CN114573047A - High-power NCM precursor and preparation method thereof - Google Patents
High-power NCM precursor and preparation method thereof Download PDFInfo
- Publication number
- CN114573047A CN114573047A CN202210219808.3A CN202210219808A CN114573047A CN 114573047 A CN114573047 A CN 114573047A CN 202210219808 A CN202210219808 A CN 202210219808A CN 114573047 A CN114573047 A CN 114573047A
- Authority
- CN
- China
- Prior art keywords
- solution
- additive
- precursor
- power
- 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.)
- Granted
Links
- 239000002243 precursor Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 59
- 230000000996 additive effect Effects 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 claims abstract description 17
- 239000010405 anode material Substances 0.000 claims abstract description 11
- 238000000975 co-precipitation Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 85
- 239000008367 deionised water Substances 0.000 claims description 37
- 229910021641 deionized water Inorganic materials 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 28
- 239000003513 alkali Substances 0.000 claims description 28
- 239000002585 base Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 28
- 239000002002 slurry Substances 0.000 claims description 27
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 24
- 239000012266 salt solution Substances 0.000 claims description 24
- 229910021529 ammonia Inorganic materials 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000007774 positive electrode material Substances 0.000 claims description 11
- 229910021645 metal ion Inorganic materials 0.000 claims description 9
- 229940044175 cobalt sulfate Drugs 0.000 claims description 8
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 8
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 8
- 238000007865 diluting Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229940099596 manganese sulfate Drugs 0.000 claims description 8
- 239000011702 manganese sulphate Substances 0.000 claims description 8
- 235000007079 manganese sulphate Nutrition 0.000 claims description 8
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 8
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 8
- 229940053662 nickel sulfate Drugs 0.000 claims description 8
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000012716 precipitator Substances 0.000 claims description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 13
- 230000000052 comparative effect Effects 0.000 description 20
- 239000000047 product Substances 0.000 description 18
- 239000002245 particle Substances 0.000 description 13
- 239000012065 filter cake Substances 0.000 description 12
- 239000010406 cathode material Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000011572 manganese Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000010884 ion-beam technique Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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 rate capability of the material are improved after the synthesized precursor is sintered into the anode material, and a high-power battery product is formed.
Description
Technical Field
The invention relates to a lithium battery production technology, in particular to a lithium ion battery anode material precursor production technology.
Background
At present, the lithium ion battery occupies a larger market share in the field of wide portable electronic equipment by virtue of the advantages of high specific capacity, long cycle life, low self-discharge rate, no memory effect, environmental friendliness and the like, and is generally recognized as the most development potential power battery for the electric vehicle. The ternary nickel-cobalt-manganese/aluminum cathode material is an important lithium ion battery cathode material, has the important advantages of better performance than lithium cobaltate, lower cost than lithium cobaltate, higher energy density than lithium iron phosphate and the like, and gradually becomes a mainstream cathode material of an automobile power battery. As the power of a new energy automobile, the cruising ability of the automobile is a performance index which is focused at present. The electrical performance of the positive electrode material, which is one of the key materials of the lithium ion battery, is also more demanding, so that the high power material is the current development direction. In order to better exert the excellent performance of the ternary cathode material, the preparation of the precursor of the ternary cathode material is crucial to the production of the ternary cathode material, and the precursor is used as the precursor of the cathode material and plays a great decisive role in the performance of the cathode material.
The nickel-cobalt-manganese/aluminum ternary precursor can be prepared by various methods such as a coprecipitation method, a sol-gel method, a high-temperature solid phase method and the like. In industrial production, the preparation of the precursor material of the cathode material is mostly carried out by adopting a coprecipitation process. Compared with the similar compact structure or high-clearance structure product, the ternary precursor with the internal compact support structure and the external high-clearance structure can effectively improve the first-effect performance, the cycle performance and the rate capability of the battery to form a high-power battery product after being prepared into the anode material.
Disclosure of Invention
In order to improve the porosity of the NCM precursor product, and further improve the first effect performance, the cycle performance and the rate capability of the material after the synthesized precursor is sintered into the anode material, thereby forming a high-power battery product. 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 consisting of SDBS, AES and SAS in a co-precipitation reaction.
As is readily understood by those skilled in the art, the terms SDBS, AES and SAS as used herein refer to sodium dodecylbenzenesulfonate, sodium fatty alcohol-polyoxyethylene ether sulfate and secondary alkyl sodium sulfonate, respectively.
As a further improvement of the invention, the additive comprises SDBS, AES and SAS according to the mass ratio of SDBS to AES to SAS being 1: 0.01-1.
As a further improvement of the invention, the addition mode of the additive is as follows: and when the coprecipitation reaction is carried out until the granularity reaches 50-80% of the granularity required by the process, adding the additive at a certain flow rate until the granularity required by the process is reached.
As a further improvement of the invention, the using amount of the additive is that the adding amount of the additive in unit time is not more than 5% of the dry weight mass of the precursor slurry generated by precipitation of the mixed salt solution entering the reaction system in the same unit time. The additive solution flow rate can be calculated specifically according to the following formula: the additive solution flow rate is the mixed salt solution flow rate x the mixed salt solution metal ion concentration x 91.7 (calculated constant, about precursor relative molecular mass) x the additive mass ratio ÷ 338 (calculated constant, about additive average relative molecular mass) ÷ additive solution concentration.
The invention can be implemented specifically according to the following steps:
s1, preparing nickel sulfate, cobalt sulfate and manganese sulfate into a mixed salt solution with metal ion concentration of 0.1-2 mol/L by using deionized water;
s2, preparing a sodium hydroxide precipitator into an alkali solution with the concentration of 3-15 mol/L by using deionized water;
s3, diluting ammonia water into an ammonia water solution of 5-10 mol/L by using deionized water;
s4, mixing and dissolving SDBS, AES and SAS with deionized water to obtain an additive solution with the concentration of 0.001-0.02 mol/L;
s5, adding a required amount of base solution into a reaction container, introducing nitrogen for air replacement, opening stirring and heating, keeping the stirring speed and the temperature in the kettle stably controlled at a certain value, adjusting the pH value of the base solution and the ammonia concentration to a required value, continuously adding the mixed salt solution, the alkali solution and the ammonia solution into the reaction kettle at a certain flow rate according to a required product proportion, and introducing the additive solution at a certain flow rate until the granularity reaches the required technological granularity when the granularity reaches 50-80% of the required technological 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 production method of the lithium battery anode material.
The invention also discloses a lithium ion battery comprising the lithium battery anode material.
The invention has the beneficial effects that: the porosity of the NCM precursor product can be obviously improved, so that the first efficiency performance, the cycle performance and the rate capability of the material are improved after the synthesized precursor is sintered into the anode material, and a 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 in accordance with one 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 comparing rate performance of the positive electrode materials of the respective examples and comparative examples.
Detailed Description
The present invention is further illustrated by the following examples.
The first embodiment is as follows:
the NCM precursor was synthesized as follows:
s1, preparing nickel sulfate, cobalt sulfate and manganese sulfate (Ni: Co: Mn: 55:20:25) into mixed salt solution with metal ion concentration of 1.5mol/L by using deionized water;
s2, preparing the sodium hydroxide precipitator 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 of SDBS to AES: SAS is 1:0.5:0.5) 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; nitrogen is introduced for air replacement, stirring and heating are started, the stirring speed is 700rpm, the temperature in the kettle is stably controlled at 60 ℃, the pH value of the base solution is adjusted to 11.70 +/-0.1, the ammonia concentration is adjusted to 0.40-0.50 mol/L, and the salt-alkali ratio is calculated according to the required proportion of the product: 2: 1-1.2, salt-ammonia ratio: and (3) continuously adding the mixed salt solution, the alkali solution and the ammonia water solution into the reaction kettle at the same time according to the flow ratio of 5: 1-1.5, introducing the additive solution when the granularity reaches 3.0 mu m, wherein the additive usage amount per hour is 2% of the dry weight mass of the precursor slurry generated by the precipitation of the mixed salt solution entering the reaction system per hour. The additive flow calculation formula is as follows: the additive solution flow rate is the mixed salt solution flow rate × 1.5mol/L × 91.7 (calculation constant, about precursor relative molecular mass) × 2% ÷ 338 (calculation constant, about additive average relative molecular mass) ÷ 0.02 mol/L. Introducing the additive solution until the particle size D50 which is required by the process is 5.0-6.0 mu m, and obtaining precursor slurry;
and S6, aging the precursor slurry for 5h, feeding the precursor slurry into a filtering device, centrifugally washing the obtained filter cake with 8 times of dilute alkali solution by weight, centrifugally washing with 10 times of deionized water by weight, filtering to obtain a filter cake after the content of each impurity reaches the standard, and drying for 24h at 130 ℃ to obtain the NCM precursor.
S7, cutting the section of the precursor particle and detecting and shooting the section by adopting an ion beam section detection method for the NCM precursor material, and detecting the internal structure of the product particle, wherein the result is shown in figure 2.
Example two:
the NCM precursor was synthesized as follows:
s1, preparing nickel sulfate, cobalt sulfate and manganese sulfate (Ni: Co: Mn: 51:20:29) into mixed salt solution with metal ion concentration of 2mol/L by using deionized water;
s2, preparing the sodium hydroxide precipitator 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 of SDBS to AES: SAS is 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; nitrogen is introduced for air replacement, stirring and heating are started, the stirring speed is 900rpm, the temperature in the kettle is stably controlled at 55 ℃, the pH value of the base solution is adjusted to 11.50-11.60, the ammonia concentration is adjusted to 0.30-0.40 mol/L, and the salt-alkali ratio is calculated according to the required proportion of the product: 2: 1-1.2, salt-ammonia ratio: and (2) continuously adding the mixed salt solution, the alkali solution and the ammonia water solution into the reaction kettle at the same time according to the flow ratio of 5: 1-1.5, introducing the additive solution when the granularity reaches 3.4 mu m, wherein the additive usage amount per hour is 2% of the dry weight mass of the precursor slurry generated by the precipitation of the salt solution entering the reaction system per hour. The calculation formula is as follows: additive solution flow rate ═ salt solution flow rate × 2.0mol/L × 91.7 (calculated constant, about precursor relative molecular mass) × 4% ÷ 338 (calculated constant, about additive average relative molecular mass) ÷ 0.01 mol/L. Introducing the additive solution until the particle size D50 which is required by the process is 4.5-5.5 mu m, and obtaining precursor slurry;
and S6, aging the precursor slurry for 5h, feeding the precursor slurry into a filtering device, centrifugally washing the obtained filter cake with 8 times of dilute alkali solution by weight, centrifugally washing with 10 times of deionized water by weight, filtering to obtain a filter cake after the content of each impurity reaches the standard, and drying for 24h at 130 ℃ to obtain the NCM precursor.
S7, cutting the section of the precursor particle and detecting and shooting the section by adopting an ion beam section detection method for the NCM precursor material, and detecting the internal structure of the product particle, wherein the result is shown in figure 3.
Comparative example one:
this comparative example is a control experiment of example one, conducted according to the same procedures and conditions as example one, except that: no additives were used. The method comprises the following specific steps:
the NCM precursor was synthesized as follows:
s1, preparing a mixed salt solution with metal ion concentration of 1.5mol/L from nickel sulfate, cobalt sulfate and manganese sulfate (Ni: Co: Mn: 55:20:25) by using deionized water;
s2, preparing the sodium hydroxide precipitator 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; nitrogen is introduced for air replacement, stirring and heating are started, the stirring speed is 700rpm, the temperature in the kettle is stably controlled at 60 ℃, the pH value of the base solution is adjusted to 11.70 +/-0.1, the ammonia concentration is adjusted to 0.40-0.50 mol/L, and the salt-alkali ratio is calculated according to the required proportion of the product: 2: 1-1.2, salt-ammonia ratio: continuously adding the mixed salt solution, the alkali solution and the ammonia water solution into a reaction kettle at a flow ratio of 5: 1-1.5 at the same time until the granularity D50 which is required by the process is 5.0-6.0 mu m, and obtaining precursor slurry;
and S5, aging the precursor slurry for 5h, feeding the precursor slurry into a filtering device, centrifugally washing the obtained filter cake with 8 times of dilute alkali solution by weight, centrifugally washing with 10 times of deionized water by weight, filtering to obtain a filter cake after the content of each impurity reaches the standard, and drying for 24h at 130 ℃ to obtain the NCM precursor.
S6, cutting the section of the precursor particle and detecting and shooting the section by adopting an ion beam section detection method for the NCM precursor material, and detecting the internal structure of the product particle, wherein the result is shown in figure 4.
Comparative example two:
this comparative example is a control experiment of example one, conducted according to the same procedures and conditions as example one, except that: the additive of example one was replaced with an equal 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 mixed salt solution with metal ion concentration of 1.5mol/L by using deionized water;
s2, preparing the sodium hydroxide precipitator 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 SDBS 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; nitrogen is introduced for air replacement, stirring and heating are started, the stirring speed is 700rpm, the temperature in the kettle is stably controlled at 60 ℃, the pH value of the base solution is adjusted to 11.70 +/-0.1, the ammonia concentration is adjusted to 0.40-0.50 mol/L, and the salt-alkali ratio is calculated according to the required proportion of the product: 2: 1-1.2, salt-ammonia ratio: continuously adding the mixed salt solution, the alkali solution and the ammonia water solution into a reaction kettle at the same time according to the flow ratio of 1: 1-1.5, and introducing the additive solution in the introduction manner and the introduction amount of the additive in the first embodiment when the granularity reaches 3.0 mu m until the granularity D50 which is the technological requirement is 5.0-6.0 mu m to obtain precursor slurry;
and S6, aging the precursor slurry for 5h, feeding the precursor slurry into a filtering device, centrifugally washing the obtained filter cake with 8 times of dilute alkali solution by weight, centrifugally washing with 10 times of deionized water by weight, filtering to obtain a filter cake after the content of each impurity reaches the standard, and drying for 24h at 130 ℃ to obtain the NCM precursor.
Comparative example three:
this comparative example is a control experiment of example one, conducted according to the same procedures and conditions as example one, except that: the additive of example one was replaced with an equal 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 mixed salt solution with metal ion concentration of 1.5mol/L by using deionized water;
s2, preparing the sodium hydroxide precipitator 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 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; nitrogen is introduced for air replacement, stirring and heating are started, the stirring speed is 700rpm, the temperature in the kettle is stably controlled at 60 ℃, the pH value of the base solution is adjusted to 11.70 +/-0.1, the ammonia concentration is adjusted to 0.40-0.50 mol/L, and the salt-alkali ratio is calculated according to the required proportion of the product: 2: 1-1.2, salt-ammonia ratio: continuously adding the mixed salt solution, the alkali solution and the ammonia water solution into a reaction kettle at the same time at a ratio of 1: 1-1.5, and introducing the additive solution in the manner and amount of introduction of the additive of the first embodiment when the particle size reaches 3.0 μm until the particle size D50 which is the process requirement is 5.0-6.0 μm, so as to obtain precursor slurry;
s6, aging the precursor slurry for 5h, then feeding the precursor slurry into a filtering device, centrifugally washing the obtained filter cake with 8 times of dilute alkali solution by weight, centrifugally washing with 10 times of deionized water by weight, filtering to obtain a filter cake after the content of each impurity reaches the standard, and drying for 24h at 130 ℃ to obtain the NCM precursor.
Comparative example four:
this comparative example is a control experiment of example one, conducted according to the same procedures and conditions as example one, except that: the additives of example one were replaced with equal amounts 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 mixed salt solution with metal ion concentration of 1.5mol/L by using deionized water;
s2, preparing the sodium hydroxide precipitator 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 SAS into 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; nitrogen is introduced for air replacement, stirring and heating are started, the stirring speed is 700rpm, the temperature in the kettle is stably controlled at 60 ℃, the pH value of the base solution is adjusted to 11.70 +/-0.1, the ammonia concentration is adjusted to 0.40-0.50 mol/L, and the salt-alkali ratio is calculated according to the required proportion of the product: 2: 1-1.2, salt-ammonia ratio: continuously adding the mixed salt solution, the alkali solution and the ammonia water solution into a reaction kettle at the same time at a ratio of 1: 1-1.5, and introducing the additive solution in the manner and amount of introduction of the additive of the first embodiment when the particle size reaches 3.0 μm until the particle size D50 which is the process requirement is 5.0-6.0 μm, so as to obtain precursor slurry;
and S6, aging the precursor slurry for 5h, feeding the precursor slurry into a filtering device, centrifugally washing the obtained filter cake with 8 times of dilute alkali solution by weight, centrifugally washing with 10 times of deionized water by weight, filtering to obtain a filter cake after the content of each impurity reaches the standard, and drying for 24h at 130 ℃ to obtain the NCM precursor.
As can be seen from the comparison of the first embodiment, the second embodiment and the comparative example in FIGS. 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 loose outer structure and high porosity is formed when the additive is used in the preparation process.
Detecting the electrochemical performance of the anode material:
the NCM precursor and lithium hydroxide of each of the above examples and comparative examples were uniformly mixed at a molar ratio M (Ni + Co + Mn): M (li): 1:1.05, and then calcined at 450 ℃ for 4 hours, then taken out and ground, and further calcined at 750 ℃ for 20 hours, and then taken out and ground to obtain a positive electrode material, and electrochemical properties of each positive electrode material were measured by the following method:
preparing the positive electrode materials prepared by the method into slurry according to the ratio of the positive electrode material to the conductive carbon to the polyvinylidene fluoride (PVDF) of 90:5:5, and preparing into a positive electrode piece (the compaction density of the electrode piece is 3.3 g/cm)2) And a metal lithium sheet is selected as a negative electrode material to assemble the button cell 2025.
1. First effect performance: calculating the formula: first-effect is first discharge capacity/first charge capacity;
2. rate capability: using 1M LiPF6 EC, DEC and DMC as 1:1: 1V% as electrolyte, respectively activating for three circles at 0.1, 0.2, 0.5, 1.0, 2.0, 5.0 and 8.0C multiplying power, cycling for 100 times at XC multiplying power, 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 of 100 cycles; calculating the formula: capacity retention (%) at 100 cycles was 100 discharge capacity at 100 cycles/discharge capacity at 1 cycle x 100%, and the specific capacity and cycle retention of the material were obtained.
3. Cycle performance: after the batteries are charged to 4.2V at constant current and constant voltage at 1C after the batteries are charged to 3.0V/battery at the temperature of 0.2C, the current is cut off to be 20mA, after the batteries are placed for 1h, the batteries are discharged to 3.0V at the temperature of 0.2C for one cycle, and after the cycle is repeated for 500 times, the capacity is more than 60 percent of the initial capacity.
The results are shown in Table 1 and FIG. 5.
TABLE 1 first Effect and cycle Performance test results
| Detecting items | Example one | Example two | Comparative example 1 | Comparative example No. two | Comparative example No. three | Comparative example No. 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 between the battery performances of the first embodiment and the first comparative example in table 1 and fig. 5, the first effect, the charge-discharge cycle performance and the rate performance of the high-power type special structure NCM product are significantly improved, and after 100 cycles, the capacity retention rate of the high-power type special structure NCM positive electrode material is higher than that of the conventional NCM ternary positive electrode material with the same proportion; the high-power NCM cathode material with the special structure has more stable cycle performance, obviously improves the rate capability and obviously improves the power.
As can be seen from table 1 and a comparison between the first example and the second comparative example, the third comparative example, and the fourth comparative example in fig. 5, when 3 additives, namely SDBS, AES, and SAS, are used alone in the production of the NCM precursor, the first effect, the charge-discharge cycle performance, and the rate performance of the battery are improved to some extent; when the three additives are combined and used according to the proportion of the invention, under the same usage amount, the improvement effect on the first effect, the charge-discharge cycle performance and the rate performance of the battery is obviously better than the effect of the respective additives used independently, and the components of the additive formula provided by the invention have obvious synergistic effect.
Claims (9)
1. 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.
2. The method for preparing a high-power NCM precursor according to claim 1, characterized in that: the additive comprises SDBS, AES and SAS according to the mass ratio of SDBS to AES to SAS being 1: 0.01-1.
3. The method for preparing a high-power NCM precursor according to claim 1, characterized in that: the addition mode of the additive is as follows: and when the coprecipitation reaction is carried out until the granularity reaches 50-80% of the granularity required by the process, adding the additive at a certain flow rate until the granularity required by the process is reached.
4. The method for producing a high-power NCM precursor according to claim 1, characterized in that: the use amount of the additive is as follows: the addition amount of the additive in unit time is not more than 5 percent of the dry weight mass of the precursor slurry generated by precipitation of the mixed salt solution entering the reaction system in the same unit time.
5. The method for preparing a high-power NCM precursor according to any one of claims 1-4, wherein the method comprises the following steps: the method comprises the following steps:
s1, preparing nickel sulfate, cobalt sulfate and manganese sulfate into a mixed salt solution with metal ion concentration of 0.1-2 mol/L by using deionized water;
s2, preparing a sodium hydroxide precipitator 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 with deionized water to obtain an additive solution with the concentration of 0.001-0.02 mol/L;
s5, adding a required amount of base solution into a reaction container, introducing nitrogen for air replacement, opening stirring and heating, keeping the stirring speed and the temperature in the kettle stably controlled at a certain value, adjusting the pH value of the base solution and the ammonia concentration to a required value, continuously adding the mixed salt solution, the alkali solution and the ammonia solution into the reaction kettle at a certain flow rate according to a required product proportion, and introducing the additive solution at a certain flow rate until the granularity reaches the required technological granularity when the granularity reaches 50-80% of the required technological granularity to obtain precursor slurry;
and S6, sequentially filtering, washing, centrifugally dewatering and drying the precursor slurry to obtain the high-power NCM precursor.
6. The high-power NCM precursor prepared by the preparation method of the high-power NCM precursor as claimed in any one of claims 1-5.
7. The production method of the lithium battery anode material is characterized by comprising the following steps: the production raw material comprises the high-power type NCM precursor described in claim 6.
8. A positive electrode material for a lithium battery produced by the method for producing a positive electrode material for a lithium battery according to claim 7.
9. A lithium ion battery comprising the positive electrode material for lithium batteries according to claim 8.
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 true CN114573047A (en) | 2022-06-03 |
| CN114573047B 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 (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103050683A (en) * | 2012-12-28 | 2013-04-17 | 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 |
| CN105244501A (en) * | 2015-09-25 | 2016-01-13 | 湖北工程学院 | Active substance precursor nickel manganese carbonate of lithium ion battery electrode |
| 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 |
| 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 |
| 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 |
-
2022
- 2022-03-08 CN CN202210219808.3A patent/CN114573047B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103050683A (en) * | 2012-12-28 | 2013-04-17 | 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 |
| CN105244501A (en) * | 2015-09-25 | 2016-01-13 | 湖北工程学院 | Active substance precursor nickel manganese carbonate of lithium ion battery electrode |
| 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 |
| 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 |
|---|---|
| CN114573047B (en) | 2023-07-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110380024B (en) | Sodium transition metal oxide with P3 structure, preparation method thereof and sodium ion battery | |
| CN104201369B (en) | A kind of lithium ion battery gradient anode material presoma and preparation method thereof | |
| CN102983326B (en) | Spherical lithium-nickel-cobalt composite oxide positive electrode material preparation method | |
| CN108767216B (en) | Lithium ion battery anode material with variable slope and full concentration gradient and synthesis method thereof | |
| CN105336941A (en) | High-voltage LiNixCoyMnzM(1-x-y-z)O2 cathode material, preparation method thereof, cathode and battery | |
| CN110429268A (en) | A kind of modified boron doping lithium-rich manganese-based anode material and the preparation method and application thereof | |
| CN103682316A (en) | Method for preparing ternary anode material of long-service-life and high-capacity lithium ion battery | |
| CN105514373A (en) | Positive electrode material of high-capacity lithium ion battery and preparation method of positive electrode material | |
| KR20150023856A (en) | Lithium rich positive electrode material, positive electrode of lithium battery and lithium battery | |
| CN107492643A (en) | A kind of titanium phosphate lithium coats LiNi1/3Co1/3Mn1/3O2Positive electrode and preparation method thereof | |
| CN110492095B (en) | Tin-doped lithium-rich manganese-based positive electrode material and preparation method thereof | |
| CN103390748B (en) | A kind of preparation method of alumina-coated lithium cobaltate cathode material | |
| CN110233261B (en) | Preparation method of single crystal ternary lithium battery positive electrode material and lithium ion battery | |
| KR20140119621A (en) | Precusor for lithium rich active material and lithium rich active material made by the same | |
| CN107311119B (en) | Hollow nanometer prism material of nickel cobalt diselenide, preparation method and application thereof | |
| CN103794782A (en) | Lithium-rich manganese-based material, preparation method thereof and lithium-ion battery | |
| US20220302446A1 (en) | Zinc ion battery positive electrode material, preparation method therefor, and application thereof | |
| 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 | |
| US20130330624A1 (en) | Lithium titanate doped with barium oxide, manufacturing method thereof and lithium ion battery using the same | |
| 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 | |
| CN113582254A (en) | Layered positive electrode material and preparation method and application thereof | |
| CN111233052A (en) | Nickel cobalt lithium manganate ternary positive electrode material, preparation method thereof, positive electrode and battery | |
| CN109994712B (en) | Surface-modified high-nickel ternary cathode material, modification method thereof and lithium ion battery | |
| CN116062797A (en) | Positive electrode material and battery containing same |
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 | ||
| CP03 | Change of name, title or address |
Address after: 644200 yangchunba Industrial Park, Jiang'an County, Yibin City, Sichuan Province Patentee after: YIBIN GUANGYUAN LITHIUM BATTERY CO.,LTD. Country or region after: China Patentee after: Yibin Lithium Treasure New Materials Co.,Ltd. Address before: 644200 yangchunba Industrial Park, Jiang'an County, Yibin City, Sichuan Province Patentee before: YIBIN GUANGYUAN LITHIUM BATTERY CO.,LTD. Country or region before: China Patentee before: Yibin Libao New Materials Co.,Ltd. |