CN107579236B - Preparation method of full-gradient high-nickel ternary precursor and full-gradient high-nickel ternary cathode material - Google Patents
Preparation method of full-gradient high-nickel ternary precursor and full-gradient high-nickel ternary cathode material Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 175
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 111
- 239000002243 precursor Substances 0.000 title claims abstract description 36
- 239000010406 cathode material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000011259 mixed solution Substances 0.000 claims abstract description 143
- 238000006243 chemical reaction Methods 0.000 claims abstract description 82
- 238000005245 sintering Methods 0.000 claims abstract description 47
- 238000005086 pumping Methods 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 230000035484 reaction time Effects 0.000 claims abstract description 14
- 150000001868 cobalt Chemical class 0.000 claims abstract description 13
- 150000002696 manganese Chemical class 0.000 claims abstract description 13
- 150000002815 nickel Chemical class 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 239000012670 alkaline solution Substances 0.000 claims abstract description 9
- 239000008139 complexing agent Substances 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000011572 manganese Substances 0.000 claims description 59
- 239000002994 raw material Substances 0.000 claims description 57
- 229910017052 cobalt Inorganic materials 0.000 claims description 37
- 239000010941 cobalt Substances 0.000 claims description 37
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 34
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 33
- 229910052748 manganese Inorganic materials 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000007795 chemical reaction product Substances 0.000 claims description 12
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 12
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 229940044175 cobalt sulfate Drugs 0.000 claims description 11
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 11
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 229940099596 manganese sulfate Drugs 0.000 claims description 10
- 239000011702 manganese sulphate Substances 0.000 claims description 10
- 235000007079 manganese sulphate Nutrition 0.000 claims description 10
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 238000010494 dissociation reaction Methods 0.000 claims description 6
- 230000005593 dissociations Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 25
- 229940053662 nickel sulfate Drugs 0.000 description 11
- 229910013716 LiNi Inorganic materials 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 6
- 239000010405 anode material Substances 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 239000011162 core material Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000011257 shell material Substances 0.000 description 4
- 229910015634 LiNi0.81 Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- 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
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- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a preparation method of a full-gradient high-nickel ternary precursor and a full-gradient high-nickel ternary cathode material, which comprises the following steps of: preparing a mixed solution A, a mixed solution B and a mixed solution C, co-currently pumping the mixed solution A, an alkaline solution and a complexing agent into a reaction kettle, continuously pumping the mixed solution B into the mixed solution A at a speed V1 after reaction time T1, and continuously pumping the mixed solution C into the mixed solution B at a speed V2 after reaction time T2; the method comprises the steps of feeding nickel salt, cobalt salt and manganese salt and continuously changing components to obtain a full-gradient high-nickel ternary precursor, mixing a lithium source compound and the full-gradient high-nickel ternary precursor according to a molar ratio, sintering the obtained mixture in an oxygen atmosphere, and performing post-treatment after sintering to obtain the full-gradient high-nickel ternary cathode material. The preparation method has strong operability and easy control, can be used for industrial production, and has high product capacity and good cycle stability.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to a full-gradient high-nickel ternary precursor and a preparation method of a full-gradient high-nickel ternary anode material.
Background
Energy crisis and energy safety are the serious examinations faced by all countries in the world at present, and the realization of energy diversification is the inevitable choice of national development by improving the energy structure. Because the lithium ion battery has the advantages of high voltage, high specific energy, good cycle performance, small environmental pollution and the like, the lithium ion battery is a key direction for the development of new energy industries of various countries at present. The lithium ion anode material is an important component of the lithium ion battery and is also a key point of the performance of the lithium ion battery.
The nickel-cobalt-manganese ternary positive electrode material is a material integrating the performances of lithium cobaltate, lithium nickelate and lithium manganate. The nickel-cobalt-manganese ternary positive electrode material has the characteristics of high specific capacity, long cycle life, low toxicity, low price and the like, has a good synergistic effect among three elements of nickel, cobalt and manganese, and is the most widely applied material at present. Due to the pursuit of the electric automobile for the high-energy-density power battery, the traditional nickel-cobalt-manganese ternary positive electrode materials such as NMC111 type, NCM424 type, NCM523 type and the like can not meet the requirements, so that the nickel-cobalt-manganese ternary positive electrode material with higher specific capacity and higher energy density is required. In the oxidation-reduction energy storage, nickel is a main component, and the specific capacity of the material can be effectively improved by increasing the content of nickel in the ternary material. Although the high nickel-based ternary cathode material, such as the material with the mole fraction of nickel in the nickel-cobalt-manganese ternary material being more than 0.6, has the advantages of high specific capacity, low price, environmental friendliness and the like, the poor cycling stability, thermal stability and storage performance of the high nickel-based ternary cathode material greatly limit the application of the high nickel-based ternary cathode material.
