CN115745019A - Porous high-specific-surface-ratio nickel-cobalt-manganese ternary precursor and preparation method and application thereof - Google Patents
Porous high-specific-surface-ratio nickel-cobalt-manganese ternary precursor and preparation method and application thereof Download PDFInfo
- Publication number
- CN115745019A CN115745019A CN202211410684.3A CN202211410684A CN115745019A CN 115745019 A CN115745019 A CN 115745019A CN 202211410684 A CN202211410684 A CN 202211410684A CN 115745019 A CN115745019 A CN 115745019A
- Authority
- CN
- China
- Prior art keywords
- cobalt
- nickel
- manganese ternary
- ternary precursor
- porous high
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002243 precursor Substances 0.000 title claims abstract description 80
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 14
- 239000011572 manganese Substances 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 88
- 239000000243 solution Substances 0.000 claims description 57
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 239000002245 particle Substances 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- -1 ammonium ions Chemical class 0.000 claims description 16
- 239000012266 salt solution Substances 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 238000000975 co-precipitation Methods 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000011164 primary particle Substances 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000011163 secondary particle Substances 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- 239000008139 complexing agent Substances 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 238000005054 agglomeration Methods 0.000 claims description 2
- 230000002776 aggregation Effects 0.000 claims description 2
- 239000007774 positive electrode material Substances 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 239000002585 base Substances 0.000 description 15
- 238000010517 secondary reaction Methods 0.000 description 13
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 102220043159 rs587780996 Human genes 0.000 description 9
- 239000010406 cathode material Substances 0.000 description 8
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 6
- 229910001429 cobalt ion Inorganic materials 0.000 description 6
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 6
- 229910001437 manganese ion Inorganic materials 0.000 description 6
- 229910001453 nickel ion Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229940044175 cobalt sulfate Drugs 0.000 description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 229940099596 manganese sulfate Drugs 0.000 description 4
- 239000011702 manganese sulphate Substances 0.000 description 4
- 235000007079 manganese sulphate Nutrition 0.000 description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229940053662 nickel sulfate Drugs 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 150000001868 cobalt Chemical class 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 150000002696 manganese Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 150000002815 nickel Chemical class 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 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
- 239000013256 coordination polymer Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of lithium ion batteries, in particular to a porous high-specific surface nickel-cobalt-manganese ternary precursor and a preparation method and application thereof. The chemical formula of the porous high-specific-surface-ratio nickel-cobalt-manganese ternary precursor is Ni x Co y Mn z (OH) 2 (ii) a Wherein, 0.30<x<0.40，0.35<y<0.40，0.30<z<0.35, and x + y + z =1; the specific surface area of the porous high-specific-surface-ratio nickel-cobalt-manganese ternary precursor is 18-30 m 2 (ii) in terms of/g. The device isThe porous high specific surface nickel cobalt manganese ternary precursor is loose and porous and has high specific surface, and has excellent rate capability and cycle performance.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a porous high-specific surface nickel-cobalt-manganese ternary precursor and a preparation method and application thereof.
Background
In recent years, the new energy lithium battery industry has been developed rapidly, and especially, ternary materials have been developed and paid attention to. Mainly due to the advantages of high capacity, good cyclicity, good rate capability and the like. The ternary precursor, which is the upper core material of the ternary cathode material, has a significant influence on the performance of the cathode material, for example, because the contact surface of the precursor with a lower specific surface for reacting with a lithium source is smaller and the activity is lower, the obtained cathode material cannot meet the requirements of the relevant charge-discharge rate performance.
At present, the preparation of the precursor generally adopts wet synthesis, namely a coprecipitation method: the sulfate, chloride or nitrate of nickel, cobalt and manganese is used as the raw material of the metal liquid, sodium hydroxide solution or sodium carbonate solution is used as a precipitator, ammonia water and the like are used as complexing agents, and then the purpose of coprecipitation is achieved.
For example, patent CN113735191A discloses a ternary precursor with a porous structure and a preparation method thereof, wherein a coprecipitation method is adopted, a certain amount of small lithium carbonate particles are prepared first, and then part of the small lithium carbonate particles are wrapped in the ternary precursor in the growth process; and introducing carbon dioxide, adjusting the pH value to generate lithium bicarbonate which is easily dissolved in water, and dissolving lithium carbonate to enable the interior of the ternary precursor to generate a porous structure so as to obtain a corresponding precursor product.
However, the patent of the invention has many processes and complicated process control, the obtained primary particles are 5-10 nm thick, the hollow periphery inside the primary particles is compact, and the prepared precursor is relatively lower than the precursor (BET =17.15 m) 2 /g) which is not favorable for the contact of the sintered ternary cathode material with the electrolyte, resulting in the reduction of lithium ion transmission efficiency and rate capability.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a porous high-specific-surface-ratio nickel-cobalt-manganese ternary precursor which has the advantages of high specific surface area, looseness, porosity and the like, so that the lithium ion transmission efficiency and the rate capability are improved.
