s3, diluting ammonia water into 5-10 mol/L ammonia water solution by using deionized water;
s4, mixing and dissolving SDBS, AES and SAS into additive solution with the concentration of 0.001-0.02 mol/L by using deionized water;
s5, adding a required amount of base solution into a reaction container, 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 the mixed salt solution, the alkali solution and the ammonia solution into the reaction kettle at the same time according to the product required proportion at a certain flow rate, and introducing the additive solution at a certain flow rate until the additive solution reaches the process required granularity when the granularity reaches 50-80% of the process required granularity to obtain precursor slurry;
and S6, sequentially filtering, washing, centrifugally dewatering and drying the precursor slurry to obtain the high-power NCM precursor.
The invention also discloses a high-power NCM precursor, which is prepared by the preparation method of the high-power NCM precursor.
The invention also discloses a production method of the lithium battery anode material, which is characterized in that the production raw material comprises the high-power NCM precursor.
The invention also discloses a lithium battery anode material which is prepared by the lithium battery anode material production method.
The invention also discloses a lithium ion battery comprising the lithium battery anode material.
The beneficial effects of the invention are as follows: the porosity of the NCM precursor product can be obviously improved, so that the first efficiency performance, the cycle performance and the multiplying power performance of the material are improved after the synthesized precursor is sintered into the positive electrode material, and the high-power battery product is formed.
Drawings
Fig. 1 is a process flow diagram of the present invention.
Fig. 2 is a cross-sectional view of a precursor material prepared according to an embodiment.
FIG. 3 is a cross-sectional view of a precursor material prepared in example two.
Fig. 4 is a cross-sectional view of a precursor material prepared in comparative example one.
Fig. 5 is a graph showing the ratio performance of the positive electrode materials of each example and comparative example.
Detailed Description
The invention is further illustrated below with reference to examples.
Embodiment one:
the NCM precursor was synthesized as follows:
s1, preparing nickel sulfate, cobalt sulfate and manganese sulfate (Ni: co: mn=55:20:25) into a mixed salt solution with metal ion concentration of 1.5mol/L by using deionized water;
s2, preparing a sodium hydroxide precipitant into an alkali solution with the concentration of 5mol/L by using deionized water;
s3, diluting ammonia water into 5mol/L ammonia water solution by using deionized water;
s4, mixing and dissolving SDBS, AES and SAS (mass ratio SDBS: AES: SAS=1:0.5:0.5) into an additive solution with concentration of 0.02mol/L by using deionized water;
s5, adding a base solution (the pH control range of the base solution is 12.00-12.20, the ammonia concentration control range of the base solution is 0.40-0.50 mol/L) into a reaction container, introducing nitrogen to perform air replacement, opening stirring and heating, keeping the stirring speed at 700rpm and the temperature in the kettle stably controlled at 60 ℃, adjusting the pH value of the base solution to 11.70+/-0.1 and the ammonia concentration to 0.40-0.50 mol/L, and mixing the base solution with the salt and alkali ratio according to the product requirement ratio: 2:1-1.2, ratio of salt to ammonia: 5:1-1.5, continuously adding the mixed salt solution, the alkali solution and the ammonia water solution into a reaction kettle at the same time, and introducing the additive solution when the granularity reaches 3.0 mu m, wherein the additive consumption per hour is 2% of the dry weight mass of the precursor slurry generated by precipitation of the mixed salt solution entering a reaction system per hour. The flow calculation formula of the additive is as follows: additive solution flow = mixed salt solution flow x 1.5mol/L x 91.7 (calculated constant, about precursor relative molecular mass) x 2%/(338 (calculated constant, about additive average relative molecular mass)/(0.02 mol/L). Introducing the additive solution until reaching the process requirement granularity D50=5.0-6.0 mu m to obtain precursor slurry;
s6, aging the precursor slurry for 5 hours, then entering a filtering device, centrifugally washing the obtained filter cake with 8 times of dilute alkali solution, centrifugally washing with 10 times of deionized water, filtering to obtain a filter cake reaching the standard after the impurity content reaches the standard, and drying at 130 ℃ for 24 hours to obtain the NCM precursor.
S7, the NCM precursor material adopts an ion beam profile detection method to cut the profile of the precursor particles, the profile is detected and shot, and the internal structure of the product particles is detected, and the result is shown in figure 2.
Embodiment two:
the NCM precursor was synthesized as follows:
s1, preparing nickel sulfate, cobalt sulfate and manganese sulfate (Ni: co: mn=51:20:29) into a mixed salt solution with metal ion concentration of 2mol/L by using deionized water;
s2, preparing a sodium hydroxide precipitant into an alkali solution with the concentration of 10mol/L by using deionized water;
s3, diluting ammonia water into 5mol/L ammonia water solution by using deionized water;
s4, mixing and dissolving SDBS, AES and SAS (mass ratio SDBS: AES: SAS=1:1:1) into an additive solution with the concentration of 0.01mol/L by using deionized water;
s5, adding a base solution (the pH control range of the base solution is 12.00-12.20, the ammonia concentration control range of the base solution is 0.30-0.40 mol/L) into a reaction container, introducing nitrogen to perform air replacement, opening stirring and heating, keeping the stirring speed of 900rpm and the temperature in the kettle stably controlled at 55 ℃, adjusting the pH value of the base solution to 11.50-11.60 and the ammonia concentration to 0.30-0.40 mol/L, and mixing the base solution with the salt and alkali ratio according to the product requirement ratio: 2:1-1.2, ratio of salt to ammonia: 5:1-1.5, continuously adding the mixed salt solution, the alkali solution and the ammonia water solution into a reaction kettle at the same time, and introducing the additive solution when the granularity reaches 3.4 mu m, wherein the additive consumption per hour is 2% of the dry weight mass of the precursor slurry generated by precipitation of the salt solution entering a reaction system per hour. The calculation formula is as follows: additive solution flow = salt solution flow x 2.0mol/L x 91.7 (calculated constant, about precursor relative molecular mass) x 4%/(338 (calculated constant, about additive average relative molecular mass)/(0.01 mol/L). Introducing the additive solution until reaching the process requirement granularity D50=4.5-5.5 mu m to obtain precursor slurry;
s6, aging the precursor slurry for 5 hours, then entering a filtering device, centrifugally washing the obtained filter cake with 8 times of dilute alkali solution, centrifugally washing with 10 times of deionized water, filtering to obtain a filter cake reaching the standard after the impurity content reaches the standard, and drying at 130 ℃ for 24 hours to obtain the NCM precursor.
S7, the NCM precursor material adopts an ion beam profile detection method to cut the profile of the precursor particles, the profile is detected and shot, and the internal structure of the product particles is detected, and the result is shown in figure 3.
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 additives are used. The method comprises the following specific steps:
the NCM precursor was synthesized as follows:
s1, preparing nickel sulfate, cobalt sulfate and manganese sulfate (Ni: co: mn=55:20:25) into a mixed salt solution with metal ion concentration of 1.5mol/L by using deionized water;
s2, preparing a sodium hydroxide precipitant into an alkali solution with the concentration of 5mol/L by using deionized water;
s3, diluting ammonia water into 5mol/L ammonia water solution by using deionized water;
s4, adding a base solution (the pH control range of the base solution is 12.00-12.20, the ammonia concentration control range of the base solution is 0.40-0.50 mol/L) into a reaction container, introducing nitrogen to perform air replacement, opening stirring and heating, keeping the stirring speed at 700rpm and the temperature in the kettle stably controlled at 60 ℃, adjusting the pH value of the base solution to 11.70+/-0.1 and the ammonia concentration to 0.40-0.50 mol/L, and mixing the base solution with the salt and alkali ratio according to the product requirement ratio: 2:1-1.2, ratio of salt to ammonia: 5:1-1.5, continuously adding the mixed salt solution, the alkali solution and the ammonia water solution into a reaction kettle at the same time until reaching the process requirement granularity D50=5.0-6.0 mu m, and obtaining precursor slurry;
s5, aging the precursor slurry for 5 hours, then entering a filtering device, centrifugally washing the obtained filter cake with 8 times of dilute alkali solution, centrifugally washing with 10 times of deionized water, filtering to obtain a filter cake reaching the standard after the impurity content reaches the standard, and drying at 130 ℃ for 24 hours to obtain the NCM precursor.
S6, the NCM precursor material adopts an ion beam profile detection method to cut the profile of the precursor particles, the profile is detected and shot, and the internal structure of the product particles is detected, and the result is shown in figure 4.
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 additive of example one was replaced with an equivalent amount of SDBS (i.e., only one additive was used). The method comprises the following specific steps:
the NCM precursor was synthesized as follows:
s1, preparing nickel sulfate, cobalt sulfate and manganese sulfate (Ni: co: mn=55:20:25) into a mixed salt solution with metal ion concentration of 1.5mol/L by using deionized water;