In recent years, researchers have tried various methods to obtain a high-nickel ternary positive electrode material having both high specific capacity and high stability. The common methods are doping and cladding, but these works are not ideal for improving the electrochemical performance of the material. In addition to the above modification means, new technologies and new methods for material preparation are developed from time to time, for example, the material is designed into a gradient core-shell material, which can greatly improve the performance of the material, such as core-shell concentration gradient materials prepared by CN103236537A and CN102347483A, but the core material and the shell material of the gradient material have obvious composition difference, and multiple cycles can cause the shell material to peel off, the effect is lost, and the material performance is reduced; the material is designed into a full-gradient material, namely, the concentration component of the material continuously changes from the core to the shell without obvious shell-core difference, so that the problem can be effectively solved, but the full-gradient material is difficult to prepare, has poor controllability, needs precise instruments and strict control conditions and is difficult to industrially produce. Therefore, a controllable preparation method with good repeatability and easy industrialization is urgently needed to be searched.
The present invention has been made in view of this situation.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a preparation method of a full-gradient high-nickel ternary precursor and a full-gradient high-nickel ternary cathode material, and solves the technical problem that the full-gradient material is difficult to realize industrial production.
In order to solve the technical problems, the invention adopts the technical scheme that:
the preparation method of the full-gradient high-nickel ternary precursor comprises the following steps:
s1: preparing a mixed solution A, a mixed solution B and a mixed solution C;
s2: reaction in a reaction kettle: co-current pumping the mixed solution A, the alkaline solution and the complexing agent into a reaction kettle, filling protective gas into the reaction kettle, controlling the temperature in the reaction kettle to be 45-70 ℃, controlling the pH value in the reaction kettle to be 10-12.5, starting a stirring device in the reaction kettle, stirring for reaction, after the reaction time is T1, continuously pumping the mixed solution B into the mixed solution A at a speed V1, and after the reaction time is T2, continuously pumping the mixed solution C into the mixed solution B at a speed V2;
s3: stopping the reaction: when the mixed solution A, the mixed solution B and the mixed solution C are completely pumped into the reaction kettle, stopping pumping the alkaline solution and the complexing agent into the reaction kettle, and stopping reaction to obtain a reaction product;
s4: and (3) product treatment: and (3) aging, filter-pressing, washing and drying the reaction product in the reaction kettle to obtain the full-gradient high-nickel ternary precursor.
In the present invention, the method for preparing the mixed solution a, the mixed solution B and the mixed solution C in S1 is as follows:
adding nickel salt, cobalt salt and manganese salt into deionized water to prepare a mixed solution A, wherein the molar concentration of nickel, the molar concentration of cobalt and the molar concentration of manganese in the mixed solution A are controlled to be (1-x-y): x: y;
adding nickel salt, cobalt salt and manganese salt into deionized water to prepare a mixed solution B, wherein the molar concentration of nickel, the molar concentration of cobalt and the molar concentration of manganese in the mixed solution B are controlled to be (1-a-B): a: b;
adding nickel salt, cobalt salt and manganese salt into deionized water to prepare a mixed solution C, and controlling the molar concentration of nickel, the molar concentration of cobalt and the molar concentration of manganese in the mixed solution C to be 1: 1: 1;
wherein 1/3 < (1-a-b) < (1-x-y).
In the invention, the nickel salt in S1 is one of nickel sulfate, nickel chloride, nickel nitrate or nickel acetate, the cobalt salt is one of cobalt sulfate, cobalt chloride, cobalt nitrate or cobalt acetate, the manganese salt is one of manganese sulfate, manganese chloride, manganese nitrate or manganese acetate, in S1, x is more than or equal to 0 and less than or equal to 0.1, and y is more than or equal to 0 and less than or equal to 0.1; in S1, a is more than or equal to 0.15 and less than or equal to 0.35, and b is more than or equal to 0.2 and less than or equal to 0.4.
In the invention, the sum of the molar concentration of nickel, the molar concentration of cobalt and the molar concentration of manganese in the mixed solution A is controlled to be 1-4.5 mol/L in S1; controlling the sum of the molar concentration of nickel, the molar concentration of cobalt and the molar concentration of manganese in the mixed solution B to be 0.5-3.5 mol/L; and controlling the sum of the molar concentration of nickel, the molar concentration of cobalt and the molar concentration of manganese in the mixed solution C to be 0.5-2.5 mol/L.
In the invention, in S2, a mixed solution A is stored in a first raw material tank, a mixed solution B is stored in a second raw material tank, a mixed solution C is stored in a third raw material tank, stirring devices are arranged in the first raw material tank, the second raw material tank and the third raw material tank, the bottom of the second raw material tank is communicated with the first raw material tank through a pipeline, a metering pump is arranged on the pipeline communicated with the second raw material tank, the bottom of the third raw material tank is communicated with the second raw material tank through a pipeline, and a metering pump is arranged on the pipeline communicated with the third raw material tank and the second raw material tank.
In the invention, the alkaline solution in S2 is one of sodium hydroxide solution or potassium hydroxide solution, the molar concentration of the alkaline solution is 2-8 mol/L, the complexing agent in S2 is one of ammonia water or ammonium salt solution, the molar concentration of the complexing agent is 2-8 mol/L, the protective gas in S2 is one of nitrogen or argon, the stirring speed of a stirring device in a reaction kettle in S2 is 300-800 rpm/min, and a device for controlling the pH value in the reaction kettle in S2 is an online pH meter.
In the invention, the reaction time T1 in S2 is 0.5-5 hours, the reaction time T2 is 2-12 hours, the speed V1 is 6L/h-20L/h, and the speed V2 is 4L/h-12L/h.
The preparation method of the full-gradient high-nickel ternary cathode material comprises the following steps of:
s01: preparing a full-gradient high-nickel ternary precursor, and preparing the full-gradient high-nickel ternary precursor according to the preparation method of the full-gradient high-nickel ternary precursor;
s02: mixing: mixing a lithium source compound and a full-gradient high-nickel ternary precursor according to a molar ratio; obtaining a mixture;
s03: and (3) sintering: and sintering the obtained mixture in an oxygen atmosphere, and performing post-treatment after sintering to obtain the full-gradient high-nickel ternary cathode material.
In the invention, the lithium source compound in S02 is one or two of lithium hydroxide and lithium carbonate, and in S02, the lithium source compound and the full-gradient high-nickel ternary precursor are mixed according to the molar ratio Li (Ni + Co + Mn) of 1-1.1: 1.
In the invention, the sintering in S03 is carried out in two stages, the sintering temperature in the first stage is controlled to be 400-550 ℃, the sintering temperature time is controlled to be 4-12 h, the sintering temperature in the second stage is controlled to be 650-900 ℃, the sintering temperature time is controlled to be 10-25 h, and the post-treatment of the sintered material in S03 is dissociation and sieving.
After the technical scheme is adopted, compared with the prior art, the invention has the following beneficial effects.
The preparation technology of the ternary precursor provided by the invention changes the preparation process of the conventional single salt solution and the conventional gradient material preparation process, and comprises the following steps of preparing a mixed solution A with high nickel content and different concentrations, a nickel-cobalt-manganese mixed solution B with medium nickel content and a molar ratio of nickel, cobalt and manganese of 1: 1:1, in the reaction stage, the high nickel mixed solution A is continuously pumped into the reaction kettle for reaction consumption, the medium nickel solution B is continuously pumped into the solution A, the solution C is continuously pumped into the solution B, the nickel content of the mixed solution entering the reaction kettle is gradually reduced actually, the cobalt content and the manganese content are gradually increased, the continuous gradual change of nickel salt, cobalt salt and manganese salt feeding and components is realized, a full-gradient high nickel ternary precursor is prepared, and the full-gradient high nickel ternary anode material is synthesized by mixing lithium and roasting. The nickel content of the material is continuously decreased from the center of the inner core to the shell, the contents of cobalt and manganese elements are continuously increased, the NCM111 with stable structure and electrical property is ensured to be arranged at the outermost layer of the material in a continuous gradient change mode through controlling the feeding time and flow of different solutions in the preparation stage of the precursor, no obvious interface exists in the material, the phase boundary resistance between the materials is reduced, and the performance of the material is optimized. The preparation method has strong operability and easy control, can be used for industrial production, and has high product capacity and good cycle stability.
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the invention without limiting the invention to its proper form. It is obvious that the drawings in the following description are only some embodiments, and that for a person skilled in the art, other drawings can be derived from them without inventive effort. In the drawings:
FIG. 1 is a schematic process flow diagram of the present invention.
It should be noted that the drawings and the description are not intended to limit the scope of the inventive concept in any way, but to illustrate it by a person skilled in the art with reference to specific embodiments.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and the following embodiments are used for illustrating the present invention and are not intended to limit the scope of the present invention.
In the description of the present invention, it should be noted that the terms "upper", "lower", "front", "rear", "left", "right", "vertical", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; may be directly connected or indirectly connected through an intermediate. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Example 1
Referring to fig. 1, a process flow diagram of a preparation method of a full-gradient high-nickel ternary cathode material is shown, wherein nickel sulfate and cobalt sulfate are added into deionized water to prepare 400L of a mixed solution a, and a ratio of a molar concentration of nickel to a molar concentration of cobalt in the mixed solution a is controlled to be 0.95: 0.05, controlling the sum of the molar concentration of nickel and the molar concentration of cobalt in the mixed solution A to be 3 mol/L; storing the mixed solution A in a first raw material tank, and starting a stirring device arranged in the first raw material tank; adding nickel sulfate, cobalt sulfate and manganese sulfate into deionized water to prepare 200L of mixed solution B, and controlling the molar concentration of nickel, the molar concentration of cobalt and the molar concentration of manganese in the mixed solution B to be 5: 2: 3, controlling the sum of the molar concentration of nickel, the molar concentration of cobalt and the molar concentration of manganese in the mixed solution B to be 2 mol/L; storing the mixed solution B in a second raw material tank, and starting a stirring device arranged in the second raw material tank; adding nickel sulfate, cobalt sulfate and manganese sulfate into deionized water to prepare 100L of mixed solution C, and controlling the molar concentration of nickel, the molar concentration of cobalt and the molar concentration of manganese in the mixed solution C to be 1: 1: 1; controlling the molar concentration of nickel, cobalt and manganese in the mixed solution CAnd 1mol/L, storing the mixed solution C in a third raw material tank, and starting a stirring device arranged in the third raw material tank; co-currently pumping the mixed solution A, a sodium hydroxide solution with the molar concentration of 4mol/L and ammonia water with the molar concentration of 5mol/L into a reaction kettle, filling nitrogen into the reaction kettle, controlling the temperature in the reaction kettle to be 60 ℃, controlling the pH value in the reaction kettle to be 11.5, starting a stirring device in the reaction kettle, controlling the stirring speed of the stirring device to be 500rpm/min, stirring for reaction, continuously pumping the mixed solution B into the mixed solution A at the speed of 11L/h after the reaction time is 2 hours, and continuously pumping the mixed solution C into the mixed solution B at the speed of 5L/h after the reaction time is 10 hours; when the mixed solution A, the mixed solution B and the mixed solution C are completely pumped into the reaction kettle, stopping pumping the 4mol/L sodium hydroxide solution and the ammonia water with the molar concentration of 5mol/L into the reaction kettle until the reaction stops; obtaining a reaction product; the mixed solution A in the first raw material tank is continuously pumped into the reaction kettle for reaction consumption, the mixed solution B in the second raw material tank is continuously pumped into the mixed solution A at the speed of 11L/h, and the mixed solution C in the third raw material tank is continuously pumped into the mixed solution B at the speed of 5L/h, so that the nickel content in the first raw material tank is gradually reduced, the cobalt and manganese content is gradually increased, and the continuous gradual change of nickel salt, cobalt salt and manganese salt feeding and components is realized; aging, filter pressing, washing and drying reaction products in the reaction kettle to obtain a full-gradient high-nickel ternary precursor Ni0.81Co0.10Mn0.09(OH)2Mixing lithium source compound and full-gradient high-nickel ternary precursor Ni0.81Co0.10Mn0.09(OH)2Mixing Li (Ni + Co + Mn) in a molar ratio of 1.03: 1; obtaining a mixture; sintering the obtained mixture in an oxygen atmosphere, wherein the sintering is carried out in two stages, the sintering temperature is controlled to be 500 ℃ in the first stage, the sintering temperature time is controlled to be 6 hours in the second stage, the sintering temperature is controlled to be 795 ℃ in the second stage, the sintering temperature time is controlled to be 15 hours, and dissociation and sieving are carried out after sintering to obtain the full-gradient high-nickel ternary cathode material LiNi0.81Co0.10Mn0.09O2。
Comparative example 1