The second purpose of the invention is to provide a preparation method of the porous high specific surface nickel cobalt manganese ternary precursor, which has the advantages of simple process, short flow, easiness in control, loose porosity and high specific surface area of the prepared porous high specific surface nickel cobalt manganese ternary precursor, and the like.
The third purpose of the invention is to provide a lithium ion battery anode material.
The fourth object of the invention is to provide a positive pole piece.
A fifth object of the present invention is to provide a lithium ion battery.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
in a first aspect, the invention provides a porous high specific surface nickel cobalt manganese ternary precursor, wherein the chemical formula of the porous high specific surface nickel cobalt manganese ternary precursor is Ni x Co y Mn z (OH) 2 。
Wherein 0.30 yarn-over x yarn-over 0.40,0.35 yarn-over y yarn-over 0.40,0.30 yarn-over z yarn-over 0.35, and x + y + z =1.
X in the above formula includes, but is not limited to, a point value of any one of 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, or a range value between any two. Y in the above formula includes, but is not limited to, a point value of any one of 0.36, 0.37, 0.38, 0.39, or a range value between any two. Z in the above formula includes, but is not limited to, a point value of any one of 0.31, 0.32, 0.33, 0.34, or a range of values between any two.
The specific surface area of the porous high-specific-surface-ratio nickel-cobalt-manganese ternary precursor is 18-30 m 2 G, including but not limited to 19m 2 /g、20m 2 /g、21m 2 /g、22m 2 /g、23m 2 /g、24m 2 /g、25m 2 /g、26m 2 /g、27m 2 /g、28m 2 /g、29m 2 A point value of any one of/g or a range value between any two.
The porous high specific surface nickel cobalt manganese ternary precursor provided by the invention is loose and porous, has high specific surface, and can solve the problem that active sites are less in reaction with a lithium source in a sintering process, so that a cathode material with better rate capability and cycle performance is obtained.
The loose and porous shape is beneficial to the infiltration (soaking) of electrolyte, so that the lithium ion transmission channel is shortened.
Preferably, the porous high ratio epi-ni-co-mn ternary precursor includes porous secondary particles formed by cross-arrangement and agglomeration of primary particles. Wherein the shape of the primary particles comprises a flake shape, the thickness of the primary particles is 1-2 nm, including but not limited to the values of any one of 1.1nm, 1.2nm, 1.3nm, 1.4nm, 1.5nm, 1.6nm, 1.7nm, 1.8nm, 1.9nm, or ranges between any two.
The primary particles prepared by the method are thin and flaky, so that the material ratio can be effectively improved, the reaction sites in the sintering process are increased, the preparation of the single crystal material is facilitated, and the rate capability and the cycle performance of the material are improved.
In some specific embodiments of the invention, the length of the primary particles is 15 to 40nm, including but not limited to values of any one of 17nm, 19nm, 20nm, 23nm, 25nm, 28nm, 30nm, 33nm, 35nm, 38nm, or ranges between any two.
Preferably, the shape of the secondary particles comprises spherical and/or spheroidal, the secondary particles having a D50 particle diameter of 3 to 5 μm, including but not limited to any one of 3.2 μm, 3.5 μm, 3.8 μm, 4 μm, 4.2 μm, 4.5 μm, 4.8 μm, or a range between any two.
In a second aspect, the invention provides a preparation method of the porous high-ratio epi-nickel cobalt manganese ternary precursor, which comprises the following steps:
under inert atmosphere, adding a nickel-cobalt-manganese ternary salt solution, a precipitator solution and a complexing agent solution into a reaction container containing a base solution to carry out coprecipitation reaction;
when the D50 particle diameter of the particles within the reaction vessel =1.5 to 2.5 μm (including but not limited to the point of any one of 1.6 μm, 1.7 μm, 1.8 μm, 1.9 μm, 2.0 μm, 2.1 μm, 2.2 μm, 2.3 μm, 2.4 μm or the range between any two), passing an oxygen-containing gas such that the volume fraction of oxygen in the reaction vessel is 3% to 10% (including but not limited to the point of any one of 4%, 5%, 6%, 7%, 8%, 9% or the range between any two).
In some embodiments of the invention, the oxygen-containing gas comprises air and/or oxygen, preferably air, the amount of which is more easily controlled.
And when the particles in the reaction container reach the target particle size, stopping the reaction and stopping introducing air, and then sequentially carrying out solid-liquid separation, drying, sieving and demagnetizing to obtain the porous high-ratio surface nickel-cobalt-manganese ternary precursor. When the particles in the reaction container reach the target particle size, stopping introducing air so as to avoid the problems of unsatisfactory appearance, over-thinness, delamination, deformation and the like, and avoid overlarge specific surface caused by over-oxidation.
The preparation method of the porous high-specific-surface-ratio nickel-cobalt-manganese ternary precursor provided by the invention is short in flow, simple to operate and easy to control, and the prepared secondary particles are loose and porous by introducing specific amount of air in a specific particle size range, so that the specific surface of the precursor can be better improved, the problem that active sites are few in reaction with a lithium source in a sintering process is further solved, and the cathode material with high rate capability and better cycle performance is obtained.
Preferably, the molar concentration of metal ions in the nickel-cobalt-manganese ternary salt solution is 1-2.5 mol/L; including but not limited to any one of 1.2mol/L, 1.5mol/L, 1.8mol/L, 2.0mol/L, 2.3mol/L or a range between any two.
In some embodiments of the invention, the metal ions in the nickel cobalt manganese ternary salt solution include nickel ions, cobalt ions, and manganese ions. Wherein the nickel ions are mainly provided by soluble nickel salts, such as nickel sulfate, nickel nitrate, etc., but not limited thereto; the cobalt ions are provided primarily by soluble cobalt salts, such as, but not limited to, cobalt sulfate, cobalt nitrate, and the like; the manganese ions are mainly provided by soluble manganese salts such as manganese sulfate, manganese nitrate, and the like, but are not limited thereto.
In some specific embodiments of the present invention, the molar ratio of nickel ions, cobalt ions and manganese ions in the nickel-cobalt-manganese ternary salt solution is x: y: z, wherein 0.30 yarn-over x yarn-over 0.40,0.35 yarn-over y yarn-over 0.40,0.30 yarn-over z yarn-over 0.35, and x + y + z =1.
In some embodiments of the present invention, the preparation method of the nickel-cobalt-manganese ternary salt solution comprises: according to the mol proportion and the required mol concentration of the nickel element, the cobalt element and the manganese element in the nickel-cobalt-manganese ternary precursor with the required porous high ratio, respectively weighing soluble nickel salt, soluble cobalt salt and soluble manganese salt, and dissolving the soluble nickel salt, the soluble cobalt salt and the soluble manganese salt in water to obtain the nickel-cobalt-manganese ternary salt solution.
Preferably, the precipitant solution comprises at least one of a sodium hydroxide solution, a potassium hydroxide solution, a sodium carbonate solution, and a potassium carbonate solution; more preferably, the molar concentration of the precipitant solution is 8-15 mol/L; including but not limited to any one of 9, 10, 11, 12, 13, 14mol/L or a range of values therebetween.
Preferably, the complexing agent solution comprises ammonia; more preferably, the mass concentration of ammonium ions in the ammonia water is 150-200 g/L, including but not limited to any one of 155g/L, 160g/L, 165g/L, 170g/L, 175g/L, 180g/L, 185g/L, 190g/L, 195g/L, or a range between any two.
In some embodiments of the invention, the inert atmosphere comprises a nitrogen atmosphere and/or an argon atmosphere.
Preferably, the mass concentration of ammonium ions in the base solution is 4-5 g/L; including but not limited to, a point value of any one of 4.2g/L, 4.4g/L, 4.5g/L, 4.7g/L, 4.9g/L, or a range of values therebetween.
In some embodiments of the present invention, the base solution is mainly prepared from a complexing agent solution, an alkaline compound and deionized water. Wherein the alkaline compound comprises at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
Preferably, the pH of the base solution is between 11.5 and 12.5, including but not limited to any of 11.7, 11.9, 12.0, 12.2, 12.4, or a range between any two.
The temperature of the base solution is 50-60 ℃, including but not limited to any one of 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃ and 59 ℃, or a range between any two.
Preferably, in the process of the coprecipitation reaction, the mass concentration of ammonium ions in the mixed material is 4-5 g/L; including but not limited to, any of 4.2g/L, 4.4g/L, 4.5g/L, 4.7g/L, 4.9g/L, or a range of values therebetween.
Preferably, during the co-precipitation reaction, the temperature of the mixed material is 50 to 60 ℃, including but not limited to any one of 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃, 59 ℃ or a range between any two.
In some embodiments of the present invention, the mixture is stirred at 200-300 rpm during the coprecipitation reaction.
In some embodiments of the invention, the inert atmosphere has a gas flow rate of 300 to 600L/h, including but not limited to any one of 350L/h, 400L/h, 450L/h, 500L/h, 550L/h or a range between any two.
Preferably, during the co-precipitation reaction, the pH of the mixed mass is between 10.5 and 12.5, including but not limited to any one of 10.7, 10.9, 11, 11.2, 11.4, 11.5, 11.7, 11.9, 12, 12.2, 12.4 or a range between any two.
In some specific embodiments of the invention, after the nickel-cobalt-manganese ternary salt solution, the precipitant solution and the complexing agent solution are added into the reaction vessel containing the base solution, the pH of the mixed material is 11.5-12.5, then the reaction is carried out for 30-60 min, and then the pH of the mixed material is 10.5-11.0. This facilitates the growth of the seed.
In some specific embodiments of the present invention, the coprecipitation reaction is performed in a reaction vessel, and the reaction vessel comprises a main reaction vessel and a secondary reaction vessel which are communicated with each other. After reacting for a period of time, when the liquid level of the main reaction kettle reaches an overflow port, starting the main reaction kettle to overflow to the secondary reaction kettle, and starting a main circulation and a secondary circulation (carrying out coprecipitation reaction by adopting an intermittent method) in the period, wherein the gas flow of the inert atmosphere of the main reaction kettle and the inert atmosphere of the secondary reaction kettle are kept between 300 and 600L/h. Wherein, the main reaction kettle is mainly used for main reaction, the secondary reaction kettle is mainly used for aging, and the overflow is carried out primary and secondary circulation, so that the uniform distribution of materials and uniform granularity can be ensured.
In some specific embodiments of the invention, the target particle size is D50=3 to 5 μm, including but not limited to any one of 3.2 μm, 3.5 μm, 3.8 μm, 4 μm, 4.2 μm, 4.5 μm, 4.8 μm, or a range between any two.
In some embodiments of the invention, the reaction system is maintained under an inert atmosphere during the period of stopping the reaction and stopping the introduction of air.
In some specific embodiments of the present invention, after the solid-liquid separation and before the drying, the method further comprises the steps of washing with a sodium hydroxide solution with a mass concentration of 50 to 100g/L, and then washing with pure water at a temperature of 60 to 80 ℃ for 2 to 3 times, wherein the washing time is 60 to 120min.
In some embodiments of the present invention, the drying temperature is 120 to 150 ℃ and the drying time is 5 to 10 hours.
In a third aspect, the invention provides a lithium ion battery cathode material, which is mainly prepared from the porous high-ratio nickel-cobalt-manganese ternary precursor or the porous high-ratio nickel-cobalt-manganese ternary precursor prepared by the preparation method of the porous high-ratio nickel-cobalt-manganese ternary precursor.
In a fourth aspect, the invention provides a positive electrode plate, which is mainly made of the above lithium ion battery positive electrode material.
In a fifth aspect, the invention provides a lithium ion battery, which includes the positive electrode plate described above.
The lithium ion battery has excellent electrochemical performance, particularly high rate performance and good cycle performance.
Compared with the prior art, the invention has the beneficial effects that:
(1) The porous high specific surface nickel cobalt manganese ternary precursor provided by the invention is loose, porous and high in specific surface, and the rate capability and the cyclicity are improved.
(2) The preparation method of the porous high-specific-surface-ratio nickel-cobalt-manganese ternary precursor has the advantages of short flow, simplicity in operation, easiness in control and the like.
(3) According to the preparation method of the porous high-ratio nickel-cobalt-manganese ternary precursor, the specific amount of air is introduced in the specific particle size range, so that the prepared secondary particles are loose and porous, the precursor ratio can be better improved, the problem that active sites are few in reaction with a lithium source in the sintering process is solved, and the cathode material with high rate capability and good cycle performance can be obtained.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is an SEM image of 5000 times magnification of a porous high ratio nickel cobalt manganese ternary precursor provided in example 1 of the present invention;
fig. 2 is an SEM image of 10000 times magnification of the porous high specific surface nickel cobalt manganese ternary precursor provided in example 1 of the present invention;
fig. 3 is an SEM image of 5000 times magnification of the porous high specific surface nickel cobalt manganese ternary precursor provided in example 2 of the present invention;
fig. 4 is an SEM image of 10000 times magnification of the porous high specific surface nickel cobalt manganese ternary precursor provided in example 2 of the present invention;
fig. 5 is an SEM image of 5000 times magnification of the porous high specific surface nickel cobalt manganese ternary precursor provided in example 3 of the present invention;
fig. 6 is an SEM image of 10000 times magnification of the porous high specific surface nickel cobalt manganese ternary precursor provided in example 3 of the present invention;
FIG. 7 is a sectional CP-SEM image of a porous high specific surface nickel cobalt manganese ternary precursor with magnification of 5000 times provided in example 3 of the present invention;
fig. 8 is a cross-sectional CP-SEM image of 10000 times magnification of the porous high ratio epi-ni-co-mn ternary precursor provided in example 3 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The embodiment provides a preparation method of a porous high-ratio nickel-cobalt-manganese ternary precursor, which comprises the following steps:
(1) Preparing nickel-cobalt-manganese ternary salt solution with total metal ion concentration of 2mol/L (120 g/L) by using nickel sulfate, cobalt sulfate and manganese sulfate, wherein the molar ratio of nickel ions to cobalt ions to manganese ions is 0.325:0.365:0.31. and preparing a sodium hydroxide solution with the concentration of 10mol/L and preparing ammonia water with the mass concentration of ammonium ions of 180 g/L.
(2) And introducing nitrogen into the sealed main reaction kettle and the sealed secondary reaction kettle, wherein the flow rate is 500L/h, and the introduction time is 5h. During the process, 200L of deionized water is added into the main reaction kettle to immerse the middle layer and stir, the stirring is started at 270rpm, and the reaction temperature (the temperature of materials in the main reaction kettle) is controlled at 60 ℃.
(3) Adding ammonia water into the main reaction kettle to prepare a base solution, controlling the mass concentration of ammonium ions in the base solution to be 5.0g/L, and adding alkali liquor (sodium hydroxide solution) to adjust the pH =12.5 of the base solution.
(4) And simultaneously adding the nickel-cobalt-manganese ternary salt solution, the sodium hydroxide solution and ammonia water into the main reaction kettle. During the reaction, the pH of the system (the material in the main reaction kettle) is maintained to be 12.5, the mass concentration of ammonium ions is 5.0g/L, the nitrogen gas is introduced at a flow rate of 500L/h, and the reaction time of the stage is 60min. The pH of the system (contents of the main reactor) was then lowered to 11.0 to allow further particle growth.
After reacting for a certain time, when the liquid level of the main reaction kettle reaches the overflow port, starting the main reaction kettle to overflow to the secondary reaction kettle, and starting the main circulation and the secondary circulation in the period, wherein the flow rates of the nitrogen introduced into the main reaction kettle and the secondary reaction kettle are both 500L/h.
(5) When the particle size of the particles in the main reaction kettle reaches D50=2.5 μm, air is introduced into the main reaction kettle, so that the volume fraction of oxygen in the main reaction kettle is controlled at 4.8%.
Stopping discharging when the particles in the main reaction kettle react to the granularity D50=3.0 μm, and stopping introducing air.
(6) After solid-liquid separation, the slurry after the reaction was washed 2 times with a sodium hydroxide solution having a concentration of 60g/L, and then washed 3 times with pure water at 70 ℃.
(7) Drying the washed ternary precursor filter cake in an oven at 130 ℃ for 5h, sieving and demagnetizing after the moisture is qualified to obtain the porous high-specific surface nickel-cobalt-manganese ternary precursor, and detecting that the BET of the porous high-specific surface nickel-cobalt-manganese ternary precursor is 20.73m 2/ g。
SEM images of the porous high ratio epi-ni-co-mn ternary precursor prepared in this example at different magnifications are shown in fig. 1 and 2. In fig. 1, the magnification is 5000 times. The magnification of fig. 2 is 10000 times.
Example 2
The preparation method of the porous high-ratio epi-nickel cobalt manganese ternary precursor provided by the embodiment comprises the following steps:
(1) Preparing nickel-cobalt-manganese ternary salt solution with total metal ion concentration of 2mol/L (120 g/L) by using nickel sulfate, cobalt sulfate and manganese sulfate, wherein the molar ratio of nickel ions to cobalt ions to manganese ions is 0.325:0.365:0.31. and preparing a sodium hydroxide solution with the concentration of 10mol/L and preparing ammonia water with the mass concentration of ammonium ions of 180 g/L.
(2) And introducing nitrogen into the sealed main reaction kettle and the sealed secondary reaction kettle, wherein the flow rate is 500L/h, and the introduction time is 5h. During the period, deionized water is added to the reactor to be stirred to submerge the middle layer, the stirring is started to be 250rpm, and the reaction temperature (the temperature of materials in the main reaction kettle) is controlled to be 50 ℃.
(3) Adding ammonia water into the main reaction kettle to prepare a base solution, controlling the mass concentration of ammonium ions in the base solution to be 4g/L, and adding an alkali liquor (a sodium hydroxide solution) to adjust the pH of the base solution to be =11.5.
(4) And simultaneously adding the nickel-cobalt-manganese ternary salt solution, the sodium hydroxide solution and ammonia water into the main reaction kettle. During the reaction, the pH of the system (the material in the main reaction kettle) is maintained to be 11.5, the mass concentration of ammonium ions is 4.0g/L, the nitrogen gas is introduced at a flow rate of 500L/h, and the reaction time of the stage is 30min. The pH of the system (contents of the main reactor) was then lowered to 10.5 to allow further particle growth.
After reacting for a certain time, when the liquid level of the main reaction kettle reaches the overflow port, starting the main reaction kettle to overflow to the secondary reaction kettle, and starting the main circulation and the secondary circulation in the period, wherein the flow rates of the nitrogen introduced into the main reaction kettle and the secondary reaction kettle are both 500L/h.
(5) When the particle size in the main reaction kettle is up to D50=1.5 μm, air is introduced into the main reaction kettle, so that the volume fraction of oxygen in the main reaction kettle is controlled at 5.0%.
Stopping discharging when the particles in the main reaction kettle react to the granularity D50=3.1 μm, and stopping introducing air.
(6) After solid-liquid separation, the slurry after the reaction was washed 2 times with a sodium hydroxide solution having a concentration of 60g/L, and then washed 3 times with pure water at 70 ℃.
(7) Drying the washed ternary precursor filter cake in an oven at 130 ℃ for 5h, sieving and demagnetizing after the moisture is qualified to obtain the porous nickel-cobalt-manganese ternary precursor with high specific surface, and detecting that the BET of the porous nickel-cobalt-manganese ternary precursor is 21.25m 2 /g。
SEM images of the porous high ratio epi-ni-co-mn ternary precursor prepared in this example at different magnifications are shown in fig. 3 and 4. In fig. 3, the magnification is 5000 times. The magnification of fig. 4 is 10000 times.
Example 3
The preparation method of the porous high-ratio epi-nickel cobalt manganese ternary precursor provided by the embodiment comprises the following steps:
(1) Preparing a nickel-cobalt-manganese ternary salt solution with the total metal ion concentration of 2mol/L (120 g/L) by using nickel sulfate, cobalt sulfate and manganese sulfate, wherein the molar ratio of nickel ions to cobalt ions to manganese ions is 0.325:0.365:0.31. and preparing a sodium hydroxide solution with the concentration of 10mol/L and preparing ammonia water with the mass concentration of ammonium ions of 180 g/L.
(2) And introducing nitrogen into the sealed main reaction kettle and the sealed secondary reaction kettle at the flow rate of 500L/h for 5h. During the process, deionized water is added to the reaction kettle to stir the mixture in the middle layer, the stirring speed is started to be 250rpm, and the reaction temperature (the temperature of materials in the main reaction kettle) is controlled to be 55 ℃.
(3) Adding ammonia water into the main reaction kettle to prepare a base solution, controlling the mass concentration of ammonium ions in the base solution to be 4.5g/L, and adding alkali liquor (sodium hydroxide solution) to adjust the pH of the base solution to be =12.
(4) And simultaneously adding the nickel-cobalt-manganese ternary salt solution, the sodium hydroxide solution and ammonia water into the main reaction kettle. During the reaction, the pH of the system (the material in the main reaction kettle) is maintained to be 12, the mass concentration of ammonium ions is 4.5g/L, the nitrogen gas introduction flow is 500L/h, and the reaction time of the stage is 45min. The pH of the system (contents of the main reactor) was then lowered to 10.8 to allow further particle growth.
After reacting for a certain time, when the liquid level of the main reaction kettle reaches the overflow port, starting the main reaction kettle to overflow to the secondary reaction kettle, and starting the main circulation and the secondary circulation in the period, wherein the flow rates of the nitrogen introduced into the main reaction kettle and the secondary reaction kettle are both 500L/h.
(5) When the particle size of the particles in the main reaction kettle reaches D50=2 μm, air is introduced into the main reaction kettle, so that the volume fraction of oxygen in the main reaction kettle is controlled to be 5.1%.
Stopping discharging when the particles in the main reaction kettle react to the granularity D50=3.2 μm, and stopping introducing air.
(6) After solid-liquid separation, the slurry after the reaction was washed 2 times with a sodium hydroxide solution having a concentration of 60g/L, and then washed 3 times with pure water having a temperature of 70 ℃.
(7) Drying the washed ternary precursor filter cake in an oven at 130 ℃ for 5h, sieving and demagnetizing after the moisture is qualified to obtain the porous high-specific surface nickel-cobalt-manganese ternary precursor, and detecting that the BET of the porous high-specific surface nickel-cobalt-manganese ternary precursor is 21.81m 2 /g。
As shown in fig. 5 and fig. 6, SEM images of the porous high ratio nickel cobalt manganese ternary precursor prepared in this example under different magnifications are shown. In fig. 5, the magnification is 5000 times. The magnification of fig. 6 is 10000 times.
In order to better observe the internal structure of the secondary agglomerate particles, CP analysis was performed on the porous high ratio epi nickel cobalt manganese ternary precursor prepared in this example. Fig. 7 and 8 are cross-sectional CP-SEM images of the porous high-ratio nickel cobalt manganese ternary precursor prepared in this example. In fig. 7, the magnification is 5000 times. The magnification of fig. 8 is 10000 times.
Comparative example 1
The preparation method of the precursor provided by the comparative example is basically the same as that of example 3, except that in step (5), air is introduced into the main reaction kettle when the particles in the main reaction kettle reach the particle size D50=1.0 μm.
Comparative example 2
The preparation method of the precursor provided in this comparative example is substantially the same as that of example 3, except that in step (5), air is introduced into the main reactor until the particle size in the main reactor reaches D50=4 μm.
Comparative example 3
The precursor provided in this comparative example was prepared in substantially the same manner as in example 3, except that the volume fraction of oxygen in the main reactor was controlled to 1% in step (5).
Comparative example 4
The preparation method of the precursor provided by the comparative example is basically the same as that of example 3, except that in step (5), the volume fraction of oxygen in the main reaction kettle is controlled to be 15%.
Experimental example 1
The key physical and chemical indexes of the precursor prepared by the above examples and various comparative examples are shown in the following table 1.
TABLE 1 Key physicochemical indices of the prepared precursors
It can be seen from the comparison of the experimental data of example 3 and comparative example 1 that in comparative example 1, the oxidation degree of the material is increased and the primary particles are thinner (i.e. the thickness is reduced) due to the advance of the oxygen introduction time, which is larger than the table.
It can be seen from the comparison of the experimental data of example 3 and comparative example 2 that the oxidation degree is insufficient and the primary particle is thicker than that in comparative example 2 due to the delayed time of air introduction.
It can be seen from the comparison of the experimental data of example 3 and comparative example 3 that the oxidation degree is insufficient and the primary particle is thicker than that in comparative example 3 due to the reduced volume fraction of oxygen.
It can be seen from the comparison of the experimental data of example 3 and comparative example 4 that the oxidation is excessive in comparative example 4 due to the excessively high oxygen content, the primary particles are thin and brittle, and the specific surface is excessively high.
While particular embodiments of the present invention have been illustrated and described, it will be appreciated that the above embodiments are merely illustrative of the technical solution of the present invention and are not restrictive; those of ordinary skill in the art will understand that: modifications may be made to the above-described embodiments, or equivalents may be substituted for some or all of the features thereof without departing from the spirit and scope of the present invention; the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention; it is therefore intended to cover in the appended claims all such alternatives and modifications that are within the scope of the invention.
Claims (10)
1. The porous high-specific-surface nickel-cobalt-manganese ternary precursor is characterized by having a chemical formula of Ni x Co y Mn z (OH) 2 ；
Wherein 0.30 yarn-over x yarn-over 0.40,0.35 yarn-over y yarn-over 0.40,0.30 yarn-over z yarn-over 0.35, and x + y + z =1;
the specific surface area of the porous nickel-cobalt-manganese ternary precursor with high specific surface area is 18-30 m 2 /g。
2. The porous high ratio epi nickel cobalt manganese ternary precursor of claim 1, wherein the porous high ratio epi nickel cobalt manganese ternary precursor comprises secondary particles formed by cross arrangement and agglomeration of primary particles; wherein the shape of the primary particles comprises a sheet shape, and the thickness of the primary particles is 1-2 nm;
preferably, the shape of the secondary particles comprises a spherical shape and/or a spheroidal shape, and the D50 particle diameter of the secondary particles is 3 to 5 μm.
3. The method for preparing the porous high-specific-surface-ratio nickel-cobalt-manganese ternary precursor according to claim 1 or 2, comprising the steps of:
under inert atmosphere, adding a nickel-cobalt-manganese ternary salt solution, a precipitator solution and a complexing agent solution into a reaction container containing a base solution to carry out coprecipitation reaction;
when the D50 particle size of the particles in the reaction container is = 1.5-2.5 μm, introducing oxygen-containing gas to make the volume fraction of oxygen in the reaction container be 3% -10%;
and when the particles in the reaction container reach the target particle size, stopping the reaction and stopping introducing air, and then sequentially carrying out solid-liquid separation, drying, sieving and demagnetizing to obtain the porous high-ratio surface nickel-cobalt-manganese ternary precursor.
4. The method for preparing the porous high-specific-surface nickel-cobalt-manganese ternary precursor according to claim 3, wherein the molar concentration of metal ions in the nickel-cobalt-manganese ternary salt solution is 1-2.5 mol/L;
preferably, the precipitant solution comprises at least one of a sodium hydroxide solution, a potassium hydroxide solution, a sodium carbonate solution, and a potassium carbonate solution; more preferably, the molar concentration of the precipitant solution is 8-15 mol/L;
preferably, the complexing agent solution comprises aqueous ammonia; more preferably, the mass concentration of ammonium ions in the ammonia water is 150 to 200g/L.
5. The preparation method of the porous high-specific-ratio nickel-cobalt-manganese ternary precursor according to claim 3, wherein the mass concentration of ammonium ions in the base solution is 4-5 g/L;
preferably, the pH of the base solution is 11.5-12.5, and the temperature of the base solution is 50-60 ℃.
6. The preparation method of the porous high-specific-surface-ratio nickel-cobalt-manganese ternary precursor according to claim 3, wherein in the coprecipitation reaction process, the mass concentration of ammonium ions in the mixed material is 4-5 g/L;
preferably, the temperature of the mixed materials is 50-60 ℃ during the coprecipitation reaction.
7. The method for preparing the porous high-specific-surface-ratio nickel-cobalt-manganese ternary precursor according to claim 3, wherein the pH of the mixed material is 10.5-12.5 during the coprecipitation reaction.
8. The lithium ion battery positive electrode material is mainly prepared from the porous high-ratio nickel-cobalt-manganese ternary precursor as set forth in any one of claims 1 to 2 or the porous high-ratio nickel-cobalt-manganese ternary precursor prepared by the preparation method of the porous high-ratio nickel-cobalt-manganese ternary precursor as set forth in any one of claims 3 to 7.
9. The positive pole piece is mainly prepared from the lithium ion battery positive pole material in claim 8.
10. A lithium ion battery comprising the positive electrode tab of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211410684.3A CN115745019A (en) | 2022-11-11 | 2022-11-11 | Porous high-specific-surface-ratio nickel-cobalt-manganese ternary precursor and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211410684.3A CN115745019A (en) | 2022-11-11 | 2022-11-11 | Porous high-specific-surface-ratio nickel-cobalt-manganese ternary precursor and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115745019A true CN115745019A (en) | 2023-03-07 |
Family
ID=85369431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211410684.3A Pending CN115745019A (en) | 2022-11-11 | 2022-11-11 | Porous high-specific-surface-ratio nickel-cobalt-manganese ternary precursor and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115745019A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107565125A (en) * | 2017-08-25 | 2018-01-09 | 湖南杉杉能源科技股份有限公司 | A kind of high voltage precursor of nickel-cobalt-lithium-manganese-oxide and preparation method thereof and high voltage nickel-cobalt lithium manganate cathode material |
| CN109244431A (en) * | 2018-11-14 | 2019-01-18 | 广东佳纳能源科技有限公司 | Nickel-cobalt-manganternary ternary anode material and its preparation method and application, lithium ion battery, electric car |
| CN113213552A (en) * | 2021-03-20 | 2021-08-06 | 长沙理工大学 | Quasi-spherical porous nickel-cobalt-manganese precursor and preparation method thereof |
| CN113461073A (en) * | 2021-07-01 | 2021-10-01 | 广东佳纳能源科技有限公司 | Ternary precursor and preparation method and application thereof |
-
2022
- 2022-11-11 CN CN202211410684.3A patent/CN115745019A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107565125A (en) * | 2017-08-25 | 2018-01-09 | 湖南杉杉能源科技股份有限公司 | A kind of high voltage precursor of nickel-cobalt-lithium-manganese-oxide and preparation method thereof and high voltage nickel-cobalt lithium manganate cathode material |
| CN109244431A (en) * | 2018-11-14 | 2019-01-18 | 广东佳纳能源科技有限公司 | Nickel-cobalt-manganternary ternary anode material and its preparation method and application, lithium ion battery, electric car |
| CN113213552A (en) * | 2021-03-20 | 2021-08-06 | 长沙理工大学 | Quasi-spherical porous nickel-cobalt-manganese precursor and preparation method thereof |
| CN113461073A (en) * | 2021-07-01 | 2021-10-01 | 广东佳纳能源科技有限公司 | Ternary precursor and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李顶根主编: "《动力机械电子控制技术》", vol. 1, 30 June 2021, 华中科技大学出版社, pages: 197 - 198 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7241875B2 (en) | Cathode material for high-power lithium-ion battery and method for producing the same | |
| US10326133B2 (en) | Methods of making inorganic compounds | |
| WO2019104473A1 (en) | Ternary precursor material and preparation method therefor | |
| KR100639526B1 (en) | 3V spinel complex-oxide as cathode material of lithium secondary batteries, the carbonate precipitation method thereof, and the lithium secondary batteries using the same | |
| US20240150196A1 (en) | Beta-nickel hydroxide doped with aluminum | |
| CN110534737B (en) | High-rate doped nickel-cobalt-manganese ternary material and preparation method thereof | |
| CN110880591A (en) | SiO2Coated lithium ion battery anode precursor material and preparation method thereof | |
| CN116588994B (en) | Sodium ion battery positive electrode precursor, sodium ion battery positive electrode material, preparation method of sodium ion battery positive electrode material and sodium ion battery | |
| CN109461893A (en) | A kind of Olivine-type Cathode Material in Li-ion Batteries and preparation method thereof | |
| CN112349885A (en) | Modified lithium ion battery positive electrode material and preparation method thereof | |
| CN108463911A (en) | The manufacturing method of nonaqueous electrolytic active material for anode of secondary cell presoma, nonaqueous electrolytic active material for anode of secondary cell, the manufacturing method of nonaqueous electrolytic active material for anode of secondary cell presoma and nonaqueous electrolytic active material for anode of secondary cell | |
| CN115124087B (en) | Aluminum-doped cobaltosic oxide, preparation method thereof and lithium cobaltate anode material | |
| CN109768275A (en) | A kind of preparation method for mixing titanium lithium ion anode material presoma | |
| CN115676902A (en) | Al gradient type lithium cobaltate-doped positive electrode material and preparation method thereof | |
| CN116588993B (en) | Ternary precursor, preparation method thereof, lithium battery positive electrode material and lithium battery | |
| WO2023160016A1 (en) | Method for preparing ternary precursor from microbubbles by pre-oxidation and application of ternary precursor | |
| CN115745019A (en) | Porous high-specific-surface-ratio nickel-cobalt-manganese ternary precursor and preparation method and application thereof | |
| CN114497526B (en) | Method for synthesizing ternary positive electrode material | |
| CN115490276A (en) | Surface-modified positive electrode material precursor and preparation method and application thereof | |
| CN114715956A (en) | Modified porous nickel-rich cathode material and preparation method thereof | |
| WO2013141317A1 (en) | Manganomanganic oxide and process for producing same | |
| CN114538535B (en) | Positive electrode material, precursor, preparation method of precursor and lithium ion battery | |
| WO2024164414A1 (en) | Nickel-cobalt-manganese hydroxide precursor having radial porous structure, and preparation method therefor | |
| CN117735624A (en) | Ternary precursor and preparation method and application thereof | |
| CN118458847A (en) | Sodium carbonate coated multi-element precursor, preparation method thereof, multi-element coating material and positive electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |