CN117980271A - Nickel-cobalt-manganese ternary precursor with high specific surface area and preparation and application thereof - Google Patents
Nickel-cobalt-manganese ternary precursor with high specific surface area and preparation and application thereof Download PDFInfo
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- 239000002243 precursor Substances 0.000 title claims abstract description 87
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000012010 growth Effects 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000001301 oxygen Substances 0.000 claims abstract description 38
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000013078 crystal Substances 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000002002 slurry Substances 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 18
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 16
- 239000010941 cobalt Substances 0.000 claims abstract description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000006911 nucleation Effects 0.000 claims abstract description 15
- 238000010899 nucleation Methods 0.000 claims abstract description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 13
- 238000000975 co-precipitation Methods 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 239000012266 salt solution Substances 0.000 claims abstract description 9
- 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 abstract description 6
- 239000011572 manganese Substances 0.000 claims description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 7
- 239000010406 cathode material Substances 0.000 claims description 3
- 230000020477 pH reduction Effects 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000002245 particle Substances 0.000 description 18
- 230000007423 decrease Effects 0.000 description 13
- 239000007774 positive electrode material Substances 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 11
- 229910017071 Ni0.6Co0.2Mn0.2(OH)2 Inorganic materials 0.000 description 10
- 239000012535 impurity Substances 0.000 description 10
- 229910021529 ammonia Inorganic materials 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 238000005245 sintering Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910003174 MnOOH Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- -1 but not limited to Chemical class 0.000 description 3
- 229940044175 cobalt sulfate Drugs 0.000 description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229940099596 manganese sulfate Drugs 0.000 description 3
- 239000011702 manganese sulphate Substances 0.000 description 3
- 235000007079 manganese sulphate Nutrition 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229940053662 nickel sulfate Drugs 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 239000012066 reaction slurry Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910017223 Ni0.8Co0.1Mn0.1(OH)2 Inorganic materials 0.000 description 1
- 229910015450 Ni1-x-yCoxMny(OH)2 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000003698 anagen phase Effects 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a nickel-cobalt-manganese ternary precursor with high specific surface area, and preparation and application thereof, wherein the preparation comprises the following steps: s1, under an inert atmosphere, flowing a mixed metal salt solution containing nickel, cobalt and manganese, strong alkali solution and ammonia water into a bottom solution of a reaction kettle, and performing a nucleation stage reaction in a coprecipitation process to obtain first slurry containing seed crystals; s2, reducing the pH value in the first slurry by 1.0-2.0 in an inert atmosphere, stirring, and performing an I-stage growth reaction to obtain a second slurry containing I-stage grains; s3, reducing the pH value in the second slurry by 0.4-0.6 in an oxygen-containing atmosphere, stirring, and carrying out a II-stage growth reaction to obtain second slurry containing II-stage crystal grains, wherein the II-stage crystal grains are nickel-cobalt-manganese ternary precursors with high specific surface areas; the D50 of the I-stage crystal grain is 1/2-4/5 of the D50 of the II-stage crystal grain, the specific surface area of the nickel-cobalt-manganese ternary precursor is improved, and the structural uniformity of the nickel-cobalt-manganese ternary precursor is maintained.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a nickel-cobalt-manganese ternary precursor with a high specific surface area, and preparation and application thereof.
Background
The lithium ion battery has the advantages of high energy, long service life, no memory effect, low pollution and the like, and is widely applied to various fields of consumer electronics, energy storage, power batteries and the like. Currently, the positive electrode materials adopted by the lithium ion battery mainly comprise lithium cobaltate, lithium iron phosphate, lithium manganate, lithium nickel cobalt manganate and the like. In recent years, the electric automobile industry rapidly develops, and higher requirements are put on the capacity of a power battery, so that the nickel cobalt lithium manganate ternary positive electrode material has a market prospect and development potential because of higher energy density than that of lithium iron phosphate and lithium manganate.
The performance of the ternary positive electrode material (nickel cobalt lithium manganate) is greatly dependent on the performance of the ternary precursor (such as nickel cobalt manganese hydroxide), wherein wet coprecipitation is a common method for preparing nickel cobalt manganese hydroxide, and the prepared nickel cobalt manganese hydroxide is added into a lithium source to synthesize the nickel cobalt lithium manganate positive electrode material through high-temperature sintering. The chemical composition, size, morphology, structure and other parameters of the nickel-cobalt-manganese ternary precursor have direct and crucial influence on the technical index of the nickel-cobalt-manganese ternary positive electrode material. At present, primary grains of the nickel-cobalt-manganese ternary precursor prepared by using conventional process parameters are coarse, primary grains are compact, the specific surface area of the nickel-cobalt-manganese ternary precursor is small, and the difficulty in sintering the rear-end positive electrode material is increased. The higher sintering temperature enables the high-nickel ternary cathode material to generate more serious Li/Ni mixed discharge, so that the performance of the battery is seriously attenuated in the subsequent charge-discharge cycle process. In addition, most of the positive electrode materials obtained by sintering inherit the structural characteristics of the precursor materials, namely, primary grains are coarse and compact, and the specific surface area is small. The contact area of the particles with small specific surface area and the electrolyte is small, so that the deintercalation migration rate of lithium ions can be reduced, and the performance requirements of high-power charge and discharge of the power battery are difficult to meet.
The specific surface area of the precursor material is increased by the relevant technicians through oxidation. For example, chinese patent CN 106684351B adds an oxidizing agent (such as potassium permanganate, sodium chlorate, hydrogen peroxide, etc.) in the precursor preparation process to obtain a precursor with a high specific surface area formed by aggregation of fibrous primary grains, but the amount of the oxidizing agent used in the method is large, the cost is high, the economic benefit is not achieved, and impurities such as additional K +、Na+ and Cl - may be introduced to affect the quality of the precursor. Chinese patent CN 115215384a discloses that high nickel precursors with both high specific surface and high compaction density are obtained by controlling ammonia and reaction atmosphere in different reaction stages, but air or oxygen atmosphere in the latter stage of the reaction easily causes excessive oxidation of more Mn to MnOOH or MnO 2 to cause a large amount of impurity introduction, resulting in serious structural non-uniformity affecting the performance of the subsequent cathode material. Although the specific surface area of the precursor can be improved by the method, the precursor structure is inevitably uneven due to the introduction of impurities, namely, in the related art, the nickel-cobalt-manganese ternary precursor has the problem that the specific surface area is improved and the structural uniformity is difficult to balance.
Therefore, it is necessary to provide a scheme for improving the specific surface area of the nickel-cobalt-manganese ternary precursor and ensuring the structural uniformity of the nickel-cobalt-manganese ternary precursor on the premise of ensuring high tap density.
Disclosure of Invention
In view of the above, the application provides a nickel-cobalt-manganese ternary precursor with high specific surface area, and preparation and application thereof, which are used for solving the problems of improving the specific surface area of the nickel-cobalt-manganese ternary precursor and maintaining the structural uniformity of the nickel-cobalt-manganese ternary precursor on the premise of ensuring high tap density.
In order to achieve the technical purpose, the application adopts the following technical scheme:
in a first aspect, the application provides a preparation method of a nickel-cobalt-manganese ternary precursor with a high specific surface area, which comprises the following steps:
s1, under an inert atmosphere, flowing a mixed metal salt solution containing nickel, cobalt and manganese, strong alkali solution and ammonia water into a bottom solution of a reaction kettle, carrying out a nucleation stage reaction in a coprecipitation process, and maintaining stirring to obtain a first slurry containing seed crystals;
S2, in an inert atmosphere, reducing the pH value in the first slurry by 1.0-2.0, gradually reducing the stirring speed according to the grain size increase, and performing an I-stage growth reaction to obtain a second slurry containing I-stage grains;
S3, reducing the pH value in the second slurry by 0.4-0.6 in an oxygen-containing atmosphere, maintaining stirring, and carrying out II-stage growth reaction to obtain second slurry containing II-stage crystal grains, wherein the II-stage crystal grains are nickel-cobalt-manganese ternary precursors with high specific surface areas;
the D50 of the I-stage grains is 1/2-4/5 of the D50 of the II-stage grains.
Preferably, the concentration of ammonia in step S1-step S3 is maintained unchanged.
Preferably, the stirring speed in step S3 is adjusted at a speed of 20-50rpm for every 1 μm increase in D50 of the I-stage grains; more preferably, the stirring speed in step S3 is adjusted at a speed of 30-40rpm for every 1 μm increase in D50 of the I-stage grains.
Preferably, the size of the II-stage grains D50 is 6-18. Mu.m.
Preferably, in step S3, the mass ratio of oxygen in the oxygen-containing atmosphere is 2-10%.
Preferably, in the mixed metal salt solution containing nickel, cobalt and manganese, the molar ratio of the nickel source to the cobalt source to the manganese source is (1-x-y): x: y, wherein x+y is more than or equal to 0.02 and less than or equal to 0.67.
Preferably, in step S1, the temperature of the coprecipitation reaction is 40-80 ℃.
Preferably, the rate of pH decrease in step S2 is (0.04-0.1)/h, and the rate of pH decrease in step S3 is (0.1-0.2)/h; the rate of pH decrease in step S3 is greater than the rate of pH decrease in step S2.
In a second aspect, the application provides a nickel-cobalt-manganese ternary precursor with a high specific surface area.
In a third aspect, the application provides an application of a nickel-cobalt-manganese ternary precursor with a high specific surface area in preparing a nickel-cobalt lithium manganate ternary positive electrode material.
The beneficial effects of the application are as follows: in the application, a precursor is obtained by a coprecipitation method, and the precursor comprises a nucleation stage and a growth stage, wherein the growth stage is divided into an I-stage growth stage and an II-stage growth stage. Nitrogen is introduced into the nucleation stage and the I-stage growth stage to ensure higher tap density, and compared with the nucleation stage, the pH value of the I-stage growth stage is reduced to finish the transformation of the nucleation-growth process, and the rotating speed is gradually reduced, so that gaps among primary particles are gradually filled and secondary particles are gradually grown; the pH value is further reduced in the II-stage growth stage, the higher rotating speed is maintained, and the reaction atmosphere is converted into the oxygen-containing atmosphere, so that the specific surface area of the I-stage crystal grains is improved. Meanwhile, oxygen-containing atmosphere is not immediately introduced after nucleation, but is introduced for oxidation when the D50 of the crystal grain grows to 1/2-4/5 of the target particle size, so that the impurity phase caused by introducing oxygen-containing atmosphere or introducing a large amount of oxygen in a short time when small particles are introduced is avoided, and the structural uniformity of the precursor is improved; in addition, in the II-stage growth stage, under the oxygen-containing atmosphere, the pH is further reduced and the higher rotating speed is maintained, so that primary grain refinement is facilitated, the specific surface area is improved, and finally, on the premise of ensuring high tap density, the specific surface area of the nickel-cobalt-manganese ternary precursor is improved and the structural uniformity of the nickel-cobalt-manganese ternary precursor is maintained.
Drawings
FIG. 1 is an SEM image of a Ni 0.6Co0.2Mn0.2(OH)2 precursor of example 1;
FIG. 2 is an XRD pattern of the Ni 0.6Co0.2Mn0.2(OH)2 precursor of example 1;
FIG. 3 is an SEM image of a Ni 0.6Co0.2Mn0.2(OH)2 precursor of comparative example 1;
Fig. 4 is an SEM image of the Ni 0.6Co0.2Mn0.2(OH)2 precursor of comparative example 3.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The application provides a preparation method of a nickel-cobalt-manganese ternary precursor with high specific surface area, which comprises the following steps:
S1, under an inert atmosphere, flowing a mixed metal salt solution containing nickel, cobalt and manganese, strong alkali solution and ammonia water into a bottom solution of a reaction kettle, carrying out a nucleation stage reaction in a coprecipitation process, and maintaining stirring to obtain a first slurry containing seed crystals; the pH of the nucleation stage reaction is 11.4-12.5;
S2, in an inert atmosphere, reducing the pH value in the first slurry by 1.0-2.0, gradually reducing the stirring speed according to the grain size increase, and performing an I-stage growth reaction to obtain a second slurry containing I-stage grains; preferably, in step S2, the pH is in the range of 10.4-11.4, e.g. 10.4, 10.6, 10.8, 11, 11.4; preferably, the pH in the first slurry is reduced by 1.0 to 1.1;
S3, reducing the pH value in the second slurry by 0.4-0.6 in an oxygen-containing atmosphere, maintaining stirring, and carrying out II-stage growth reaction to obtain second slurry containing II-stage crystal grains, wherein the II-stage crystal grains are nickel-cobalt-manganese ternary precursors with high specific surface areas; preferably, in step S3, the pH is in the range of 10-11, e.g. 10, 10.2, 10.5, 11;
The D50 of the I-stage crystal grain is 1/2-4/5 of the D50 of the II-stage crystal grain, and preferably, the D50 of the I-stage crystal grain is 2/3-4/5 of the D50 of the II-stage crystal grain.
The application achieves the aim of simultaneously increasing the specific surface area and structural uniformity of the precursor on the premise of keeping higher tap density by controlling pH, stirring speed and reaction atmosphere in the nucleation-I-order growth-II-order growth process, and the specific mechanism is as follows:
In the application, a precursor is obtained by a coprecipitation method, and the precursor comprises a nucleation stage and a growth stage, wherein the growth stage is divided into an I-stage growth stage and an II-stage growth stage. Nitrogen is introduced into the nucleation stage and the I-stage growth stage to ensure higher tap density, and compared with the nucleation stage, the pH value of the I-stage growth stage is reduced to finish the transformation of the nucleation-growth process, and the rotating speed is gradually reduced, so that gaps among primary particles are gradually filled and secondary particles are gradually grown; the step II growth stage further reduces the pH value, maintains a higher rotating speed, and simultaneously converts the reaction atmosphere into an oxygen-containing atmosphere, so that primary grains of the step I grains are refined, and the specific surface area of the precursor is improved. Meanwhile, oxygen-containing atmosphere is not immediately introduced after nucleation, but is introduced for oxidation when the D50 of the crystal grain grows to 1/2-4/5 of the target particle size, so that the impurity phase caused by introducing oxygen-containing atmosphere or introducing a large amount of oxygen in a short time when small particles are introduced is avoided, and the uniformity of the precursor is improved; in addition, in the II-stage growth stage, under the oxygen-containing atmosphere, the pH is further reduced and the higher rotating speed is maintained, so that primary grain refinement is facilitated, the specific surface area is improved, and finally, on the premise of ensuring high tap density, the specific surface area of the nickel-cobalt-manganese ternary precursor is improved, and the structural uniformity of the nickel-cobalt-manganese ternary precursor is maintained.
In some embodiments, the nickel source is a nickel soluble salt including, but not limited to, nickel sulfate, nickel nitrate, nickel chloride; cobalt sources are cobalt soluble salts including, but not limited to, cobalt sulfate, cobalt nitrate, cobalt chloride; manganese sources are manganese soluble salts including, but not limited to, manganese sulfate, manganese nitrate, manganese chloride; preferably, the nickel source is nickel sulfate, the cobalt source is cobalt sulfate, and the manganese source is manganese sulfate; in the step S1, the mass concentration of total metal ions in the mixed solution of the nickel source, the cobalt source and the manganese source is 60-120g/L, for example, 60g/L, 80g/L, 100g/L and 120g/L, and can be any value in the range; the flow rate of the mixed solution is 2-5% V/h, wherein V is the volume of the reaction kettle.
The concentration of ammonia water in the steps S1-S3 of the scheme is kept unchanged. The alkali solution comprises one or more of sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution and sodium bicarbonate solution, preferably, the alkali solution is sodium hydroxide solution; the mass fraction of the alkali liquor is 20-40%. The mass fraction of the aqueous ammonia used in this scheme is 12-30%, and the ammonia concentration of the supernatant of the reaction slurry in steps S1-S3 is maintained relatively constant. In some embodiments, the concentration of ammonia is 2-12g/L, e.g., the concentration of ammonia in the supernatant of the reaction slurry in steps S1-S3 is maintained at one of 2g/L, 5g/L, 8g/L, 10g/L, 12g/L, or at any value in the above ranges. The whole process of the scheme maintains the constant pH value and the concentration of the ammonia water in each reaction stage by adjusting the flow rates of the strong alkali solution and the ammonia water. The ammonia concentration is maintained stable in the whole process, so that the great fluctuation of the ammonia concentration of the system caused by greatly adjusting the flow of the volatile ammonia solution is avoided, the product consistency is high, and the method is easy to repeat and produce in a large scale.
The stirring speed of step S2 is adjusted by decreasing the speed of 20-50rpm every 1 μm on the basis of the seed crystal-containing slurry obtained in step S1, while the stirring speed of step S3 is maintained not to decrease again until the reaction is completed after the end of the growth stage I. Step S1-step S3 are reacted in a stirring environment, wherein the stirring speed of step S1 is 400-800rpm; after the D50 of the reaction slurry reaches a certain particle size in the step S2, the stirring speed is reduced to 250-400rpm according to a certain reduction rate; the stirring speed in step S3 maintains the stirring speed at the end of step S2.
In this embodiment, the size of the II-stage crystal grains D50 is 6 to 18. Mu.m, preferably, the size of the II-stage crystal grains D50 is 10 to 15. Mu.m.
In the step S3, the mass ratio of oxygen in the oxygen-containing atmosphere is 2-10%, the oxygen-containing atmosphere can be air, mixed gas of air and inert atmosphere, and the like, and in the application, the flow of the oxygen-containing atmosphere is 0.5-3V/h, wherein V is the volume of the reaction kettle.
In the scheme, the molar ratio of the nickel source to the cobalt source to the manganese source is (1-x-y): x: y, wherein x+y is more than or equal to 0.02 and less than or equal to 0.67, the chemical formula of the nickel-cobalt-manganese ternary precursor is Ni 1-x-yCoxMny(OH)2, wherein x+y is more than or equal to 0.02 and less than or equal to 0.67, and the chemical formula of the nickel-cobalt-manganese ternary precursor is matched by controlling the molar ratio of a nickel source, a cobalt source and a manganese source, for example, the molar ratio of the nickel source, the cobalt source and the manganese source is set to be 6:2:2 and corresponds to Ni 0.6Co0.2Mn0.2(OH)2, and the molar ratio of the nickel source, the cobalt source and the manganese source is set to be 8:1:1 and corresponds to Ni 0.8Co0.1Mn0.1(OH)2, or other defined ratios are met.
In some embodiments, the temperature of the coprecipitation reaction in step S1 is 40-80℃and the reaction temperature in steps S1-S3 is kept constant.
In some embodiments, the rate of pH decrease in step S2 is (0.04-0.1)/h, the rate of pH decrease in step S3 is (0.1-0.2)/h, and nucleation-growth stage I employs a lower pH ramp down and gradually decreases the stirring speed to increase tap density; the growth stage I-II adopts higher pH to reduce speed and maintains higher stirring rotation speed so as to quickly reach target pH and refine primary grains by matching with oxidization, thereby improving specific surface area.
The nickel-cobalt-manganese ternary precursor provided by the application has the advantages that the specific surface area is large, the tap density is high, primary particles are in a flake shape, secondary particles are loose and porous, the reactivity is higher when the nickel-cobalt-manganese ternary precursor is mixed with a lithium source for sintering to prepare the positive electrode material, the sintering can be performed at a lower sintering temperature, the Li/Ni mixing degree of the obtained positive electrode active material is lower, the specific surface area is larger, and the cycle performance and the multiplying power performance of the positive electrode material can be remarkably improved.
The application provides application of a nickel-cobalt-manganese ternary precursor with high specific surface area in preparation of a nickel-cobalt-lithium manganate ternary positive electrode material.
The present invention is further illustrated by the following specific examples.
Raw material preparation
Mixing metal salt solution: mixing and dissolving nickel sulfate, cobalt sulfate and manganese sulfate in deionized water according to the molar ratio of 6:2:2, and preparing a mixed metal salt solution with the mass concentration of total metal ions of 100 g/L.
Example 1
The preparation method of the nickel-cobalt-manganese ternary precursor with high specific surface area comprises the following steps:
S1, adding 20L of pure water into a 100L reaction kettle, adding alkali liquor and ammonia water to prepare a reaction base solution with pH of 11.6 and ammonia concentration of 6g/L, and introducing nitrogen. Adding a mixed metal salt solution according to the flow rate of 3L/h, synchronously adding a 30% sodium hydroxide solution and a 15% ammonia solution, adjusting the flow rates of the sodium hydroxide solution and the ammonia water, controlling the pH value in a reaction kettle to be maintained at 11.6+/-0.2, the ammonia concentration to be maintained at 6+/-0.5 g/L, controlling the stirring rotating speed to be 550r/min, performing coprecipitation reaction at the reaction temperature of 60 ℃, and maintaining nucleation for 4h to obtain a first slurry containing seed crystals, wherein the D50 is about 2 mu m;
S2, continuously introducing nitrogen into the reaction kettle in the step S1, reducing the feeding flow of the sodium hydroxide solution, gradually reducing the pH value in the first slurry to 10.6, stirring, and performing an I-stage growth reaction to obtain second slurry containing I-stage crystal grains until the D50 of the I-stage crystal grains reaches 7 mu m; the rate of pH decrease in step S2 was 0.05/h, D50 reached 3 μm and started to decrease the stirring speed by 30rpm per 1 μm increase, i.e., 3 μm-520rpm, 4 μm-490rpm, 5 μm-460rpm, 6 μm-430rpm and 7 μm-400 rpm.
S3, in the reaction kettle in the step S2, the introduced nitrogen is switched into a mixed gas of air and nitrogen containing 2% of oxygen, the feeding flow rate of a sodium hydroxide solution is reduced, the pH value in the second slurry is reduced to 10.2, the II-stage growth reaction is carried out until the D50 of the crystal grains reaches 10 mu m, and the feeding is stopped, so that the second slurry containing the II-stage crystal grains is obtained. In the step S3, the flow rate of the mixed gas was 120L/h, the pH value was lowered at 0.15/h, and the stirring speed was maintained at 400rpm. And (3) carrying out solid-liquid separation on the second slurry, and washing and drying a solid product to obtain a nickel-cobalt-manganese ternary precursor with a high specific surface area, wherein the nickel-cobalt-manganese ternary precursor is a Ni 0.6Co0.2Mn0.2(OH)2 precursor. FIG. 1 is an SEM image of a Ni 0.6Co0.2Mn0.2(OH)2 precursor of the present example; fig. 2 is an XRD pattern of the Ni 0.6Co0.2Mn0.2(OH)2 precursor of this example.
Example 2
A preparation method of a nickel-cobalt-manganese ternary precursor with high specific surface area is the same as that of the embodiment 1 except that the pH value in the step S2 is reduced at a rate of 0.1/h and the stirring speed is reduced at a rate of 50rpm/h; the rate of pH decrease in step S3 was 0.1/h.
Example 3
A preparation method of a nickel-cobalt-manganese ternary precursor with high specific surface area is the same as in example 1, except that the pH value of step S1 is 12.5, the pH value of step S2 is 11.2, and the pH value of step S3 is 10.6.
Comparative example 1
The preparation method of the nickel-cobalt-manganese ternary precursor with high specific surface area is the same as that of the embodiment 1 except that in the step S3, the mixed gas containing 2% of oxygen is replaced by introducing nitrogen. Fig. 3 is an SEM image of the precursor of the present comparative example Ni 0.6Co0.2Mn0.2(OH)2.
Comparative example 2
The preparation method of the nickel-cobalt-manganese ternary precursor with high specific surface area is the same as that of the embodiment 1 except that the nitrogen gas introduced in the step S1 and the step S2 is changed into the mixed gas containing 2% of oxygen as in the step S3. Fig. 4 is an XRD pattern of the Ni 0.6Co0.2Mn0.2(OH)2 precursor of this example.
Comparative example 3
The preparation method of the nickel-cobalt-manganese ternary precursor with high specific surface area is the same as that of the embodiment 1 except that the nitrogen introduced in the step S2 is changed into the same mixed gas containing 2% of oxygen as that in the step S3.
Comparative example 4
A method for preparing a nickel cobalt manganese ternary precursor with a high specific surface area, which is otherwise the same as example 1, except that the pH in step S3 is maintained the same as the pH in step S2.
Comparative example 5
A preparation method of a nickel-cobalt-manganese ternary precursor with high specific surface area, which is otherwise the same as that of example 1, except that the stirring speed in step S3 is maintained at the same speed reduction as that in step S2 until the reaction is completed.
Comparative example 6
The preparation method of the nickel-cobalt-manganese ternary precursor with high specific surface area is the same as that of the embodiment 1 except that in the step S3, the mixed gas containing 2% of oxygen is replaced by introducing nitrogen; in step S3, the pH is maintained the same as in step S2.
Comparative example 7
The preparation method of the nickel-cobalt-manganese ternary precursor with high specific surface area is the same as that of the embodiment 1 except that in the step S3, the mixed gas containing 2% of oxygen is replaced by introducing nitrogen; in step S3, the stirring speed is maintained at the same speed as in step S2 until the reaction is completed.
Comparative example 8
A preparation method of a nickel-cobalt-manganese ternary precursor with high specific surface area is the same as that of the embodiment 1, except that the step S3 is started when the D50 of the I-stage crystal grain of the step S2 reaches 4 mu m, and the feeding is stopped until the D50 of the crystal grain reaches 10 mu m.
Comparative example 9
A method for preparing a nickel cobalt manganese ternary precursor with high specific surface area, which is otherwise the same as example 1, except that the pH value in the first slurry is reduced by 0.4, i.e., the pH value is reduced to 11.2; the pH in the second slurry was reduced by 1.0, i.e. to a pH of 10.2.
Testing and application
The precursor materials obtained in the examples and comparative examples were subjected to D50, TD, AD, BET tests in which:
d50, representing 50% of the particle size of the particles, tested using a malvern 3000 particle sizer;
TD/AD, wherein the larger the value is, the higher the density of the precursor is, the more compact the filling between particles is, and the measurement is carried out by adopting a Shenzhen Sanuo JZ-1 type tap density measuring instrument;
BET: the larger the specific surface area, the higher the porosity of the particles, and the measurement is carried out by adopting a An Dongpa Nova 800 type specific surface analyzer.
Impurity content: the method is characterized in that the larger the numerical value is, the more the impurity phases are, the poor structural nonuniformity of the precursor is, the measurement is carried out by using a Rigaku MiniFlex600 type X-ray diffractometer, the testing angle is 5-90 degrees, the testing speed is2 degrees/min, and the testing step length is 0.01 degree.
Table 1 test results
As can be seen from the data in Table 1, examples 1-3 of the present invention all have a high specific surface area (BET >14m 2/g) and very low impurity content while maintaining a high tap density (TD >1.85g/cm 3).
Compared with the example 1, the comparative example 1 is not oxidized by the whole nitrogen gas, the tap density is greatly improved but the specific surface area is greatly reduced, and the SEM pictures (shown in figures 1 and 3) also show that the primary grains of the comparative example 1 are thicker and very dense among grains, which is mainly that the oxidation can destroy the combination between precursor layers, the growth of the primary grains in the thickness direction is inhibited, and the comparative example 1 lacks oxidation, so that the primary grains become thicker and continuously fill gaps among the grains to be dense;
Compared with the example 1, the comparative example 2 is filled with oxygen-containing atmosphere in the whole process, the specific surface area is obviously increased, but the tap density is sharply reduced, and the impurity content is obviously increased, because the damage effect of oxidation on the combination between precursor layers is obviously inhibited, and meanwhile, because the oxidation is introduced when particles are very small, hetero phases such as MnOOH or MnO 2 and the like are easy to form (the peaks of the hetero phases can be seen in comparison with fig. 2 and 4 and fig. 4), serious structural non-uniformity is caused, and the electrochemical performance of the positive electrode material is not favorably exerted. In comparative example 3, nitrogen is introduced only in the step S1, and an oxygen-containing mixed gas is introduced in the steps S2 and S3, wherein the oxidation degree is slightly lower than that of comparative example 2, so that the tap density is slightly higher than that of comparative example 2, and the specific surface area is slightly lower than that of comparative example 2;
Compared with example 1, the pH of comparative example 4 is not further reduced in the process of the growth stage I-growth stage II, the tap density is slightly increased, and the specific surface area is obviously reduced, because in the oxygen-containing atmosphere of the growth stage II, the pH reduction can further reduce the precipitation rate and inhibit the growth of primary grains in the thickness direction, so that the pH of comparative example 4 in the growth stage II is slightly higher, the thickness of the primary grains is properly increased, and the specific surface area is not increased;
Compared with example 1, in comparative example 5, the stirring rotation speed is continuously reduced in the growth stage II, the tap density is slightly increased, and the specific surface area is obviously reduced, because in the oxygen-containing atmosphere in the growth stage II, the lower rotation speed is favorable for the further attachment and growth of solute on primary grains and promotes the growth of the primary grains along the thickness direction, so that the tap density of comparative example 5 is slightly increased, and the specific surface area is obviously reduced; meanwhile, the tap density is slightly lower than that of comparative example 4, and the specific surface area is slightly higher than that of comparative example 4, which shows that maintaining higher pH is easier to improve the tap density and reduce the specific surface area;
Compared to example 1, comparative example 6 had nitrogen gas fully purged while not further lowering pH during growth stage II, tap density: example 1< comparative example 4< comparative example 6, specific surface area: comparative example 6< comparative example 4< example 1, structural uniformity: example 1 ≡ comparative example 4< comparative example 6. This is because the oxygen-containing atmosphere is not introduced to oxidize and maintain a higher pH in the growth stage II, and the synergistic effect of the oxygen-containing atmosphere and the pH greatly promotes the growth of primary grains in the thickness direction, so that the tap density of comparative example 6 is remarkably increased and the specific surface area is remarkably reduced compared with that of example 1;
Compared with example 1, comparative example 7 was fully purged with nitrogen while continuing to decrease the stirring speed during growth phase II, its tap density: example 1< comparative example 5< comparative example 7, specific surface area: comparative example 7< comparative example 5< example 1, structural uniformity: example 1-comparative example 5< comparative example 7. This is because the oxygen-containing atmosphere is not introduced to oxidize and maintain a higher pH in the growth stage II, and the synergistic effect of the oxygen-containing atmosphere and the pH greatly promotes the growth of primary grains in the thickness direction, so that the tap density of comparative example 6 is remarkably increased and the specific surface area is remarkably reduced compared with that of example 1;
Compared with example 1, comparative example 8 completes the reaction of the growth stage I at a lower particle diameter, enters the reaction of the growth stage II and is oxidized by introducing oxygen-containing atmosphere, the tap density is obviously reduced, the specific surface area is slightly increased, and the structural uniformity is poor, because oxidation at a smaller particle diameter can lead to serious oxidation, inhibit the growth of primary grains in the thickness direction, reduce the tap density, improve the specific surface area and simultaneously lead to the appearance of impurity phases such as MnOOH or MnO 2;
The tap density of comparative example 9 was slightly lower and the specific surface area was slightly higher than in example 1, because growth was carried out while maintaining a higher pH in the growth stage I, accompanied by proper nucleation of small particles, and the particle size distribution was wider than in example 1. This portion of the primary grains of the particles having the smaller particle diameter is further inhibited from growing in the growth stage II, thus resulting in a decrease in the tap density of the whole and a slight increase in the specific surface area.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention.
Claims (10)
1. The preparation method of the nickel-cobalt-manganese ternary precursor with the high specific surface area is characterized by comprising the following steps of:
s1, under an inert atmosphere, flowing a mixed metal salt solution containing nickel, cobalt and manganese, strong alkali solution and ammonia water into a bottom solution of a reaction kettle, carrying out a nucleation stage reaction in a coprecipitation process, and maintaining stirring to obtain a first slurry containing seed crystals;
S2, reducing the pH value in the first slurry by 1.0-2.0 in an inert atmosphere, and performing an I-stage growth reaction to obtain a second slurry containing I-stage grains;
S3, reducing the pH value in the second slurry by 0.4-0.6 in an oxygen-containing atmosphere, maintaining stirring, and carrying out II-stage growth reaction to obtain second slurry containing II-stage crystal grains, wherein the II-stage crystal grains are nickel-cobalt-manganese ternary precursors with high specific surface areas;
the D50 of the I-stage crystal grain is 1/2-4/5 of the D50 of the II-stage crystal grain.
2. The method for preparing a nickel-cobalt-manganese ternary precursor with high specific surface area according to claim 1, wherein the concentration of ammonia water in the steps S1-S3 is kept unchanged.
3. The method for preparing a nickel-cobalt-manganese ternary precursor having a high specific surface area according to claim 1, wherein the stirring speed in the step S3 is adjusted at a speed of 20 to 50rpm per 1 μm increase in D50 of the I-stage crystal grains.
4. The method for preparing a nickel-cobalt-manganese ternary precursor with a high specific surface area according to claim 1, wherein the size of the grains D50 of the II-stage is 6-18 μm.
5. The method for preparing a nickel-cobalt-manganese ternary precursor with a high specific surface area according to claim 1, wherein in the step S3, the mass ratio of oxygen in the oxygen-containing atmosphere is 2-10%.
6. The method for preparing a nickel-cobalt-manganese ternary precursor with high specific surface area according to claim 1, wherein in the mixed metal salt solution containing nickel, cobalt and manganese, the molar ratio of a nickel source to a cobalt source to a manganese source is (1-x-y): x: y, wherein x+y is more than or equal to 0.02 and less than or equal to 0.67.
7. The method for preparing a nickel-cobalt-manganese ternary precursor with high specific surface area according to claim 1, wherein in the step S1, the temperature of the coprecipitation reaction is 40-80 ℃.
8. The method for preparing a nickel-cobalt-manganese ternary precursor with a high specific surface area according to claim 1, wherein the rate of pH reduction in step S2 is (0.04-0.1)/h, and the rate of pH reduction in step S3 is (0.1-0.2)/h.
9. A high specific surface area nickel cobalt manganese ternary precursor obtained by the method of any one of claims 1-8.
10. Use of the high specific surface area nickel cobalt manganese ternary precursor according to claim 9 in the preparation of nickel cobalt lithium manganate ternary cathode materials.
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