CN115947385A - Preparation method of low-cobalt and cobalt-free precursor and lithium-poor low-cobalt and cobalt-free cathode material and product thereof - Google Patents
Preparation method of low-cobalt and cobalt-free precursor and lithium-poor low-cobalt and cobalt-free cathode material and product thereof Download PDFInfo
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- 239000002243 precursor Substances 0.000 title claims abstract description 46
- 239000010406 cathode material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910017052 cobalt Inorganic materials 0.000 title claims description 39
- 239000010941 cobalt Substances 0.000 title claims description 39
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 26
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 229910052744 lithium Inorganic materials 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 230000002950 deficient Effects 0.000 claims description 13
- 239000011572 manganese Substances 0.000 claims description 11
- 239000010405 anode material Substances 0.000 claims description 10
- 150000001868 cobalt Chemical class 0.000 claims description 10
- 150000002696 manganese Chemical class 0.000 claims description 10
- 150000002815 nickel Chemical class 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000002572 peristaltic effect Effects 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 239000011164 primary particle Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000007774 positive electrode material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 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 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229960005076 sodium hypochlorite Drugs 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of synthesis of ternary cathode materials, in particular to a preparation method of a low-cobalt-free precursor and a lithium-poor low-cobalt-free cathode material and a product thereof. A precursor which is loose and porous in the interior, fine in primary particles and large in BET is prepared by an oxidation method with low PH or low ammonia concentration or air/oxidant introduction, and then the precursor and lithium salt are mixed and roasted in a mixing mode of Me: li =1 (1-0.9), so that Li ions can be rapidly diffused into the material through concentration gradient to react in the roasting process, the volatilization of the lithium salt at high temperature is inhibited, the lithium salt and the precursor are fully reacted, and the cathode material with excellent electrochemical performance is obtained.
Description
Technical Field
The invention relates to the technical field of synthesis of ternary cathode materials, in particular to a preparation method of a low-cobalt-free precursor and a lithium-poor low-cobalt-free cathode material and a product thereof.
Background
With the continuous fire explosion of new energy automobiles, the demand of power batteries is greatly increased, so that the price of lithium battery raw materials is high, and global lithium, cobalt and nickel ore resources are mostly concentrated overseas and monopolized by head mining groups. The price of lithium as "white petroleum" is increasing dramatically, and has been doubled in the last year, which leads to the rapid rise of the cost of the positive electrode material, and the cost of the positive electrode material in lithium batteries can account for 60%, so that the cost of producing the positive electrode material is extremely reduced.
However, at present, the usage amount of lithium salt in the roasting process of the positive electrode material is excessive, and the problems of volatilization of the lithium salt and the like in the roasting process are faced, so that the usage amount of the lithium salt is inevitably increased, and the insufficient usage of the lithium salt can cause various problems of capacity reduction, poor cycle performance, poor rate performance and the like of the positive electrode material, for example, a wet preparation process of a lithium ion battery ternary positive electrode material disclosed in chinese patent application (with the grant number of CN 103151512B) realizes the rapid preparation of a nickel cobalt lithium manganate ternary positive electrode material with good electrochemical performance and a uniform submicron structure by optimizing a synthesis route, but still has the problem of high usage amount of the lithium salt. Therefore, how to improve the utilization rate of lithium salt through the improvement of the process is the central focus of the current research in this field.
According to the current situation, the invention provides a lithium-poor sintering technology, which can reduce the use amount of lithium salt under the condition of not influencing the performance of a positive electrode material, thereby achieving the purpose of reducing the cost.
Disclosure of Invention
The invention provides a preparation method of a low-cobalt and cobalt-free precursor and a lithium-poor low-cobalt and cobalt-free anode material, which at least comprises the following steps:
(1) Introducing gas into a reaction kettle, adding a base solution into the reaction kettle through a peristaltic pump, respectively adding aqueous solutions of nickel salt, cobalt salt and manganese salt into the reaction kettle according to a certain molar ratio through a coprecipitation method, adding a precipitant solution into the reaction kettle for reaction, simultaneously adjusting the pH value and the ammonia concentration of a system with strong ammonia water, and filtering, washing and drying precipitates generated in the reaction to obtain a precursor;
(2) The precursor and the lithium salt are proportioned according to a proportion, the additive is added and uniformly mixed, and then the lithium-poor low-cobalt-free anode material is obtained after roasting, cooling, roll crushing, sieving and magnetic removal.
As a preferable technical scheme, the gas in the step (1) is one of nitrogen and argon.
As a preferred technical scheme, the base solution in the step (1) is dilute ammonia solution; preferably, the concentration of the dilute ammonia liquid is 1-2mol/L.
As a preferable technical scheme, in the step (1), the nickel salt, the cobalt salt and the manganese salt are one of sulfate, nitrate and acetate.
As a preferable technical scheme, the precipitant solution in the step (1) is an aqueous sodium hydroxide solution. Preferably, the concentration of the sodium hydroxide aqueous solution is 4-6mol/L.
As a preferable technical scheme, the molar ratio of the nickel salt, the cobalt salt and the manganese salt in the step (1) is 55.
As a preferred technical scheme, the specific conditions of the reaction in the step (1) are as follows: continuously stirring and reacting for 20-200h at 35-65 ℃ and controlling the pH of the reaction system to be =10.0-12.0 and the ammonia concentration to be 0-2g/L.
As a preferable technical solution, in the step (1), the precursor is one of hydroxide, carbonate and acetate of nickel, cobalt and manganese.
As a preferred technical solution, the molar ratio of the precursor to the lithium salt in the step (2) is Me (nickel + cobalt + manganese): li =1: (1-0.9);
as a preferable technical solution, in the step (2), the lithium salt is one of lithium carbonate, lithium hydroxide, lithium nitrate and lithium chloride;
as a preferable technical scheme, the element in the additive in the step (2) comprises at least one of Mg, sr, B, F, P, ti, zr, mo, W, Y, la and Ce.
As a preferred technical solution, the roasting conditions in the step (2) are specifically: in the presence of air or oxidant, the roasting temperature is controlled at 600-1000 deg.C, and the roasting time is 6-30h.
Preferably, the oxidizing agent is one of hydrogen peroxide, peracetic acid, sodium dichromate, chromic acid, nitric acid, potassium permanganate, ammonium persulfate, sodium hypochlorite, sodium percarbonate, sodium perborate, potassium perborate, bromine, and iodine.
Based on the preparation method of the low-cobalt and cobalt-free precursor and the lithium-poor low-cobalt and cobalt-free anode material provided by the invention, the precursor which is loose and porous inside, fine in primary particles and large in BET (BET) is prepared by using a low-PH or low-ammonia concentration or an oxidation method of introducing air/an oxidant, and then the precursor and lithium salt are mixed and roasted by using a mixing mode of Me: li =1 (1-0.9), so that Li ions can be rapidly diffused into the material through concentration gradient to react in the roasting process, the volatilization of the lithium salt at high temperature is inhibited, the lithium salt and the precursor are fully reacted, and the anode material with excellent electrochemical performance is obtained.
The invention also provides a lithium-poor low-cobalt-free cathode material, wherein the first discharge specific capacity of the lithium-poor low-cobalt-free cathode material is 168.2mAh/g-176.3mAh/g.
Has the beneficial effects that:
1. aiming at the current situation, the invention provides a lithium-poor sintering technology, which can use less lithium salt under the condition of not influencing the performance of a positive electrode material, thereby achieving the purpose of reducing the cost.
2. Based on the preparation method of the low-cobalt and cobalt-free precursor and the lithium-poor low-cobalt and cobalt-free anode material provided by the invention, the precursor which is loose and porous inside, fine in primary particles and large in BET (BET) is prepared by using a low-PH or low-ammonia concentration or an oxidation method of introducing air/an oxidant, and then the precursor and lithium salt are mixed and roasted by using a mixing mode of Me: li =1 (1-0.9), so that Li ions can be rapidly diffused into the material through concentration gradient to react in the roasting process, the volatilization of the lithium salt at high temperature is inhibited, the lithium salt and the precursor are fully reacted, and the anode material with excellent electrochemical performance is obtained.
Drawings
FIG. 1 shows Ni prepared in example 1 (a) and comparative example 1 (b) of the present invention 0.55 0Co 0.05 Mn 0.40 (OH) 2 Fig. 1 shows that the primary particles of the precursor prepared by the process of example 1 are finer.
FIG. 2 shows Li prepared in example 1 (a) and comparative example 1 (b) 0.98 Ni 0.55 Co 0.05 Mn 0.40 O 2 Scanning electron microscope photographs of the cathode material, and fig. 1 shows that the material prepared by the method is polycrystalline secondary particles.
FIG. 3 shows Li prepared in example 1 and comparative example 1 0.98 Ni 0.55 Co 0.05 Mn 0.40 O 2 The charge and discharge curves of the cathode material are compared with each other.
FIG. 4 shows Li prepared in example 1 and comparative example 1 0.98 Ni 0.55 Co 0.05 Mn 0.40 O 2 The cycle performance of the positive electrode material at normal temperature (25 ℃, a) and high temperature (45 ℃, b) is compared.
Detailed Description
Example 1
The invention provides a preparation method of a low-cobalt-free precursor and a lithium-poor low-cobalt-free anode material, which at least comprises the following steps:
(1) Introducing gas into a 10L reaction kettle, adding 5L of base solution into the reaction kettle through a peristaltic pump, and performing coprecipitation according to the weight ratio of Ni: co: respectively adding aqueous solutions of nickel salt, cobalt salt and manganese salt into a reaction kettle at the same time according to the molar ratio of Mn = 55;
(2) The precursor and the lithium salt are proportioned according to a proportion, the additive is added and uniformly mixed, and then the lithium-poor low-cobalt-free anode material is obtained after roasting, cooling, roll crushing, sieving and magnetic removal.
The gas in the step (1) is nitrogen.
The molar ratio of the nickel salt to the cobalt salt to the manganese salt in the step (1) is 55.
The base solution in the step (1) is dilute ammonia solution; the concentration of the dilute ammonia solution is 1mol/L. Specifically, strong ammonia water with mass concentration of 22% is diluted by adding water to prepare dilute ammonia liquid with concentration of 1mol/L.
The nickel salt, the cobalt salt and the manganese salt in the step (1) are respectively nickel sulfate, cobalt sulfate and manganese sulfate. The concentration of the aqueous solution of the nickel salt, the cobalt salt and the manganese salt is 2mol/L.
And (2) the precipitant solution in the step (1) is a sodium hydroxide aqueous solution. The concentration of the sodium hydroxide aqueous solution is 5mol/L. The mass concentration of the strong ammonia water is 22%.
The specific conditions of the reaction in the step (1) are as follows: the reaction was continuously stirred at a temperature of 45 ℃ for 10 hours with controlling the pH of the reaction system =11.0 and the ammonia concentration at 0.5g/L.
Referring to fig. 1, in the step (1), the precursor is a hydroxide of nickel, cobalt and manganese.
The molar ratio of the precursor to the lithium salt in the step (2) is Me (nickel + cobalt + manganese): li =1:0.98 of;
the lithium salt in the step (2) is lithium carbonate;
the additive in the step (2) is zirconia.
The roasting conditions in the step (2) are as follows: in the presence of air, the roasting temperature is controlled to be 850 ℃, and the roasting time is 12h.
Referring to fig. 2, example 1 of the present invention provides, in another aspect, a lithium-deficient low-cobalt-free cathode material having a specific first discharge capacity of 176.3mAh/g.
Example 2
The embodiment 2 of the present invention provides a preparation method of a low-cobalt and cobalt-free precursor and a lithium-deficient low-cobalt and cobalt-free cathode material, which is the same as that in the embodiment 1, except that the molar ratio of nickel salt, cobalt salt and manganese salt in the step (1) is 60.
Example 3
The embodiment 3 of the present invention provides a preparation method of a low-cobalt-free precursor and a lithium-deficient low-cobalt-free cathode material, and the specific implementation manner is the same as that in the embodiment 1, except that the specific conditions of the reaction in the step (1) are as follows: the reaction was continuously stirred at a temperature of 45 ℃ for 10 hours with controlling the pH of the reaction system =11.0 and the ammonia concentration at 0g/L.
Example 4
example 5
Embodiment 5 of the present invention provides a method for preparing a low-cobalt-free precursor and a lithium-deficient low-cobalt-free cathode material, and the specific implementation manner is the same as that in embodiment 1, except that the conditions for the calcination in step (2) are specifically: in the presence of air, the roasting temperature is controlled to be 800 ℃, and the roasting time is 12h.
Comparative example 1
The comparative example 1 of the present invention provides a preparation method of a low-cobalt-free precursor and a lithium-deficient low-cobalt-free cathode material, and the specific implementation manner is the same as that of example 1, except that the specific conditions of the reaction in the step (1) are as follows: the reaction was continuously stirred at a temperature of 45 ℃ for 10 hours and the pH of the reaction system was controlled to =11.5 and the ammonia concentration was 3g/L.
Performance test method
1. Scanning electron microscope characterization is carried out on the precursors prepared in the examples and the comparative examples and the lithium-poor low-cobalt-free cathode material, and the results are shown in figures 1 and 2.
2. The lithium-poor low-cobalt-free cathode material prepared in the examples and the comparative examples is used as a cathode, the metal lithium is used as an anode material, and the assembled battery is tested under the conditions that the discharge cutoff voltage is 3.0V and the charge cutoff voltage is 4.3V, and the test results are shown in Table 1, wherein the first discharge specific capacity is 176.3mAh/g and is 21.1mAh/g higher than that of the comparative example 1.
TABLE 1,
3. The lithium-poor low-cobalt-free positive electrode materials prepared in example 1 and comparative example 1 were subjected to charge and discharge performance tests and normal-temperature and high-temperature cycle performance tests, and the results are shown in fig. 3 and fig. 4.
Claims (10)
1. A preparation method of a low-cobalt-free precursor and a lithium-poor low-cobalt-free cathode material is characterized by at least comprising the following steps:
(1) Introducing gas into a reaction kettle, adding a base solution into the reaction kettle through a peristaltic pump, respectively adding aqueous solutions of nickel salt, cobalt salt and manganese salt into the reaction kettle according to a certain molar ratio through a coprecipitation method, adding a precipitant solution for reaction, adjusting the pH value and the ammonia concentration of a system with concentrated ammonia water, and filtering, washing and drying precipitates generated by the reaction to obtain a precursor;
(2) The precursor and the lithium salt are proportioned according to a proportion, the additive is added and uniformly mixed, and then the lithium-poor low-cobalt-free anode material is obtained after roasting, cooling, roll crushing, sieving and magnetic removal.
2. The method for preparing the low-cobalt and cobalt-free precursor and the lithium-deficient low-cobalt and cobalt-free cathode material according to claim 1, wherein the gas in the step (1) is one of nitrogen and argon.
3. The method for preparing the low-cobalt and cobalt-free precursor and the lithium-poor low-cobalt and cobalt-free cathode material according to claim 2, wherein the base solution in the step (1) is a dilute ammonia solution; the concentration of the dilute ammonia solution is 1-2mol/L.
4. The method for preparing the low-cobalt and cobalt-free precursor and the lithium-poor low-cobalt and cobalt-free cathode material according to claim 3, wherein the nickel salt, the cobalt salt and the manganese salt in the step (1) are one of sulfate, nitrate and acetate.
5. The method for preparing the low-cobalt and cobalt-free precursor and the lithium-poor low-cobalt and cobalt-free cathode material according to claim 4, wherein the precipitant solution in the step (1) is an aqueous sodium hydroxide solution, and the concentration of the aqueous sodium hydroxide solution is 4-6mol/L.
6. The method for preparing the low-cobalt and cobalt-free precursor and the lithium-deficient low-cobalt and cobalt-free cathode material according to claim 5, wherein the specific conditions of the reaction in the step (1) are as follows: continuously stirring and reacting for 20-200h at 35-65 ℃ and controlling the pH of the reaction system to be =10.0-12.0 and the ammonia concentration to be 0-2g/L.
7. The method for preparing the low-cobalt and cobalt-free precursor and the lithium-deficient low-cobalt and cobalt-free cathode material according to claim 6, wherein the precursor in the step (1) is one of hydroxide, carbonate and acetate of nickel, cobalt and manganese.
8. The method for preparing the low-cobalt and cobalt-free precursor and the lithium-poor low-cobalt and cobalt-free cathode material according to claim 1, wherein the molar ratio of the precursor to the lithium salt in the step (2) is Me: li =1: (1-0.9).
9. The method for preparing the low-cobalt and cobalt-free precursor and the lithium-deficient low-cobalt and cobalt-free cathode material according to claim 8, wherein the conditions for the calcination in the step (2) are specifically: the roasting temperature is 600-1000 ℃, and the roasting time is 6-30h.
10. A lithium-deficient, low-cobalt and cobalt-free cathode material synthesized by the method for preparing the low-cobalt and cobalt-free precursor and the lithium-deficient, low-cobalt and cobalt-free cathode material according to any one of claims 1 to 9, wherein the lithium-deficient, low-cobalt and cobalt-free cathode material has a specific first discharge capacity of 168.2mAh/g to 176.3mAh/g.
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