CN114956206B - Pre-oxidation method of high-nickel ternary material precursor and precursor material obtained by pre-oxidation method - Google Patents
Pre-oxidation method of high-nickel ternary material precursor and precursor material obtained by pre-oxidation method Download PDFInfo
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- 239000002243 precursor Substances 0.000 title claims abstract description 141
- 239000000463 material Substances 0.000 title claims abstract description 127
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 52
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 41
- 230000003647 oxidation Effects 0.000 title claims abstract description 38
- 239000007800 oxidant agent Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 230000001590 oxidative effect Effects 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 13
- 238000000975 co-precipitation Methods 0.000 claims abstract description 8
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 47
- 239000011572 manganese Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 2
- 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 claims description 2
- 230000001502 supplementing effect Effects 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims 1
- 239000001569 carbon dioxide Substances 0.000 claims 1
- 238000005245 sintering Methods 0.000 abstract description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052744 lithium Inorganic materials 0.000 abstract description 13
- 150000003624 transition metals Chemical group 0.000 abstract description 13
- 238000002360 preparation method Methods 0.000 abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 abstract description 6
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000005119 centrifugation Methods 0.000 abstract description 4
- 238000007781 pre-processing Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 25
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 24
- 239000000460 chlorine Substances 0.000 description 18
- 239000011148 porous material Substances 0.000 description 14
- 239000004155 Chlorine dioxide Substances 0.000 description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 12
- 235000019398 chlorine dioxide Nutrition 0.000 description 12
- 229910052748 manganese Inorganic materials 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 230000014759 maintenance of location Effects 0.000 description 10
- 229910052723 transition metal Inorganic materials 0.000 description 10
- 238000010981 drying operation Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000005324 grain boundary diffusion Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004978 peroxycarbonates Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- 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
-
- 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
Abstract
The invention discloses a pre-oxidation method of a high-nickel ternary material precursor and a precursor material obtained by the pre-oxidation method, and belongs to the technical field of lithium battery materials. The pre-oxidation method of the high-nickel ternary material precursor comprises the following steps: the high-nickel ternary material precursor with the water content less than 10% obtained by coprecipitation precipitation and centrifugal treatment is reacted with a strong oxidizing substance to realize the pre-oxidation of the high-nickel ternary material precursor, wherein the strong oxidizing substance is ClO 2 、Cl 2 、O 3 、Cl 2 O and Cl 2 O 7 One or more of them. The invention utilizes the characteristic of strong oxidization of strong oxidizing substances to enable the strong oxidizing substances to react with the precursor after centrifugation. The preparation method of the invention ensures that the transition metal forms a high valence state which accords with the target product before high-temperature sintering by preprocessing the precursor, can obviously reduce the reaction difficulty and is beneficial to fully playing the electric property of the material.
Description
Technical Field
The invention relates to the technical field of lithium battery materials, in particular to a pre-oxidation method of a high-nickel ternary material precursor and the obtained precursor material.
Background
The ternary material or lithium-rich manganese and other lithium battery materials are generally composed of two or more transition metals, so that the ternary material or the lithium-rich manganese and other lithium battery materials are usually synthesized by coprecipitating the transition metals, adding lithium salt, mixing and then sintering at high temperature.
Generally, multiple transition metals are co-usedThe precipitate forms hydroxides or carbonates in a low valence (+2 valence) form, whereas for high nickel or manganese rich materials these low valence transition metals tend to form high valence Mn with oxygen in high temperature sintering 4+ Or Ni 3+ In high temperature solid phase reactions, the conversion of valence states of these transition metal elements often means structural reforming of various atoms, which easily results in incomplete oxidation reactions. By preprocessing the precursor, the transition metal forms a high valence state which accords with a target product before high-temperature sintering, the reaction difficulty can be obviously reduced, and the full play of the electrical property of the material is facilitated.
However, the pre-oxidation of the precursor mostly adopts a method of adding an oxidizing agent in an aqueous solution, which brings a lot of difficulties in processing the existing precursor preparation, such as how to ensure the synchronism of the reaction kinetics of the oxidizing agent and the growth of the precursor balls under a continuous process? How does the residual problem of the used oxidizing agents such as persulfates, peroxycarbonates, peroxides in the continuous process? Such drawbacks of the similar techniques have resulted in the related art not being widely used. Therefore, how to pre-oxidize the precursor rapidly and effectively is a problem to be solved.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a pre-oxidation method of a high-nickel ternary material precursor and the precursor material obtained by the pre-oxidation method.
The invention is realized in the following way:
the invention provides a pre-oxidation method of a high-nickel ternary material precursor, which comprises the following steps: the high-nickel ternary material precursor with the water content less than 10% obtained by coprecipitation precipitation and centrifugal treatment is reacted with a strong oxidizing substance to realize the pre-oxidation of the high-nickel ternary material precursor, wherein the strong oxidizing substance is ClO 2 、Cl 2 、O 3 、Cl 2 O and Cl 2 O 7 One or more of them.
The invention also provides a lithium battery precursor material prepared by the preparation method.
The invention has the following beneficial effects:
the invention provides a pre-oxidation method of a high-nickel ternary material precursor and the precursor material obtained by the pre-oxidation method. It comprises the following steps: the high-nickel ternary material precursor with the water content less than 10% obtained by coprecipitation precipitation and centrifugal treatment is reacted with a strong oxidizing substance to realize the pre-oxidation of the high-nickel ternary material precursor, wherein the strong oxidizing substance is ClO 2 、Cl 2 、O 3 、Cl 2 O and Cl 2 O 7 One or more of them. ClO with strong oxidizing substance 2 By way of example, the method utilizes the characteristic that the strong oxidizing substance has strong oxidation to enable the strong oxidizing substance to react with the precursor which is precipitated in a coprecipitation mode and centrifuged and has the water content of less than 10 percent, and oxidizes the transition metal ions in low valence state into the metal ions in high valence state, so that the transition metal forms the high valence state which accords with the target product before high-temperature sintering, the reaction difficulty is obviously reduced, and the full play of the electric property of the material is facilitated.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of example 1;
fig. 2 is a graph of the rate stability of examples 1 and 2 and comparative examples 1 and 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention aims to provide a pre-oxidation method of a high-nickel ternary material precursor and the precursor material obtained by the pre-oxidation method.
In order to achieve the above object of the present invention, the following technical means are specifically adopted.
The embodiment of the invention provides a pre-oxidation method of a high-nickel ternary material precursor, which comprises the following steps: the high-nickel ternary material precursor with the water content less than 10% obtained by coprecipitation precipitation and centrifugal treatment is reacted with a strong oxidizing substance to realize the pre-oxidation of the high-nickel ternary material precursor, wherein the strong oxidizing substance is ClO 2 、Cl 2 、O 3 、Cl 2 O and Cl 2 O 7 One or more of them.
The embodiment of the invention provides a pre-oxidation method of a high-nickel ternary material precursor, which abandons a mode of adding an oxidant into an aqueous solution to pre-oxidize the precursor, and adopts a gas-phase strong oxidant such as ClO 2 Pre-oxidizing the precursor in the powder state (obtained by centrifugation) to oxidize +2 valent metal ions in the precursor into higher valent metal ions, wherein the chlorine dioxide has the following properties: chlorine dioxide is a strong oxidizing agent and reacts vigorously with many substances. Chlorine dioxide has strong oxidizing ability in +4 valence state, and can be subjected to oxidation-reduction reaction with a plurality of organic and inorganic compounds; meanwhile, chlorine dioxide gas is very soluble in water, has a solubility about 5 times that of chlorine gas, and is dissolved to form a yellowish green solution, and has a pungent and pungent smell similar to that of chlorine gas. The concentration of chlorine dioxide in the liquid phase at 25 ℃ equilibrium is 23 times that in the gas phase. In contrast to chlorine gas hydrolysis in water, chlorine dioxide cannot hydrolyze to any significant amount in water but instead remains in solution as a dissolved gas. The chlorine dioxide solution is slightly acidified (ph=6), i.e. stability is enhanced by inhibiting its disproportionation, but in alkaline solutions disproportionation reactions occur rapidly, yielding a mixture of chlorite and chlorate. Therefore, the precursor with the water content less than 10 percent, which is obtained by coprecipitation and centrifugal treatment, is directly used as a reactant and is notThe precursor is not required to be specially treated, the water content is too high or too low, which is unfavorable for the reaction, but the material with the water content after centrifugal treatment is directly used as the reactant, wherein the water content is more favorable for the reaction with ClO 2 Not only the moisture increases the amount of chlorine dioxide adsorbed on the surface of the lithium battery material, but also the ClO 2 The oxidation-reduction reaction occurs rapidly in alkaline solutions, involving the following reactions:
5Ni(OH) 2 +ClO 2 →5NiOOH+2H 2 O+HCl
5Mn(OH) 2 +2ClO 2 →5MnO 2 +4H 2 O+2HCl
therefore, the pre-oxidation method of the high-nickel ternary material precursor provided by the embodiment of the invention. The precursor is not pre-oxidized in the solution, but pre-oxidized in the powder state (obtained by centrifugation), and the transition metal is formed into a high-valence state which accords with the target product before high-temperature sintering, so that the reaction difficulty can be obviously reduced, and the full play of the electric property of the material is facilitated. The whole reaction process does not change the prior art, and impurities are not easy to remain; the use of a gas phase strong oxidizer facilitates adequate contact between the reactants and the byproducts produced are also easily separated from the system.
In an alternative embodiment, the strongly oxidizing species is ClO 2 。
In an alternative embodiment, the high nickel ternary material precursor is one or more of a high nickel ternary hydroxide precursor and a high nickel ternary carbonate precursor.
In an alternative embodiment, where the transition metal precursor is a transition metal precursor comprising nickel and manganese, the molar ratio of transition metal precursor to strongly oxidizing species is ni:strongly oxidizing species=1:0.25 and mn:strongly oxidizing species=1:0.5.
In an alternative embodiment, the reaction vessel is a device having both heating and vacuum functions (e.g., a double cone rotary vacuum dryer or a vibratory dryer). The pre-oxidation comprises the following steps: placing the high-nickel ternary material precursor in a reaction container, and vacuumizing until the pressure is less than or equal to 0.02MPa; and then, filling mixed gas containing a strong oxidizing substance into a reaction container, and simultaneously keeping the pressure in the container to be lower than one atmosphere pressure to pre-oxidize the high-nickel ternary material precursor.
In an alternative embodiment, when the reaction vessel is a reaction vessel of a non-vacuum apparatus, the high nickel ternary material precursor is placed in the reaction vessel; and then introducing mixed gas containing a strong oxidizing substance into a closed container, and carrying out circulating mixing under normal pressure to realize the pre-oxidation of the high-nickel ternary material precursor.
The pressure in the reaction vessel is controlled under one atmosphere or normal pressure mainly for safety, so that the strong oxidizing substances such as chlorine dioxide gas are not easy to explode, and the whole reaction is smoothly and safely carried out.
In an alternative embodiment, the mixed gas containing the strong oxidizing substance is a mixed gas having a strong oxidizing substance concentration of 1% to 10%, and the mixed gas is a mixed gas containing a strong oxidizing substance and a non-oxidizing gas.
Taking strong oxidizing substances as examples, gaseous chlorine dioxide is unstable and is easily decomposed into oxygen and chlorine when being heated or in light, so that explosion is caused; explosion can also occur when substances such as organic substances which promote oxidation are encountered. The gaseous chlorine dioxide is more safe when diluted with air to a concentration below 10% (V/V).
In an alternative embodiment, the reaction time for the pre-oxidation is from 0.1h to 5h.
In an alternative embodiment, the method further comprises: after the pre-oxidation is completed, detecting the gas concentration of the strong oxidizing substances in the reaction container, and opening a gas valve when the gas concentration of the strong oxidizing substances is less than or equal to 1%, supplementing compressed air or nitrogen, and keeping the internal pressure and the external pressure consistent.
In an alternative embodiment, the method further comprises: and (3) heating and drying the materials in the reaction container, and taking out the materials when the water content is less than or equal to 1% to obtain the target precursor.
Taking chlorine dioxide as an example, a strong oxidizing substance is used in the subsequent drying treatment processClO with incomplete system failure 2 The water and HCl generated by the reaction can be removed in the subsequent drying process, and no impurity is introduced, so that the method has the advantages of simple process, easiness in operation and the like.
In a second aspect, the embodiment of the invention also provides a lithium battery precursor material prepared by the preparation method.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
The embodiment of the invention provides a pre-oxidation method of a high-nickel ternary material precursor, which comprises the following specific steps:
(1) Preparing transition metal precursor composite hydroxide or composite carbonate according to a conventional production process, and obtaining a precursor with water content less than 10% after a centrifugal process.
(2) Transferring the precursor to a drying device (such as a biconical vacuum dryer or a vibratory dryer) having heating and vacuum functions;
(3) Pumping the container to a vacuum state (the pressure is less than or equal to 0.02 MPa);
(4) ClO is to 2 Filled into container, clO 2 The dosage is determined according to the content of nickel and manganese in the precursor, and the specific standard is Ni to ClO 2 =1:0.25 and Mn:ClO 2 =1:0.5 while maintaining the vessel pressure below one atmosphere.
(5) Starting vibration or double cone operation, and continuously maintaining for about 3 hours;
(6) Detection of ClO in a Container 2 When the concentration is less than or equal to 1%, an air valve can be opened to supplement compressed air or nitrogen, and the internal pressure and the external pressure are kept consistent;
(7) And heating and drying to obtain the target precursor with water content less than or equal to 1%.
Example 1
The embodiment provides a ternary material, which is a pre-oxidized ternary material precursor and has a molar mass ratio of 1:1.05, then presintering at 600 ℃ for 3 hours, and then sintering at 780 ℃ for 10 hours.
Wherein, preparation of pre-oxidized ternary material precursorThe method comprises the following steps: placing the ternary material precursor in a vacuum container, discharging gas in the pores of the ternary material precursor, and then introducing ClO 2 Gas, clO 2 The dosage is determined according to the content of nickel and manganese in the precursor, and the specific standard is Ni to ClO 2 =1:0.25 and Mn:ClO 2 =1:0.5 while maintaining the vessel pressure below one atmosphere, vibration or bipyramid operation is turned on for about 3 hours to allow ClO to 2 The gas adsorbs to the pores and pre-oxidizes the surface of the ternary material precursor. Finally, heating and drying operation is carried out, and the target precursor is obtained after the water content is less than or equal to 1%.
Example 2
The embodiment provides a ternary material, which is a pre-oxidized ternary material precursor and has a molar mass ratio of 1:1.05, then presintering at 600 ℃ for 3 hours, and then sintering at 780 ℃ for 10 hours.
The preparation method of the pre-oxidized ternary material precursor comprises the following steps: placing the ternary material precursor in a vacuum container, discharging gas in the pores of the ternary material precursor, and then introducing ClO 2 Gas, clO 2 The dosage is determined according to the content of nickel and manganese in the precursor, and the specific standard is Ni to ClO 2 =1:0.5 and Mn:ClO 2 =1:1 while maintaining the vessel pressure below one atmosphere, vibration or bipyramid operation is turned on for about 3 hours to allow ClO to 2 The gas adsorbs to the pores and pre-oxidizes the surface of the ternary material precursor. Finally, heating and drying operation is carried out, and the target precursor is obtained after the water content is less than or equal to 1%.
That is, this example differs from example 1 only in the introduction of gaseous ClO 2 The amounts of (3) vary.
Example 3
The embodiment provides a ternary material, which is a pre-oxidized ternary material precursor and has a molar mass ratio of 1:1.05, then presintering at 600 ℃ for 3 hours, and then sintering at 780 ℃ for 10 hours.
The preparation method of the pre-oxidized ternary material precursor comprises the following steps: placing ternary material precursor in vacuum containerExhausting the gas in the pores of the ternary material precursor, and then introducing ClO 2 Gas, clO 2 The dosage is determined according to the content of nickel and manganese in the precursor, and the specific standard is Ni to ClO 2 =1:0.75 and Mn:ClO 2 =1:1.5 while maintaining the vessel pressure below one atmosphere, vibration or bipyramid operation is turned on for about 3 hours to allow ClO to 2 The gas adsorbs to the pores and pre-oxidizes the surface of the ternary material precursor. Finally, heating and drying operation is carried out, and the target precursor is obtained after the water content is less than or equal to 1%.
That is, this example differs from example 1 only in the introduction of gaseous ClO 2 The amounts of (3) vary.
Example 4
The embodiment provides a ternary material, which is a pre-oxidized ternary material precursor and has a molar mass ratio of 1:1.05, then presintering at 600 ℃ for 3 hours, and then sintering at 780 ℃ for 10 hours.
The preparation method of the pre-oxidized ternary material precursor comprises the following steps: placing the ternary material precursor in a vacuum container, discharging gas in the pores of the ternary material precursor, and then introducing Cl 2 Gas, cl 2 The dosage is determined according to the content of nickel and manganese in the precursor, and the specific standard is Ni to Cl 2 =1:0.5 and Mn:ClO 2 =1:1 while maintaining the vessel pressure below one atmosphere, vibration or bipyramid operation is turned on for about 3 hours to allow Cl 2 The gas adsorbs to the pores and pre-oxidizes the surface of the ternary material precursor. Finally, heating and drying operation is carried out, and the target precursor is obtained after the water content is less than or equal to 1%.
That is, this example differs from example 1 only in the type of oxidizing gas introduced.
Example 5
The embodiment provides a ternary material, which is a pre-oxidized ternary material precursor and has a molar mass ratio of 1:1.05, then presintering at 600 ℃ for 3 hours, and then sintering at 780 ℃ for 10 hours.
Wherein, preparation of pre-oxidized ternary material precursorThe method comprises the following steps: placing the ternary material precursor in a vacuum container, discharging gas in the pores of the ternary material precursor, and then introducing Cl 2 O gas, cl 2 The O dosage is determined according to the content of nickel and manganese in the precursor, and the specific standard is Ni to ClO 2 =1:0.25 and Mn:ClO 2 =1:0.5 while maintaining the vessel pressure below one atmosphere, vibration or bipyramid operation is started for about 3 hours to allow Cl 2 The O gas adsorbs to the pores and pre-oxidizes the surface of the ternary material precursor. Finally, heating and drying operation is carried out, and the target precursor is obtained after the water content is less than or equal to 1%.
That is, this example differs from example 1 only in the type of oxidizing gas introduced.
Comparative example 1
The comparative example provides a ternary material which is a pre-oxidized ternary material precursor and has a molar mass ratio of 1:1.05, then presintering at 600 ℃ for 3 hours, and then sintering at 780 ℃ for 10 hours.
The preparation method of the pre-oxidized ternary material precursor comprises the following steps: precursor of ternary material and ClO 2 Mixing the solutions, clO 2 The dosage is determined according to the content of nickel and manganese in the precursor, ni:ClO 2 =1:0.25 and Mn:ClO 2 =1:0.5, pre-oxidation with ternary material precursor surface in aqueous solution. Finally, heating and drying operation is carried out, and the target precursor is obtained after the water content is less than or equal to 1%.
That is, this comparative example differs from example 1 only in that: clO (ClO) 2 The manner of pre-oxidation is different.
Comparative example 2
The embodiment provides a ternary material, which is a pre-oxidized ternary material precursor and has a molar mass ratio of 1:1.05, then presintering at 600 ℃ for 3 hours, and then sintering at 780 ℃ for 10 hours.
The preparation method of the pre-oxidized ternary material precursor comprises the following steps: placing the ternary material precursor in a vacuum container, discharging gas in the pores of the ternary material precursor, and then introducing ClO 2 Gas, clO 2 The dosage is determined according to the content of nickel and manganese in the precursor, and the specific standard is Ni to ClO 2 =1:0.25 and Mn:ClO 2 =1:0.5 while maintaining the vessel pressure below one atmosphere, vibration or bipyramid operation is turned on for about 3 hours to allow ClO to 2 The gas adsorbs to the pores and pre-oxidizes the surface of the ternary material precursor. Finally, heating and drying operation is carried out, and the target precursor is obtained after the water content is less than or equal to 1%.
That is, this comparative example differs from example 1 only in that: the moisture content of the precursor was 20%.
Comparative example 3
The embodiment provides a ternary material, wherein the molar mass ratio of a pre-oxidized ternary material precursor to lithium hydroxide is 1:1.05, followed by presintering at 600℃for 3h and then sintering at 780℃for 10h.
The preparation method of the pre-oxidized ternary material precursor comprises the following steps: placing the ternary material precursor in a vacuum container, discharging gas in the pores of the ternary material precursor, and then introducing ClO 2 Gas, clO 2 The dosage is determined according to the content of nickel and manganese in the precursor, and the specific standard is Ni to ClO 2 =1:0.25 and Mn:ClO 2 =1:0.5 while maintaining the vessel pressure below one atmosphere, vibration or bipyramid operation is turned on for about 6 hours to allow ClO to 2 The gas adsorbs to the pores and pre-oxidizes the surface of the ternary material precursor. Finally, heating and drying operation is carried out, and the target precursor is obtained after the water content is less than or equal to 1%.
That is, this comparative example differs from example 1 only in that: the reaction time was 6h.
Comparative example 4
Similar to the procedure of example 1, the only difference is that: precursor and gaseous ClO 2 Not mixed with the ternary material precursor in a vacuum vessel under vibrating conditions.
Comparative example 5
Similar to the procedure of example 1, the only difference is that: and finally, heating and drying are not adopted.
Test results
The ternary materials obtained in the examples and the comparative examples, the conductive carbon black Super P and the binder PVDF are prepared into pole pieces according to the mass ratio of 90:5:5. The specific process is as follows: PVDF is added into NMP and stirred to be dissolved to form glue solution. Adding the glue solution, the conductive carbon black Super P and the ternary material into a deaeration machine for preparing battery slurry; coating the slurry on aluminum foil uniformly on a coating machine to form a pole piece, wherein the single-sided surface density is controlled at 8-12mg/cm 2 And drying left and right and then preparing the battery.
The button cell testing method comprises the following steps: and (3) placing the pole piece coated with the single side into a vacuum drying oven at 105 ℃ for vacuum drying for 12 hours, taking out the pole piece, and rolling on a roll squeezer for standby. The cell assembly was performed in an argon filled glove box with 1m lipf6ec as electrolyte: DEC: dmc=1: 1:1 (volume ratio), the metallic lithium sheet is the counter electrode. Battery model: 2025.
testing in a battery test cabinet:
1) Specific capacity test, charging to 4.3V at constant current of 0.1C, and standing for 5min; and 0.1C constant current discharge is carried out to 3.0V, and the specific discharge capacity is the specific capacity of the ternary material.
2) Testing high-temperature cycle performance, namely after the test 1) is completed, charging to 4.3V by adopting 1C constant current in a constant temperature cabinet at 25 ℃, and standing for 5min; constant current discharge of 0.2C to 3.0V; the above steps were then repeated again to complete 50 cycles. Performance tests were performed on lithium batteries assembled using the ternary materials prepared in examples 1 to 3 and comparative examples 1 to 5, and the results are shown in table 1.
TABLE 1 Performance test results
| Cell performance | |
| Example 1 | The initial discharge specific capacity is 219mAh/g, and the capacity retention rate is more than or equal to 98 percent after the cycle is carried out for 50 times at 25 DEG C |
| Example 2 | The initial discharge specific capacity is 214mAh/g, and the capacity retention rate is more than or equal to 92 percent after the cycle is carried out for 100 times at 25 DEG C |
| Example 3 | The initial discharge specific capacity is 216mAh/g, and the capacity retention rate is more than or equal to 98 percent after the cycle is carried out for 50 times at 25 DEG C |
| Example 4 | The initial discharge specific capacity is 217mAAh/g, and the capacity retention rate is more than or equal to 99 percent after 50 times of circulation at 25 DEG C |
| Example 5 | The initial discharge specific capacity is 218mAh/g, and the capacity retention rate is more than or equal to 98 percent after the cycle is carried out for 50 times at 25 DEG C |
| Comparative example 1 | The initial discharge specific capacity is 211mAh/g, and the capacity retention rate is more than or equal to 98 percent after the cycle is carried out for 50 times at 25 DEG C |
| Comparative example 2 | The initial discharge specific capacity is 206mAh/g, and the capacity retention rate is more than or equal to 98 percent after the cycle is carried out for 50 times at 25 DEG C |
| Comparative example 3 | The initial discharge specific capacity is 203mAh/g, and the capacity retention rate is more than or equal to 98 percent after the cycle is carried out for 50 times at 25 DEG C |
| Comparative example 4 | The initial discharge specific capacity is 196mAh/g, and the capacity retention rate is more than or equal to 90 percent after the cycle is carried out for 50 times at 25 DEG C |
| Comparative example 5 | The initial discharge specific capacity is 186mAh/g, and the capacity retention rate is about 80 percent after the cycle is 100 times at 25 DEG C |
As can be seen from table 1: the lithium batteries assembled by the ternary materials prepared in examples 1-5 have better electrical performance indexes than the lithium batteries assembled by the ternary materials prepared in comparative examples 1-5. With direct use of gaseous ClO 2 Compared with the preoxidation mode of the (2), whether the mode of dissolving in water or the precursor with more water content is used in the comparative example 1, the preoxidation effect of the material is poor, the performance of the final material is improved only limitedly, and the specific capacity index is slightly lower. In comparative example 3, the integrity of the particle morphology is affected due to the overlong vibration operation time, and further the capacity of the material is adversely affected. Comparative example 4 does not employ a vibration operation, resulting in a very insufficient pre-oxidation of the precursor and a large capacity loss. Comparative example 5 was a material in which chlorine residue was large and capacity loss was severe due to the heating and drying.
Further, SEM electron microscope scanning was performed on the modified material precursor obtained in example 1, and the result is shown in fig. 1, which shows: the surface of the modified material precursor obtained by the modification method provided in example 1 is relatively smooth.
Further, the rate performance test was performed on examples 1 and 2 and comparative examples 1 and 2, and the results are shown in fig. 2, which shows: the precursor properties of the modified materials obtained by the modification methods provided in examples 1 and 2 are better than those of comparative examples 1 and 2. Comparative examples 1 and 2 ClO was hindered by the presence of more water 2 The diffusion effect of the voids in the precursor is unfavorable for oxidation of the inner surfaces of the precursor voids, and thus the grain boundary diffusion channels of the final product are not abundant enough, and the rate performance is adversely affected.
In summary, the embodiment of the invention provides a pre-oxidation method of a high-nickel ternary material precursor and the precursor material obtained by the pre-oxidation method. The pre-oxidation method of the high-nickel ternary material precursor comprises the following steps: precipitating by coprecipitation and centrifuging to obtain a solution containingThe high-nickel ternary material precursor with the water content less than 10% reacts with a strong oxidizing substance to pre-oxidize the high-nickel ternary material precursor, wherein the strong oxidizing substance is ClO 2 、Cl 2 、O 3 、Cl 2 O and Cl 2 O 7 One or more of them. The pre-oxidation method provided by the embodiment of the invention utilizes the characteristic that the strong oxidizing substance has strong oxidation to enable the strong oxidizing substance to react with the precursor after centrifugation. By preprocessing the precursor, the transition metal forms a high valence state which accords with a target product before high-temperature sintering, the reaction difficulty can be obviously reduced, and the full play of the electrical property of the material is facilitated.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A method for pre-oxidizing a high nickel ternary material precursor, comprising the steps of: placing a high-nickel ternary material precursor with the water content less than 10% obtained by coprecipitation precipitation and centrifugal treatment in a reaction container, and vacuumizing until the pressure is less than or equal to 0.02MPa; then filling mixed gas containing strong oxidizing substances into a reaction container, keeping the pressure in the container to be lower than one atmosphere, starting vibration or bipyramid operation, continuously keeping for 0.1-5 h to pre-oxidize the high-nickel ternary material precursor, detecting the gas concentration of the strong oxidizing substances in the reaction container after the pre-oxidation is finished, opening a gas valve when the gas concentration of the strong oxidizing substances is less than or equal to 1%, supplementing compressed air or nitrogen, keeping the internal and external pressures of the reaction container consistent, heating and drying the materials in the reaction container, and taking out the materials when the water content of the materials is less than or equal to 1%, thereby obtaining the target precursor, wherein the strong oxidizing substances are ClO (carbon dioxide) 2 。
2. The method of claim 1, wherein the high nickel ternary material precursor is one or more of a high nickel ternary hydroxide precursor and a high nickel ternary carbonate precursor.
3. The method according to claim 2, wherein when the high-nickel ternary material precursor is a precursor containing nickel and manganese, the molar ratio of the high-nickel ternary material precursor to the strongly oxidizing substance is Ni:strongly oxidizing substance 1:0.25 or less and Mn:strongly oxidizing substance 1:0.5 or less.
4. The method according to claim 1, wherein the mixed gas containing a strongly oxidizing substance is a mixed gas containing a strongly oxidizing substance in a volume fraction of 1 to 10%, and the mixed gas is a mixed gas containing a strongly oxidizing substance and a non-oxidizing gas.
5. A precursor material prepared according to the method of any one of claims 1-4.
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