CN112850807B - Ternary precursor, preparation method, ternary material and lithium ion battery - Google Patents
Ternary precursor, preparation method, ternary material and lithium ion battery Download PDFInfo
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- 239000002243 precursor Substances 0.000 title claims abstract description 85
- 239000000463 material Substances 0.000 title claims description 53
- 238000002360 preparation method Methods 0.000 title claims description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 13
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 13
- 239000002245 particle Substances 0.000 claims abstract description 52
- 238000009826 distribution Methods 0.000 claims abstract description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 6
- 239000011734 sodium Substances 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 239000011593 sulfur Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 53
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 239000003513 alkali Substances 0.000 claims description 38
- 238000005406 washing Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 4
- 229910001437 manganese ion Inorganic materials 0.000 claims description 4
- 229910001453 nickel ion Inorganic materials 0.000 claims description 4
- 229910017698 Ni 1-x-y Co Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229940053662 nickel sulfate Drugs 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 28
- 239000007774 positive electrode material Substances 0.000 abstract description 7
- 230000002349 favourable effect Effects 0.000 abstract description 5
- 230000001276 controlling effect Effects 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 239000000843 powder Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- 230000001105 regulatory effect Effects 0.000 description 9
- 230000009286 beneficial effect Effects 0.000 description 7
- 239000012266 salt solution Substances 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 6
- 239000011163 secondary particle Substances 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000006138 lithiation reaction Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 230000029219 regulation of pH Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000705 flame atomic absorption spectrometry Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- 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 application provides a ternary precursor, wherein the particle size distribution D50 of the ternary precursor is 2.5-4.5 mu m, (D90-D10)/D50 is 0.7-1.3, and the ternary precursor contains 150-400ppm of sulfur element and less than 100ppm of sodium element. The ternary precursor has the advantages of small particle size, large specific surface area, uniform particle size distribution, high tap density, low content of sodium, sulfur and other impurities, and is favorable for preparing the ternary positive electrode material with excellent performance.
Description
Technical Field
The application relates to the technical field of ternary cathode materials of lithium ion batteries, in particular to a ternary precursor, a preparation method, a ternary material and a lithium ion battery.
Background
The ternary positive electrode material has high capacity, high circularity and high safety, and is a main stream positive electrode material in an electric automobile battery. In the prior art, a ternary precursor is generally prepared firstly, and then a ternary positive electrode material is obtained through a high-temperature lithiation process, so that the physical and chemical properties of the ternary precursor influence the electrochemical performance of the final ternary positive electrode material. Research shows that compared with larger ternary material secondary particles, the submicron monocrystalline ternary material has higher interface electrochemical stability and shorter lithium ion transmission path, and can show better electrochemical performance, namely, is favorable for improving the performance of the ternary battery. Therefore, in order to finally obtain the monocrystal ternary material, a ternary precursor with smaller particle size needs to be prepared. Furthermore, the impurity content in the ternary material has an impact on the quality improvement of the ternary material, which requires that fewer impurities be contained in the ternary precursor from which the ternary material is prepared.
Disclosure of Invention
In order to solve the technical problems that the ternary precursor prepared in the prior art has large particle size, contains more impurities and the like and affects the electrochemical performance of the ternary material prepared by the ternary precursor, the preparation method of the ternary precursor, the ternary material and the lithium ion battery are provided. The ternary precursor has the advantages of small particle size, large specific surface area, uniform particle size distribution, high tap density, low content of sodium, sulfur and other impurities, and is favorable for preparing the ternary positive electrode material with excellent performance.
To achieve the above object, in a first aspect, the present application provides a ternary precursor, wherein the ternary precursor has a particle size distribution D50 of 2.5-4.5 μm and (D90-D10)/D50 of 0.7-1.3, and the ternary precursor contains 150-400ppm of sulfur element and less than 100ppm of sodium element.
Compared with the prior art, the ternary precursor provided by the application has the advantages of small particle size, uniform particle size distribution and low impurity content, and can be used for preparing the ternary material with high performance. The ternary precursor with small particle size can improve calcination activity when preparing ternary materials, is favorable for preparing single crystal ternary materials with small particle size, has higher interfacial electrochemical stability and shorter lithium ion transmission path compared with ternary materials with large particle size, and can show excellent thermal and electrochemical properties, and is favorable for improving the cycling stability of ternary batteries and the like. In addition, the particle size distribution of the ternary precursor provided by the application is even, and the fine powder with larger particles or too small particle size cannot exist, because the particles with larger particle size are not beneficial to the exertion of the material capacity, and the fine powder with too small particle size is easy to be screened to cause loss, so that the promotion of the battery capacity is not beneficial. Moreover, the content of impurities in the ternary precursor is low, and because the impurities cannot provide capacity, the gram capacity of the material can be low due to the existence of the impurities, so that the ternary precursor with low impurity content is prepared by the ternary precursor with low impurity content, and the content of the impurities in the ternary material is low, so that the improvement of the material capacity is facilitated.
In a second aspect, the present application provides a method for preparing the ternary precursor, including the following steps:
(1) Preparing a mixed sulfate solution with a certain concentration, a first alkali solution with a certain concentration and containing sodium hydroxide, and a second alkali solution with a certain concentration;
(2) Adding mixed sulfate solution and second alkali solution into the first alkali solution for reaction, controlling the PH of the reaction to be 11.3-12.5, and controlling the reaction time to be 0.1-20h;
(3) Continuously adding mixed sulfate solution into the mixed solution in the step (2) for reaction, and controlling the PH of the reaction to be 11.0-11.8, wherein the reaction time is 1-20h;
(4) Continuously adding mixed sulfate solution into the mixed solution in the step (3) to react, controlling the PH of the reaction to be 10.3-11.0, and stopping the reaction until the particle size is required;
(5) And (3) cleaning the product obtained in the step (4) by adopting a centrifugal separation and water bath stirring mode to obtain the ternary precursor.
Unlike the method for preparing ternary precursor in the prior art, the method provided by the application comprises three PH control stages, namely, the PH value of the reaction and the reaction time under the PH value are regulated and controlled, so that the reaction process is regulated and controlled, the nucleation and growth process of the material is regulated and controlled, and finally the ternary precursor meeting the requirements is obtained. Step (2), namely a first stage of PH regulation, which mainly takes the core of the prepared material as a main part, and simultaneously accompanies a continuous nucleation process, and can control the particle size D50 of a reaction product to be less than 2.0 mu m; step (3), namely a second stage of PH regulation, wherein the second stage is only a kernel growth stage of the material, and the D50 of the controllable product is less than 2.8 mu m; step (4), the third stage of PH control, relies primarily on stacking and epitaxial elongation of the primary particles, ultimately manifesting as secondary particle enlargement of the material and uniformity of particle size. By regulating and controlling the reaction PH and the reaction time, the ternary precursor with smaller particle size and uniform particle size distribution can be prepared. The ternary precursor with low impurity content can be prepared by cleaning the reaction product in the step (5), namely mother liquor carried in the powder can be reduced by centrifugal separation, so that the impurity removal rate can be improved, and the exchange of the powder and the washing liquid substances can be improved by stirring in a water bath, so that the washing effect can be improved. By the preparation method of the ternary precursor, the ternary precursor with small particle size, uniform particle size distribution and low impurity content can be prepared, so that the ternary material and the ternary battery with excellent properties such as high gram capacity and long cycle performance can be prepared.
In a third aspect, the present application provides a ternary material, where the ternary material is prepared by mixing the ternary precursor or the ternary precursor prepared by the preparation method described above with a lithium source.
In a fourth aspect, the present application provides a lithium ion battery comprising the ternary material described above.
Additional features and advantages of the present application will be set forth in the detailed description which follows.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects solved by the present application more clear, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application.
In a first aspect, the present application provides a ternary precursor, where the ternary precursor has a particle size distribution D50 of 2.5-4.5 μm and a (D90-D10)/D50 of 0.7-1.3, and the ternary precursor contains 150-400ppm of sulfur element and less than 100ppm of sodium element.
Compared with the ternary material with larger particle size, the ternary precursor provided by the application has higher interface electrochemical stability and shorter lithium ion transmission path, thereby being beneficial to the improvement of the ternary battery performance;
the primary particles of the ternary precursor stacked by the primary nano sheets have the thickness of more than 200nm, the particles are tightly combined, and the secondary particles are more regular and less in agglomeration adhesion. The high-energy {010} surface of the crystal is fully exposed on the outer surface of the sphere, the {001} surface is buried inside the sphere, and the crystal is compact in structure and low in specific surface area in a macroscopic manner. Yuifeng Su, gang Chen, lai Chen et al demonstrate that the rate performance of layered cathode materials can be enhanced by increasing the area of the exposed 010 high-energy crystal planes, however the 010 planes tend to disappear during calcination. The invention effectively controls the stacking degree of the primary nano-sheets in the coprecipitation process along the {001} crystal axis regularly through three-step pH adjustment, so that the increase of the {010} effective plane area is realized during the calcination, and the rate performance is obviously improved.
The (D90-D10)/D50 of the ternary precursor is 0.7-1.3, namely the ternary precursor is in narrow particle size distribution, the particle size is uniform, too large particles and too small fine powder do not exist, the large particles are not beneficial to the exertion of the ternary material capacity, the fine powder is easily screened to cause the loss of the material, and the ternary precursor with uniform particle size distribution is more beneficial to preparing ternary materials with excellent electrochemical performance and does not cause the waste of the precursor materials; moreover, the ternary precursor contains a smaller amount of impurities, and the impurities are not removed in the process of preparing the ternary material from the ternary precursor, so that the precursor with a small impurity content can be used for preparing the ternary material with a small impurity content, and the impurities can not provide the battery capacity, so that the gram capacity of the ternary material can be effectively improved, and the energy density of the battery can be further improved.
In one embodiment, the ternary precursor has a specific surface BET of 3.5-25m 2 Preferably, the ternary precursor has a specific surface BET of 3.5-6.0m 2 /g。
The BET value of the specific surface is related to the morphology and the particle size of the ternary precursor, namely the ternary precursor secondary particles provided by the application are more regular, less in agglomeration and adhesion, compact in structure and low in specific surface area.
In one embodiment, the ternary precursor has a tap density of 1.4-2.2g/cm 3 Preferably, the tap density of the ternary precursor is 1.9-2.2g/cm 3 。
The ternary precursor provided by the application is a high-tap-weight precursor, so that the loading amount of a calcination sagger can be increased in the process of preparing the ternary material by calcination, and the production efficiency can be further improved; in addition, the ternary precursor with high tap is obtained by orderly stacking primary particles, so that the ordering degree of the lithium ion migration active surface can be improved, and the electrochemical performance of the material can be improved.
In one embodiment, the ternary precursor has the expression Ni 1-x-y Co x Mn y (OH) 2 （0.03≤x≤0.3，0.03≤y≤0.3,（1-x-y）≥0.5）。
In a second aspect, the present application provides a method for preparing the ternary precursor, including the following steps:
(1) Preparing a mixed salt solution with a certain concentration, wherein the mixed salt solution comprises soluble nickel salt, cobalt salt and manganese salt, preferably nickel sulfate, cobalt sulfate and manganese sulfate, and the total concentration of nickel, cobalt and manganese ions is 1.0-2.5mol/L; preparing a first alkali solution and a second alkali solution with certain concentration, wherein the first alkali solution is a mixed solution of a precipitator and a complexing agent, and contains strong alkali with the concentration of 4-8mol/L and ammonia with the concentration of 0.4-1.8mol/L, and the strong alkali is preferably sodium hydroxide in the application; the second alkali solution is ammonia water with the concentration of 0.3-1.3 mol/L;
(2) Controlling the temperature of the second alkali liquor to be 40-65 ℃, simultaneously adding the mixed salt solution and the first alkali liquor in the step (1), controlling the adding flow of the first alkali liquor, further regulating the PH of the reaction solution in the step to be 11.3-12.5, and reacting for 0.1-20h at the PH value;
(3) Stopping adding the first alkali solution after the reaction of the step (2) is finished, continuously adding the mixed salt solution, and controlling the adding amount of the mixed salt solution to keep the pH value of the reaction solution at 11.0-11.8, and reacting for 1-20h at the pH value;
(4) After the reaction of the step (3) is finished, continuously adding a mixed salt solution, and controlling the adding amount of the mixed salt solution to keep the pH value of the reaction solution at 10.3-11.0, and reacting at the pH value to the required particle size, namely monitoring the particle size of a reaction product in the process;
(5) And (3) cleaning the product obtained in the step (4) in an alternating manner of centrifugal separation and water bath stirring, so as to obtain the ternary precursor.
In one embodiment, step (4) is reacted to a desired particle size of 2.0-4.5 μm.
In one embodiment, the reaction product obtained in step (4) is aged first, and the washing in step (5) is performed, wherein the washing includes water washing and alkali washing; the concentration of the alkali solution adopted in the alkaline washing process is 0.5-1.5mol/L, and the liquid-solid ratio is 1-12; the alkali washing treatment is carried out before and after the water washing treatment, and then the ternary precursor is obtained through drying, filtering and demagnetizing.
According to the preparation method provided by the application, the ternary precursor with small particle size, uniform distribution and low impurity content can be prepared, the ternary precursor can be better prepared into the monocrystal ternary material with small particle size and low impurity content, and compared with the larger ternary material secondary particles, the monocrystal ternary material with small particle size has higher interfacial electrochemical stability and a shorter lithium ion transmission path, can show better electrochemical performance, and is beneficial to the improvement of the ternary battery performance; and the impurities in the ternary material cannot provide capacity, so that the low content of the impurities also contributes to the improvement of the capacity of the ternary material.
The preparation method mainly controls the pH value and the reaction time of the reaction liquid so as to regulate and control the nucleation and growth processes of the reaction product, thereby obtaining the particle size meeting the requirements; and the impurity content in the product is further reduced through special cleaning operation. The method comprises three PH regulating and controlling stages, wherein the first stage is the step (2), the stage mainly takes the kernel of the prepared product as the main part, and the particle diameter D50 of the reaction product can be controlled to be smaller than 2.0 mu m along with the continuous nucleation process; the second stage, namely the step (3), is only a kernel growth stage of the product, and the D50 of the product can be controlled to be less than 2.8 mu m; the third stage, step (4), relies mainly on stacking and epitaxial elongation of primary particles of the product pre-growth, and finally manifests itself in secondary particle enlargement and uniformity of particle size of the product. By regulating and controlling the reaction PH and the reaction time, the ternary precursor with smaller particle size and uniform particle size distribution can be prepared. The cleaning operation, namely the step (5), can prepare and obtain the ternary precursor with low impurity content, namely the mother liquor carried and adsorbed in the powder can be reduced through centrifugal separation, so that the impurity removal rate can be improved, and the exchange of the powder and the washing liquid substances can be improved through water bath stirring, so that the washing effect can be improved.
In a third aspect, the present application provides a ternary material, which is obtained by mixing the ternary precursor or the ternary precursor prepared by the preparation method described above with a lithium source and performing a lithiation process.
In a fourth aspect, the present application provides a lithium ion battery comprising a positive electrode active material selected from the ternary materials described above.
The present application is further illustrated in detail by the following examples, which are provided for the purpose of illustration and explanation only and are not intended to be limiting.
Example 1
Preparing a ternary precursor:
(1) Preparing a mixed sulfate solution containing nickel, cobalt and manganese ions, so that the total concentration of the nickel, cobalt and manganese ions is 2mol/L, and continuously introducing high-purity nitrogen into the mixed sulfate solution; preparing a mixed solution of a precipitator and a complexing agent, namely a first alkali solution, wherein the mixed solution contains NaOH with the concentration of 6mol/L and ammonia with the concentration of 1.5 mol/L; preparing ammonia water with the concentration of 0.6mol/L, namely a second alkali solution;
(2) Controlling the temperature of the second alkali solution to 55 ℃, simultaneously introducing high-purity nitrogen, stirring, controlling the stirring frequency to 22HZ, simultaneously adding the mixed sulfate solution and the first alkali solution in the step (1), and controlling the adding flow of the first alkali solution, so as to adjust the PH of the reaction solution to 12.2, and continuously carrying out the reaction for 18 hours;
(3) Stopping adding the first alkali solution after the reaction of the step (2) is finished, continuously adding the mixed sulfate solution, reducing the pH of the reaction solution to 11.6, and continuously reacting for 6 hours;
(4) After the reaction of the step (3) is finished, continuously adding mixed sulfate solution to reduce the pH of the reaction solution to 10.8, detecting the granularity of laser in the process, and stopping feeding when the D50 is 3-4 mu m;
(5) After stopping the reaction, the stirring frequency is reduced, aging is carried out for 2 hours, and after the aging is finished, water washing and alkali washing are carried out in an alternating manner of centrifugal separation and water bath stirring and slurry washing, so that impurity particles can be removed. Wherein, the concentration of alkali liquor in the alkaline washing process is 0.5mol/L, and the liquid-solid ratio is 2; the alkali washing treatment is carried out before and after the water washing treatment, and then the ternary precursor is obtained through drying, filtering and demagnetizing.
And mixing the ternary precursor obtained by the preparation with a lithium source to obtain a ternary material, and assembling a battery to test the battery performance.
Example 2
A ternary precursor was prepared according to the preparation method of example 1, differing from example 1 in that: in the step (1), the first alkali solution contains 4mol/L NaOH and 0.8mol/L ammonia, and the second alkali solution is 0.4mol/L ammonia water; in the step (2), the PH of the reaction solution is regulated to be 12.0, and the reaction is continuously carried out for 16 hours; the PH of the reaction solution in the step (3) is reduced to 11.5, and the reaction is continued for 18 hours; the PH of the reaction solution in the step (4) is reduced to 10.6; the concentration of the alkali liquor in the step (5) is 0.55mol/L.
And mixing the ternary precursor obtained by the preparation with a lithium source to obtain a ternary material, and assembling a battery to test the battery performance.
Example 3
A ternary precursor was prepared according to the preparation method of example 2, differing from example 2 in that: in the step (2), the reaction is continuously carried out for 6 hours; the PH of the reaction solution in the step (3) is reduced to 11.1, and the reaction is continued for 18 hours; the pH of the reaction solution in the step (4) was lowered to 10.4.
And mixing the ternary precursor obtained by the preparation with a lithium source to obtain a ternary material, and assembling a battery to test the battery performance.
Comparative example 1
A ternary precursor was prepared according to the preparation method of example 1, differing from example 1 in that: in the step (2), the PH of the reaction solution is regulated to be 12.1, and the reaction is continuously carried out for 3 hours; the PH of the reaction solution in the step (3) is reduced to 11.7, and the reaction is continued for 13h; there is no step (4).
And mixing the ternary precursor obtained by the preparation with a lithium source to obtain a ternary material, and assembling a battery to test the battery performance.
Comparative example 2
A ternary precursor was prepared according to the preparation method of example 1, differing from example 1 in that: the stirring frequency of the step (2) is 18HZ, the pH value is 13.0, and the continuous reaction time is 6h; the pH of the reaction solution in the step (3) is reduced to 12.0; the pH in the step (4) is reduced to 9.2;
and mixing the ternary precursor obtained by the preparation with a lithium source to obtain a ternary material, and assembling a battery to test the battery performance.
SEM test
The microstructure of the adsorbent powder was measured by a scanning electron microscope model JSM-7800 manufactured by Japanese Kogyo Co., ltd, and the scanning voltage was 5 KV and the magnification was 5K×. And (3) adhering the powder sample to the conductive adhesive tape, performing metal spraying treatment, and drying and preserving the sample in a vacuum drying oven before testing.
Specific surface area test
The specific surface area of the adsorbent powder was measured using a BET multipoint method using a specific surface area and pore analyzer model 3H-3000PS2 manufactured by Bei Shide Instrument technology Co., ltd. The test results are shown in Table 1.
Malvern granularity test
The particle size distribution of the material was tested using a Mastersizer 3000. The test results are shown in Table 1.
Element content determination
EPA 6010D-2014 inductively coupled plasma atomic emission spectrometry, GB/T9723-2007 general rules for chemical reagent flame atomic absorption spectrometry. The test results are shown in Table 1.
Battery performance test
The batteries in the above examples and comparative examples were tested according to the test method of GB/T30835, and the test results are shown in Table 2.
TABLE 1
TABLE 2
Claims (4)
1. The preparation method of the ternary precursor is characterized by comprising the following steps of:
(1) Preparing a mixed sulfate solution with a certain concentration, a first alkali solution with a certain concentration and containing sodium hydroxide and a second alkali solution with a certain concentration, wherein the first alkali solution contains 4-8mol/L of sodium hydroxide and 0.4-1.8mol/L of ammonia, and the second alkali solution is 0.3-1.3mol/L of ammonia water;
(2) Adding mixed sulfate solution and second alkali solution into the first alkali solution for reaction, controlling the pH value of the reaction to be 11.3-12.5, and the reaction time to be 0.1-20h;
(3) Continuously adding mixed sulfate solution into the mixed solution in the step (2) for reaction, and controlling the pH of the reaction to be 11.0-11.8, wherein the reaction time is 1-20h;
(4) Continuously adding mixed sulfate solution into the mixed solution in the step (3) to react, controlling the pH of the reaction to be 10.4-10.8, and stopping the reaction until the particle size is required;
(5) Cleaning the product obtained in the step (4) by adopting a centrifugal separation and water bath stirring mode to obtain a ternary precursor;
wherein the mixed sulfate solution in the step (1) is a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate, and the sum of the concentration of nickel, cobalt and manganese ions is 1.0-2.5mol/L; the particle size of the product is required to be monitored in the preparation process of the step (4), and the required particle size is D50 of 2.0-4.5 mu m; the washing in the step (5) comprises water washing and alkali washing, wherein the concentration of the alkali solution used for the alkali washing is 0.5-1.5mol/L.
2. A ternary precursor obtained by the method of claim 1; the particle size distribution D50 of the ternary precursor is 3.39-3.76 mu m, the (D90-D10)/D50 is 0.82-1.07, the ternary precursor contains 150-400ppm of sulfur element, and the content of sodium element is lower than 100ppm; the specific surface BET of the ternary precursor is 4.684-6.765m 2 /g; the tap density of the ternary precursor is 1.58-2.05g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The expression of the ternary precursor is Ni 1-x-y Co x Mn y (OH) 2 (0.03≤x≤0.3，0.03≤y≤0.3,(1-x-y)≥0.5)。
3. A ternary material, characterized in that the ternary material is prepared by mixing a ternary precursor prepared by the preparation method of claim 1 with a lithium source.
4. A lithium ion battery comprising the ternary material of claim 3.
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