s2, preparing a sodium hydroxide precipitant into an alkali solution with the concentration of 5mol/L by using deionized water;
s3, diluting ammonia water into 5mol/L ammonia water solution by using deionized water;
s4, dissolving SDBS into additive solution with concentration of 0.02mol/L by using deionized water;
s5, adding a base solution (the pH control range of the base solution is 12.00-12.20, the ammonia concentration control range of the base solution is 0.40-0.50 mol/L) into a reaction container, introducing nitrogen to perform air replacement, opening stirring and heating, keeping the stirring speed at 700rpm and the temperature in the kettle stably controlled at 60 ℃, adjusting the pH value of the base solution to 11.70+/-0.1 and the ammonia concentration to 0.40-0.50 mol/L, and mixing the base solution with the salt and alkali ratio according to the product requirement ratio: 2:1-1.2, ratio of salt to ammonia: 5:1-1.5, continuously adding the mixed salt solution, the alkali solution and the ammonia water solution into a reaction kettle at the same time, and introducing the additive solution in the additive introducing mode and the introducing amount of the first embodiment when the granularity reaches 3.0 mu m until reaching the process requirement granularity D50=5.0-6.0 mu m to obtain precursor slurry;
s6, aging the precursor slurry for 5 hours, then entering a filtering device, centrifugally washing the obtained filter cake with 8 times of dilute alkali solution, centrifugally washing with 10 times of deionized water, filtering to obtain a filter cake reaching the standard after the impurity content reaches the standard, and drying at 130 ℃ for 24 hours to obtain the NCM precursor.
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: the additive of example one was replaced with an equivalent amount of AES (i.e. only one additive was used). The method comprises the following specific steps:
the NCM precursor was synthesized as follows:
s1, preparing nickel sulfate, cobalt sulfate and manganese sulfate (Ni: co: mn=55:20:25) into a mixed salt solution with metal ion concentration of 1.5mol/L by using deionized water;
s2, preparing a sodium hydroxide precipitant into an alkali solution with the concentration of 5mol/L by using deionized water;
s3, diluting ammonia water into 5mol/L ammonia water solution by using deionized water;
s4, dissolving AES into additive solution with concentration of 0.02mol/L by using deionized water;
s5, adding a base solution (the pH control range of the base solution is 12.00-12.20, the ammonia concentration control range of the base solution is 0.40-0.50 mol/L) into a reaction container, introducing nitrogen to perform air replacement, opening stirring and heating, keeping the stirring speed at 700rpm and the temperature in the kettle stably controlled at 60 ℃, adjusting the pH value of the base solution to 11.70+/-0.1 and the ammonia concentration to 0.40-0.50 mol/L, and mixing the base solution with the salt and alkali ratio according to the product requirement ratio: 2:1-1.2, ratio of salt to ammonia: 5:1-1.5, continuously adding the mixed salt solution, the alkali solution and the ammonia water solution into a reaction kettle at the same time, and introducing the additive solution in the additive introducing mode and the introducing amount of the first embodiment when the granularity reaches 3.0 mu m until the granularity D50=5.0-6.0 mu m required by the process is reached, so as to obtain precursor slurry;
s6, aging the precursor slurry for 5 hours, then entering a filtering device, centrifugally washing the obtained filter cake with 8 times of dilute alkali solution, centrifugally washing with 10 times of deionized water, filtering to obtain a filter cake reaching the standard after the impurity content reaches the standard, and drying at 130 ℃ for 24 hours to obtain the NCM precursor.
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 additive of example one was replaced with an equivalent amount of SAS (i.e., only one additive was used). The method comprises the following specific steps:
the NCM precursor was synthesized as follows:
s1, preparing nickel sulfate, cobalt sulfate and manganese sulfate (Ni: co: mn=55:20:25) into a mixed salt solution with metal ion concentration of 1.5mol/L by using deionized water;
s2, preparing a sodium hydroxide precipitant into an alkali solution with the concentration of 5mol/L by using deionized water;
s3, diluting ammonia water into 5mol/L ammonia water solution by using deionized water;
s4, dissolving the SAS into an additive solution with the concentration of 0.02mol/L by using deionized water;
s5, adding a base solution (the pH control range of the base solution is 12.00-12.20, the ammonia concentration control range of the base solution is 0.40-0.50 mol/L) into a reaction container, introducing nitrogen to perform air replacement, opening stirring and heating, keeping the stirring speed at 700rpm and the temperature in the kettle stably controlled at 60 ℃, adjusting the pH value of the base solution to 11.70+/-0.1 and the ammonia concentration to 0.40-0.50 mol/L, and mixing the base solution with the salt and alkali ratio according to the product requirement ratio: 2:1-1.2, ratio of salt to ammonia: 5:1-1.5, continuously adding the mixed salt solution, the alkali solution and the ammonia water solution into a reaction kettle at the same time, and introducing the additive solution in the additive introducing mode and the introducing amount of the first embodiment when the granularity reaches 3.0 mu m until the granularity D50=5.0-6.0 mu m required by the process is reached, so as to obtain precursor slurry;