Adding nickel sulfate, cobalt sulfate and manganese sulfate into deionized water to prepare 700L of mixed solution, wherein the ratio of the molar concentration of nickel to the molar concentration of cobalt to the molar concentration of manganese in the mixed solution is controlled to be 0.81: 0.1: 0.09, controlling the sum of the molar concentration of nickel, the molar concentration of cobalt and the molar concentration of manganese in the mixed solution to be 3 mol/L; co-currently pumping the mixed solution, a sodium hydroxide solution with a molar concentration of 4mol/L and ammonia water with a molar concentration of 5mol/L into a reaction kettle, filling nitrogen into the reaction kettle, controlling the temperature in the reaction kettle to be 60 ℃, controlling the pH value in the reaction kettle to be 11.5, starting a stirring device in the reaction kettle, controlling the stirring speed of the stirring device to be 500rpm/min, and stopping pumping the sodium hydroxide solution with a molar concentration of 4mol/L and the ammonia water with a molar concentration of 5mol/L into the reaction kettle after the mixed solution is completely pumped into the reaction kettle until the reaction stops; obtaining a reaction product; aging, filter pressing, washing and drying the reaction product in the reaction kettle to obtain the high-nickel ternary precursor Ni0.81Co0.10Mn0.09(OH)2Mixing lithium source compound and high-nickel ternary precursor Ni0.81Co0.10Mn0.09(OH)2Mixing Li (Ni + Co + Mn) in a molar ratio of 1.03: 1; obtaining a mixture; sintering the obtained mixture in an oxygen atmosphere, wherein the sintering process comprises two stages, the sintering temperature of the first stage is controlled to be 500 ℃, the sintering temperature time is controlled to be 6 hours, the sintering temperature of the second stage is controlled to be 795 ℃, the sintering temperature time is controlled to be 15 hours, and dissociation and sieving are carried out after sintering to obtain the high-nickel ternary cathode material LiNi0.81Co0.10Mn0.09O2。
The full-gradient high-nickel ternary cathode material LiNi prepared in the example 1 is used0.81Co0.10Mn0.09O2And the high-nickel ternary cathode material LiNi prepared in comparative example 10.81Co0.10Mn0.09O22032 button cells are respectively prepared, a blue test system is adopted to test at 25 ℃, the test voltage range is 2.8-4.3V, and the full-gradient high-nickel ternary cathode material LiNi prepared in the embodiment 10.81Co0.10Mn0.09O2The 1C first discharge capacity of the prepared 2032 button cell is 186.8 mAh/g; the capacity retention rate of the full cell after 1000 cycles was 93.8%, compared to the high-nickel tri-compound prepared in comparative example 1Meta-anode material LiNi0.81Co0.10Mn0.09O2The 1C first discharge capacity of the prepared 2032 button cell is 183.7 mAh/g; the capacity retention rate of the full battery after 1000 cycles was 85.3%. The product obtained by the invention has higher capacity and good cycling stability, and the preparation methods of the full-gradient high-nickel ternary precursor and the anode material have strong operability and are easy to control, and can be used for industrial production.
Example 2
Referring to fig. 1, a process flow diagram of a preparation method of a full-gradient high-nickel ternary cathode material is shown, nickel sulfate, cobalt sulfate and manganese sulfate are added into deionized water to prepare 300L of a mixed solution a, and a ratio of a molar concentration of nickel, a molar concentration of cobalt and a molar concentration of manganese in the mixed solution a is controlled to be 8: 1:1, controlling the sum of the molar concentration of nickel and the molar concentration of cobalt in the mixed solution A to be 2 mol/L; storing the mixed solution A in a first raw material tank, and starting a stirring device arranged in the first raw material tank; adding nickel sulfate, cobalt sulfate and manganese sulfate into deionized water to prepare 100L of mixed solution B, and controlling the molar concentration of nickel, the molar concentration of cobalt and the molar concentration of manganese in the mixed solution B to be 6: 2: 2, controlling the sum of the molar concentration of nickel, the molar concentration of cobalt and the molar concentration of manganese in the mixed solution B to be 1 mol/L; storing the mixed solution B in a second raw material tank, and starting a stirring device arranged in the second raw material tank; adding nickel sulfate, cobalt sulfate and manganese sulfate into deionized water to prepare 100L of mixed solution C, and controlling the molar concentration of nickel, the molar concentration of cobalt and the molar concentration of manganese in the mixed solution C to be 1: 1: 1; controlling the sum of the molar concentration of nickel, the molar concentration of cobalt and the molar concentration of manganese in the mixed solution C to be 1mol/L, storing the mixed solution C in a third raw material tank, and starting a stirring device arranged in the third raw material tank; co-current pumping the mixed solution A, a sodium hydroxide solution with the molar concentration of 4mol/L and ammonia water with the molar concentration of 6mol/L into a reaction kettle, filling nitrogen into the reaction kettle, controlling the temperature in the reaction kettle to be 60 ℃, controlling the pH value in the reaction kettle to be 11.2, starting a stirring device in the reaction kettle, controlling the stirring speed of the stirring device to be 600rpm/min, stirring for reaction, and after the reaction time is 1.5h, mixing the mixed solution A and the ammonia waterContinuously pumping the solution B into the mixed solution A at the speed of 8L/h, and continuously pumping the mixed solution C into the mixed solution B at the speed of 5L/h after the reaction time is 7.0 h; when the mixed solution A, the mixed solution B and the mixed solution C are completely pumped into the reaction kettle, stopping pumping the 4mol/L sodium hydroxide solution and the ammonia water with the molar concentration of 6mol/L into the reaction kettle until the reaction is stopped; obtaining a reaction product; the mixed solution A in the first raw material tank is continuously pumped into the reaction kettle for reaction consumption, the mixed solution B in the second raw material tank is continuously pumped into the mixed solution A at the rate of 8L/h, and the mixed solution C in the third raw material tank is continuously pumped into the mixed solution B at the rate of 5L/h, so that the nickel content in the first raw material tank is gradually reduced, the cobalt and manganese content is gradually increased, and the continuous gradual change of nickel salt, cobalt salt and manganese salt feeding and components is realized; aging, filter pressing, washing and drying reaction products in the reaction kettle to obtain a full-gradient high-nickel ternary precursor Ni0.72Co0.14Mn0.14(OH)2Mixing lithium source compound and full-gradient high-nickel ternary precursor Ni0.72Co0.14Mn0.14(OH)2Mixing Li (Ni + Co + Mn) in a molar ratio of 1.05: 1; obtaining a mixture; sintering the obtained mixture in an oxygen atmosphere, wherein the sintering process comprises two stages, the sintering temperature of the first stage is controlled to be 500 ℃, the sintering temperature time is controlled to be 8 hours, the sintering temperature of the second stage is controlled to be 820 ℃, the sintering temperature time is controlled to be 16 hours, and dissociation and sieving are carried out after sintering to obtain the full-gradient high-nickel ternary cathode material LiNi0.72Co0.14Mn0.14O2. The full-gradient high-nickel ternary cathode material LiNi prepared in the example 2 is used0.72Co0.14Mn0.14O2A 2032 button cell is prepared, a blue test system is adopted to test at 25 ℃, the test voltage range is 2.8-4.3V, and the full-gradient high-nickel ternary cathode material LiNi prepared in the embodiment 20.72Co0.14Mn0.14O2The 1C first discharge capacity of the prepared 2032 button cell is 176.5 mAh/g; the battery capacity retention rate after 1000 cycles of the full battery was 94.9%.
Example 3
Referring to fig. 1, a method for preparing a full-gradient high-nickel ternary cathode materialAdding nickel sulfate into deionized water to prepare 300L of mixed solution A, and controlling the molar concentration of nickel in the mixed solution A to be 4 mol/L; storing the mixed solution A in a first raw material tank, and starting a stirring device arranged in the first raw material tank; adding nickel sulfate, cobalt sulfate and manganese sulfate into deionized water to prepare 100L of mixed solution B, and controlling the molar concentration of nickel, the molar concentration of cobalt and the molar concentration of manganese in the mixed solution B to be 4: 2: 4, controlling the sum of the molar concentration of nickel, the molar concentration of cobalt and the molar concentration of manganese in the mixed solution B to be 2 mol/L; storing the mixed solution B in a second raw material tank, and starting a stirring device arranged in the second raw material tank; adding nickel sulfate, cobalt sulfate and manganese sulfate into deionized water to prepare 100L of mixed solution C, and controlling the molar concentration of nickel, the molar concentration of cobalt and the molar concentration of manganese in the mixed solution C to be 1: 1: 1; controlling the sum of the molar concentration of nickel, the molar concentration of cobalt and the molar concentration of manganese in the mixed solution C to be 1mol/L, storing the mixed solution C in a third raw material tank, and starting a stirring device arranged in the third raw material tank; co-currently pumping the mixed solution A, a sodium hydroxide solution with the molar concentration of 4mol/L and ammonia water with the molar concentration of 5mol/L into a reaction kettle, filling nitrogen into the reaction kettle, controlling the temperature in the reaction kettle to be 60 ℃, controlling the pH value in the reaction kettle to be 11.6, starting a stirring device in the reaction kettle, controlling the stirring speed of the stirring device to be 500rpm/min, stirring for reaction, continuously pumping the mixed solution B into the mixed solution A at the speed of 10L/h after the reaction lasts for 1h, and continuously pumping the mixed solution C into the mixed solution B at the speed of 6L/h after the reaction lasts for 5 h; when the mixed solution A, the mixed solution B and the mixed solution C are completely pumped into the reaction kettle, stopping pumping the 4mol/L sodium hydroxide solution and the ammonia water with the molar concentration of 5mol/L into the reaction kettle until the reaction stops; obtaining a reaction product; as the mixed solution A of the first raw material tank is continuously pumped into the reaction kettle for reaction consumption, the mixed solution B of the second raw material tank is continuously pumped into the mixed solution A at the speed of 10L/h, and the mixed solution C of the third raw material tank is continuously pumped into the mixed solution B at the speed of 6L/h, the nickel content in the first raw material tank is gradually reduced, the cobalt and manganese content is gradually increased, and the feeding and the forming of nickel salt, cobalt salt and manganese salt are realizedContinuous gradual change of the components; aging, filter pressing, washing and drying reaction products in the reaction kettle to obtain a full-gradient high-nickel ternary precursor Ni0.88Co0.05Mn0.07(OH)2Mixing lithium source compound and full-gradient high-nickel ternary precursor Ni0.88Co0.05Mn0.07(OH)2Mixing Li (Ni + Co + Mn) in a molar ratio of 1.02: 1; obtaining a mixture; sintering the obtained mixture in an oxygen atmosphere, wherein the sintering process comprises two stages, the sintering temperature of the first stage is controlled to be 500 ℃, the sintering temperature time is controlled to be 8 hours, the sintering temperature of the second stage is controlled to be 750 ℃, the sintering temperature time is controlled to be 18 hours, and after sintering, dissociation and sieving are carried out to obtain the full-gradient high-nickel ternary cathode material LiNi0.88Co0.05Mn0.07O2. The full-gradient high-nickel ternary cathode material LiNi prepared in the example 3 is used0.88Co0.05Mn0.07O2A 2032 button cell is prepared, a blue test system is adopted to test at 25 ℃, the test voltage range is 2.8-4.3V, and the full-gradient high-nickel ternary cathode material LiNi prepared in the embodiment 30.88Co0.05Mn0.07O2The 1C first discharge capacity of the manufactured 2032 button cell is 198.6 mAh/g; the battery capacity retention rate after 1000 cycles of the full battery was 92.5%.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. The preparation method of the full-gradient high-nickel ternary precursor is characterized by comprising the following steps of:
s1: preparing a mixed solution A, a mixed solution B and a mixed solution C; the methods for preparing the mixed solution a, the mixed solution B and the mixed solution C are as follows:
adding nickel salt, cobalt salt and manganese salt into deionized water to prepare a mixed solution A, wherein the molar concentration of nickel, the molar concentration of cobalt and the molar concentration of manganese in the mixed solution A are controlled to be (1-x-y): x: y;
adding nickel salt, cobalt salt and manganese salt into deionized water to prepare a mixed solution B, wherein the molar concentration of nickel, the molar concentration of cobalt and the molar concentration of manganese in the mixed solution B are controlled to be (1-a-B): a: b;
adding nickel salt, cobalt salt and manganese salt into deionized water to prepare a mixed solution C, and controlling the molar concentration of nickel, the molar concentration of cobalt and the molar concentration of manganese in the mixed solution C to be 1: 1: 1;
wherein 1/3 < (1-a-b) < (1-x-y); the nickel salt is one of nickel sulfate, nickel chloride, nickel nitrate or nickel acetate, the cobalt salt is one of cobalt sulfate, cobalt chloride, cobalt nitrate or cobalt acetate, the manganese salt is one of manganese sulfate, manganese chloride, manganese nitrate or manganese acetate, in S1, x is more than or equal to 0 and less than or equal to 0.1, and y is more than or equal to 0 and less than or equal to 0.1; in S1, a is more than or equal to 0.15 and less than or equal to 0.35, and b is more than or equal to 0.2 and less than or equal to 0.4;
s2: reaction in a reaction kettle: co-current pumping the mixed solution A, the alkaline solution and the complexing agent into a reaction kettle, filling protective gas into the reaction kettle, controlling the temperature in the reaction kettle to be 45-70 ℃, controlling the pH value in the reaction kettle to be 10-12.5, starting a stirring device in the reaction kettle, stirring for reaction, after the reaction time is T1, continuously pumping the mixed solution B into the mixed solution A at a speed V1, and after the reaction time is T2, continuously pumping the mixed solution C into the mixed solution B at a speed V2;
s3: stopping the reaction: when the mixed solution A, the mixed solution B and the mixed solution C are completely pumped into the reaction kettle, stopping pumping the alkaline solution and the complexing agent into the reaction kettle, and stopping reaction to obtain a reaction product;
s4: and (3) product treatment: and (3) aging, filter-pressing, washing and drying the reaction product in the reaction kettle to obtain the full-gradient high-nickel ternary precursor.
2. The preparation method of the full-gradient high-nickel ternary precursor according to claim 1, wherein the sum of the molar concentration of nickel, the molar concentration of cobalt and the molar concentration of manganese in the mixed solution A is controlled to be 1-4.5 mol/L in S1; controlling the sum of the molar concentration of nickel, the molar concentration of cobalt and the molar concentration of manganese in the mixed solution B to be 0.5-3.5 mol/L; and controlling the sum of the molar concentration of nickel, the molar concentration of cobalt and the molar concentration of manganese in the mixed solution C to be 0.5-2.5 mol/L.
3. The method according to claim 1, wherein in step S2, the mixed solution A is stored in a first raw material tank, the mixed solution B is stored in a second raw material tank, the mixed solution C is stored in a third raw material tank, stirring devices are arranged in the first raw material tank, the second raw material tank and the third raw material tank, the bottom of the second raw material tank is communicated with the first raw material tank through a pipeline, a metering pump is arranged on the pipeline through which the second raw material tank is communicated with the first raw material tank, the bottom of the third raw material tank is communicated with the second raw material tank through a pipeline, and a metering pump is arranged on the pipeline through which the third raw material tank is communicated with the second raw material tank.
4. The preparation method of the full-gradient high-nickel ternary precursor according to claim 1, wherein the alkaline solution in S2 is one of a sodium hydroxide solution and a potassium hydroxide solution, the molar concentration of the alkaline solution is 2 to 8mol/L, the complexing agent in S2 is one of ammonia water and an ammonium salt solution, the molar concentration of the complexing agent is 2 to 8mol/L, the protective gas in S2 is one of nitrogen gas and argon gas, the stirring speed of a stirring device in the reaction kettle in S2 is 300 to 800rpm, and the device for controlling the pH value in the reaction kettle in S2 is an online pH meter.
5. The preparation method of the full-gradient high-nickel ternary precursor according to claim 1, wherein the reaction time T1 in S2 is 0.5-5 hours, the reaction time T2 is 2-12 hours, the speed V1 is 6-20L/h, and the speed V2 is 4-12L/h.
6. The preparation method of the full-gradient high-nickel ternary cathode material is characterized by comprising the following steps of:
s01: preparing a full-gradient high-nickel ternary precursor, and preparing the full-gradient high-nickel ternary precursor according to the preparation method of the full-gradient high-nickel ternary precursor in any one of claims 1 to 5;
s02: mixing: mixing a lithium source compound and a full-gradient high-nickel ternary precursor according to a molar ratio; obtaining a mixture;
s03: and (3) sintering: and sintering the obtained mixture in an oxygen atmosphere, and performing post-treatment after sintering to obtain the full-gradient high-nickel ternary cathode material.
7. The preparation method of the full-gradient high-nickel ternary cathode material according to claim 6, wherein the lithium source compound in S02 is one or two of lithium hydroxide and lithium carbonate, and the lithium source compound and the full-gradient high-nickel ternary precursor are mixed in S02 according to a molar ratio of Li (Ni + Co + Mn) = 1-1.1: 1.
8. The preparation method of the full-gradient high-nickel ternary cathode material as claimed in claim 7, wherein the sintering in S03 is carried out in two stages, the sintering temperature in the first stage is controlled to be 400-550 ℃, the sintering temperature time is controlled to be 4-12 h, the sintering temperature in the second stage is controlled to be 650-900 ℃, the sintering temperature time is controlled to be 10-25 h, and the post-treatment is dissociation and sieving after sintering in S03.
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Effective date of registration: 20220803 Address after: No. 78, Baishi West Road, Jiuhua Demonstration Zone, Xiangtan City, Hunan Province, 411100 Patentee after: Hunan Sangrui New Material Co.,Ltd. Address before: Room g0232, headquarters building, Changsha Zhongdian Software Park, No. 39, Jianshan Road, Changsha hi tech Development Zone, Hunan 410000 Patentee before: Thornton New Energy Technology (Changsha) Co.,Ltd. |
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Denomination of invention: Preparation method of full gradient high nickel ternary precursor and full gradient high nickel ternary cathode material Effective date of registration: 20230104 Granted publication date: 20211105 Pledgee: China Everbright Bank Co.,Ltd. Changsha Huafeng Sub branch Pledgor: Hunan Sangrui New Material Co.,Ltd. Registration number: Y2023430000001 |
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Granted publication date: 20211105 Pledgee: China Everbright Bank Co.,Ltd. Changsha Huafeng Sub branch Pledgor: Hunan Sangrui New Material Co.,Ltd. Registration number: Y2023430000001 |
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Denomination of invention: Preparation method of full gradient high nickel ternary precursor and full gradient high nickel ternary cathode material Granted publication date: 20211105 Pledgee: China Everbright Bank Co.,Ltd. Changsha Huafeng Sub branch Pledgor: Hunan Sangrui New Material Co.,Ltd. Registration number: Y2024980002053 |