s6, aging the precursor slurry for 5 hours, then entering a filtering device, centrifugally washing the obtained filter cake with 8 times of dilute alkali solution, centrifugally washing with 10 times of deionized water, filtering to obtain a filter cake reaching the standard after the impurity content reaches the standard, and drying at 130 ℃ for 24 hours to obtain the NCM precursor.
As can be seen from the first, second and first comparison examples in fig. 2, 3 and 4, the product has a compact particle structure when no additive is used, and a special structure with a compact inner structure and a high porosity and a loose outer structure is formed when the additive is used in the preparation process.
And (3) detecting electrochemical performance of the positive electrode material:
the NCM precursor and lithium hydroxide of each of the above examples and comparative examples were uniformly mixed in a molar ratio of M (ni+co+mn): M (Li) =1:1.05, pre-burned at 450 ℃ for 4 hours, then taken out and ground, and then calcined at 750 ℃ for 20 hours, and then taken out and ground to finally obtain a positive electrode material, and electrochemical performance of each positive electrode material was measured, by the following method:
preparing the positive electrode materials prepared by the method into slurry according to the ratio of conductive carbon to polyvinylidene fluoride (PVDF) =90:5:5The material is manufactured into a positive pole piece (the compacted density of the pole piece is 3.3 g/cm) 2 ) And a metal lithium sheet is selected as a negative electrode material, and the 2025 button cell is assembled.
1. First-effect performance: the calculation formula is as follows: first effect = first discharge capacity/first charge capacity;
2. rate capability: taking 1M LiPF6 EC:DEC:DMC =1:1:1v% as electrolyte, activating for three circles at 0.1, 0.2, 0.5, 1.0, 2.0, 5.0 and 8.0C multiplying power respectively, and then circulating for 100 times at XC multiplying power, respectively measuring the discharge capacity at the 1 st circulation and the discharge capacity at the 100 th circulation, and calculating the 100-time capacity retention rate of circulation; the calculation formula is as follows: the specific capacity and cycle retention of the material were obtained by cycling 100 times the capacity retention (%) =discharge capacity at 100 th cycle/discharge capacity at 1 st cycle.
3. Cycle performance: after the battery is charged to 4.2V at a constant current and a constant voltage of 0.2C to 3.0V/branch, the cut-off current is 20mA, after the battery is placed for 1h, the battery is discharged to 3.0V at 0.2C as a cycle, and the capacity is more than 60% of the initial capacity after repeated circulation for 500 times.
The results are shown in Table 1 and FIG. 5.
TABLE 1 first-effect and cycle performance test results
Detecting items Example 1 Example two Comparative example one Comparative example two Comparative example three Comparative example four
First effect 89.4％ 88.7％ 84.6％ 85.7％ 86.1％ 85.9％
Cycle performance 75.4％ 74.6％ 65.7％ 68.8％ 69.2％ 68.9％
As can be seen from the comparison of the battery performances of the first embodiment and the first comparative embodiment in table 1 and fig. 5, the high-power type NCM product with special structure of the invention has obvious improvement of initial efficiency, charge-discharge cycle performance and multiplying power performance, and after 100 cycles, the capacity retention rate of the high-power type NCM positive electrode material with special structure of the invention is higher than that of the conventional NCM ternary positive electrode material with the same proportion; the high-power NCM positive electrode material with the special structure has more stable cycle performance, obviously improves the multiplying power performance and obviously improves the power.
As can be seen from the comparison of the first example, the second example, the third example and the fourth example in the table 1 and the fig. 5, in the production of the NCM precursor, when the 3 additives of SDBS, AES and SAS are used independently, the first effect, the charge-discharge cycle performance and the multiplying power performance of the battery are improved to a certain extent; when the three additives are combined according to the proportion of the invention, the effect of improving the initial effect, the charge-discharge cycle performance and the multiplying power performance of the battery is obviously better than the effect of each additive used independently under the same using amount, and the components of the additive formula provided by the invention have obvious synergistic effect.

Claims (3)

1. The preparation method of the high-power NCM precursor is characterized by comprising the following steps: the method comprises the step of using an additive in a coprecipitation reaction, wherein the additive consists of SDBS, AES and SAS according to the mass ratio of SDBS to AES to SAS=1 and 0.01-1 to 0.01-1;
the method specifically comprises the following steps:
s1, preparing nickel sulfate, cobalt sulfate and manganese sulfate into mixed salt solution with metal ion concentration of 0.1-2 mol/L by using deionized water;
s2, preparing a sodium hydroxide precipitant into an alkali solution with the concentration of 3-15 mol/L by using deionized water;
s3, diluting ammonia water into 5-10 mol/L ammonia water solution by using deionized water;
s4, mixing and dissolving SDBS, AES and SAS into additive solution with the concentration of 0.001-0.02 mol/L by using deionized water;
s5, adding a required amount of base solution into a reaction container, 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 the mixed salt solution, the alkali solution and the ammonia solution into the reaction kettle at the same time according to the product required proportion at a certain flow rate, and introducing the additive solution at a certain flow rate until the additive solution reaches the process required granularity when the granularity reaches 50-80% of the process required granularity to obtain precursor slurry;
and S6, sequentially filtering, washing, centrifugally dewatering and drying the precursor slurry to obtain the high-power NCM precursor.
2. The method for preparing a high power NCM precursor according to claim 1, wherein: the addition mode of the additive is as follows: and adding the additive at a certain flow rate when the coprecipitation reaction is carried out until the granularity reaches 50-80% of the process required granularity, and until the process required granularity is reached.
3. The method for preparing a high power NCM precursor according to claim 1, wherein: the usage amount of the additive is as follows: the addition amount of the additive in unit time is not more than 5% of the dry weight of the precursor slurry produced by precipitation of the mixed salt solution which enters the reaction system in the same unit time.
CN202210219808.3A 2022-03-08 2022-03-08 High-power NCM precursor and preparation method thereof Active CN114573047B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210219808.3A CN114573047B (en) 2022-03-08 2022-03-08 High-power NCM precursor and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210219808.3A CN114573047B (en) 2022-03-08 2022-03-08 High-power NCM precursor and preparation method thereof

Publications (2)

Publication Number Publication Date
CN114573047A CN114573047A (en) 2022-06-03
CN114573047B true CN114573047B (en) 2023-07-11

Family

ID=81779288

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210219808.3A Active CN114573047B (en) 2022-03-08 2022-03-08 High-power NCM precursor and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114573047B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112357976A (en) * 2020-09-30 2021-02-12 宜宾光原锂电材料有限公司 Synthesis of high-dispersion multi-element 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

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103050683B (en) * 2012-12-28 2015-04-15 深圳市贝特瑞新能源材料股份有限公司 Polyphase manganese base solid solution composite cathode material and preparation method thereof
CN105244501B (en) * 2015-09-25 2018-02-02 湖北工程学院 A kind of active material of lithium ion battery electrode presoma manganese carbonate nickel
CN107845784A (en) * 2017-09-15 2018-03-27 深圳市沃特玛电池有限公司 A kind of nickel-cobalt-manganternary ternary anode material preparation method
CN110718686A (en) * 2018-07-11 2020-01-21 西北大学 Preparation method of lithium-rich manganese-based positive electrode material and preparation method of precursor thereof
WO2021134153A1 (en) * 2019-12-30 2021-07-08 荆门市格林美新材料有限公司 Preparation method for high nickel ternary precursor capable of preferential growth of crystal planes by adjusting and controlling addition amount of seed crystals

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112357976A (en) * 2020-09-30 2021-02-12 宜宾光原锂电材料有限公司 Synthesis of high-dispersion multi-element 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

Also Published As

Publication number Publication date
CN114573047A (en) 2022-06-03

Similar Documents

Publication Publication Date Title
CN103682316B (en) The preparation method of long-life, high-capacity lithium ion cell tertiary cathode material
CN105336941A (en) High-voltage LiNixCoyMnzM(1-x-y-z)O2 cathode material, preparation method thereof, cathode and battery
CN107492643A (en) A kind of titanium phosphate lithium coats LiNi1/3Co1/3Mn1/3O2Positive electrode and preparation method thereof
CN105514373A (en) Positive electrode material of high-capacity lithium ion battery and preparation method of positive electrode material
CN103682304A (en) Lithium-rich solid solution anode composite and preparation method thereof, lithium ion battery anode plate and lithium ion battery
CN103390748B (en) A kind of preparation method of alumina-coated lithium cobaltate cathode material
CN102655232A (en) Preparation method of lithium manganese base-enriched ternary composite anode material
CN102931383A (en) Preparation method of composite anode material of lithium-ion power battery
CN103682315A (en) Method for preparing high-capacity long-life lithium ion battery lithium manganate cathode material
CN105024065A (en) Lithium ion battery cathode material and preparation method thereof
CN103825014B (en) A kind of preparation method of high-voltage anode material of lithium ion batteries lithium nickel manganese composite oxide
CN105591099A (en) Lithium molybdate surface modified lithium ion battery nickel-rich positive pole material and preparation method thereof
CN105047898B (en) A kind of twin spherical lithium ion secondary battery lithium-rich anode material and preparation method thereof
CN112701271A (en) Element doping method based on ternary precursor positive electrode material
CN104466139A (en) Preparation method of polyaniline-clad germanium-doped lithium manganate composite cathode material
CN103545507A (en) Negative material, namely porous zinc cobalt oxide, of lithium ion battery, as well as preparation method and applications of porous zinc cobalt oxide
CN103367705A (en) Double-layer cladded composite lithium ion positive material and preparation method thereof
CN113582254A (en) Layered positive electrode material and preparation method and application thereof
CN104638259A (en) Method for improving cycling performance of lithium nickel manganese oxide lithium ion cathode material
CN102070199B (en) Method for preparing micron frame-shaped manganese series lithium ion battery cathode material
CN114573047B (en) High-power NCM precursor and preparation method thereof
CN109994712B (en) Surface-modified high-nickel ternary cathode material, modification method thereof and lithium ion battery
CN110729481A (en) Lithium ion battery negative active material MnxFe1-xC2O4Synthetic method and application
CN105895906A (en) Lithium-doped ternary lithium-ion battery positive electrode material and preparation method thereof
CN114455643B (en) High-magnification high-nickel monocrystal NCA precursor and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant