CN112661205A - Multi-oxide-coated ternary lithium ion battery positive electrode material and preparation method thereof - Google Patents
Multi-oxide-coated ternary lithium ion battery positive electrode material and preparation method thereof Download PDFInfo
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 37
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 41
- 239000010405 anode material Substances 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000003825 pressing Methods 0.000 claims abstract description 9
- 238000007873 sieving Methods 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 4
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 4
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 239000010406 cathode material Substances 0.000 claims description 22
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 36
- 239000011248 coating agent Substances 0.000 abstract description 34
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000009827 uniform distribution Methods 0.000 abstract description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 23
- 239000000203 mixture Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 23
- 238000005245 sintering Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 239000012065 filter cake Substances 0.000 description 10
- 239000002243 precursor Substances 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 239000002344 surface layer Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 241001168730 Simo Species 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910018058 Ni-Co-Al Inorganic materials 0.000 description 2
- 229910018060 Ni-Co-Mn Inorganic materials 0.000 description 2
- 229910018144 Ni—Co—Al Inorganic materials 0.000 description 2
- 229910018209 Ni—Co—Mn Inorganic materials 0.000 description 2
- 229910020881 PMo12O40 Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- -1 nickel-cobalt-aluminum (manganese) Chemical compound 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a multi-oxide coated ternary lithium ion battery anode material and a preparation method thereof. The preparation method comprises the following steps: uniformly mixing a ternary positive electrode material, deionized water and a polyethyleneimine solution, then adding a polyoxometallate solution, uniformly stirring, and performing filter pressing and drying to obtain a material A; calcining the material A in an oxygen atmosphere, and then cooling, sieving and removing iron to obtain the polyoxide-coated ternary lithium ion battery anode materialFeeding; the general structural formula of the polyoxometallate is (NH)4)nXM12O40Or (NH)4)nX2M18O62N is one of 3, 4, 5 or 6, X is one of P, Si, Ge, As, B, Co or Cu, and M is one of Mo, W, V, Nb or Ta. The method has the advantages of single coating raw material, uniform distribution of various coating elements, controllable coating thickness, simple process flow and the like, can improve the cycle stability and safety performance of the anode material to a greater extent, and is easy to realize industrial production.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a multi-oxide coated ternary lithium ion battery positive electrode material and a preparation method thereof.
Background
The lithium ion battery as a novel energy storage and conversion device has the advantages of high working voltage, high energy/power density, long cycle life, environmental friendliness and the like, and is widely applied to the fields of portable electronic equipment, energy storage power grids, electric vehicles and the like. As one of the four most important main materials of lithium ion batteries, a nickel-cobalt-aluminum (manganese) ternary positive electrode material has a high energy/power density, and thus has been the focus of research.
In the ternary material, as the content of nickel increases, the capacity gradually increases, but at the same time, the defects of short cycle life, poor safety performance and the like are also brought, so that the capacity and power of the ternary cathode material are improved, and the cycle stability and safety performance of the ternary cathode material are improved, which becomes one of the key problems to be solved by researchers. Research shows that the stability of the two-phase interface of the electrode/electrolyte is one of the key factors influencing the electrochemical performance of the ternary cathode material. In the process of charging and discharging, a high-activity interface is easy to generate oxidation-reduction reaction with electrolyte to generate an inactive rock salt phase structure, so that the electrolyte is decomposed, and simultaneously a large amount of heat is released, so that the problems of cell inflation, reduction of safety performance, attenuation of discharge capacity, deterioration of cycle stability and the like are caused.
In order to improve and enhance the interface stability of the positive electrode material, one of the main technical means at present is to perform a surface coating treatment, and the coating is mainly an oxide, a fluoride, or the like. The surface layer coating can effectively avoid direct contact between a high-activity positive electrode interface and electrolyte, and relieve side reaction, and the coating can be used as an excellent fast ion conductor and can also provide a good diffusion channel for lithium ions, so that the multiplying power performance of the material is improved. At present, dry coating is mainly adopted as a coating method, and the coating method is to mechanically stir and mix the positive electrode material to be coated and the coating(s) and then perform high-temperature calcination treatment. The method has the defect of uneven distribution of the surface layer of the coating, so that the surface layer of the anode material is exposed, and the coating also forms an independent dispersed island-shaped structure, thereby greatly influencing the performance of the anode material; in addition, when multi-element coating is performed, the dispersion degree of each coating is worse, and different coating raw materials are used, so that the operation is complex, and the purpose of finally improving the interface stability of the cathode material cannot be achieved.
Disclosure of Invention
In view of the above, it is necessary to provide a multi-oxide coated ternary lithium ion battery positive electrode material and a preparation method thereof, so as to solve the technical problems of complicated coating steps and poor dispersion degree of the coating in the prior art.
The invention provides a preparation method of a multi-oxide coated ternary lithium ion battery positive electrode material, which comprises the following steps:
uniformly mixing a ternary positive electrode material, deionized water and a polyethyleneimine solution, then adding a polyoxometallate solution, uniformly stirring, and performing filter pressing and drying to obtain a material A;
calcining the material A in an oxygen atmosphere, and then cooling, sieving and removing iron to obtain a polyoxide-coated ternary lithium ion battery anode material;
general structure of polyoxometallateIs of the formula (NH)4)nXM12O40Or (NH)4)nX2M18O62N is one of 3, 4, 5 or 6, X is one of P, Si, Ge, As, B, Co or Cu, and M is one of Mo, W, V, Nb or Ta.
The second aspect of the invention provides a multi-oxide-coated ternary lithium ion battery anode material, which is obtained by the preparation method of the multi-oxide-coated ternary lithium ion battery anode material provided by the first aspect of the invention.
Compared with the prior art, the invention has the beneficial effects that:
the method has the advantages of single coating raw material, uniform distribution of various coating elements, controllable coating thickness, simple process flow (simultaneous washing and coating), and the like, can greatly improve the cycle stability and safety performance of the anode material, and is easy to realize industrial production.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a preparation method of a multi-oxide coated ternary lithium ion battery positive electrode material, which comprises the following steps:
s1: uniformly mixing a ternary positive electrode material, deionized water and a Polyethyleneimine (PEI) solution, then adding a polyoxometallate solution (POM), uniformly stirring, and performing filter pressing and drying to obtain a material A; wherein the general structural formula of the polyoxometallate is (NH)4)nXM12O40Or (NH)4)nX2M18O62N is one of 3, 4, 5 or 6, X is one of P, Si, Ge, As, B, Co or Cu, and M is one of Mo, W, V, Nb or Ta; further, the polyoxometallate is (NH4)3PMo12O40、(NH4)4SiMo12O40、(NH4)3PW12O40One or more of (a).
S2: calcining the material A in an oxygen atmosphere, and then cooling, sieving and removing iron to obtain the polyoxide-coated ternary lithium ion battery anode material.
In the step S1, the mass ratio of the ternary cathode material to the deionized water is 1: (1-5), preferably 1: (1-2).
In the step S1, the concentration of polyethyleneimine is 20 to 300mg/mL, preferably 50 to 200 mg/mL; the molecular weight Mw is 100000-1000000, preferably 500000; the mass ratio of the finally added polyethyleneimine to the ternary positive electrode material is (0.01-2): 1, preferably (0.05-0.5): 1. if the amount of PEI is too large, the surface coating layer is too thick, and the battery capacity is reduced.
In the step S1, the stirring time after the polyethyleneimine is added is 10-90 min, and the stirring time after the polyoxometallate is added is 20-120 min.
In the step S1, the concentration of the polyoxometallate is 1 to 100mg/mL, preferably 10 to 100 mg/mL; the mass ratio of the finally added polyoxometallate to the ternary positive electrode material is (0.001-0.12): 1, preferably (0.004-0.012): 1.
in the step S1, the drying temperature is 80-120 ℃, and the drying time is 5-20 h.
In the step S2, the calcination temperature is 400-800 ℃, preferably 450-600 ℃; the calcination time is 3-15 h, preferably 4-8 h. The invention decomposes the polyoxometallate coated on the surface layer into oxides corresponding to different elements or oxometallates containing lithium by high-temperature sintering, thereby being beneficial to further improving the performance of the battery; the polyoxometallate can not be effectively decomposed on the one hand, and the oxide can not be effectively combined with the anode material of the body on the other hand, so that the acting force is poor, and the coating layer is easy to fall off; too high a sintering temperature easily affects the crystal structure of the bulk of the positive electrode material, thereby deteriorating the performance.
Whether the ternary cathode material is doped or not is not limited by the invention, and the person skilled in the art can select the ternary cathode material according to the requirement. In some preferred embodiments of the present invention, the ternary cathode material is a doped ternary cathode material. The specific type of the doping element is not limited in the invention, and can be one or more of Zr, Fe, Sm, Pr, Ga, Zn, Y, Mg, Al, Cr, Ca, Na, Ti, Cu, K, Sr and Mo. Further, the doped ternary cathode material is obtained by uniformly mixing a ternary precursor, a lithium source and a dopant, followed by sintering. The ternary precursor is one or more of oxides, hydroxides and oxyhydroxides of nickel-cobalt-manganese or nickel-cobalt-aluminum; the lithium source is one or a mixture of lithium carbonate, lithium oxide and lithium hydroxide; the molar ratio of lithium in the ternary precursor to lithium in the lithium source is 1: (1.01-1.15); the mass ratio of the ternary precursor to the dopant is 100: (0.01-2). The sintering temperature is 600-800 ℃, and the sintering time is 8-16 h.
The second aspect of the invention provides a multi-oxide-coated ternary lithium ion battery anode material, which is obtained by the preparation method of the multi-oxide-coated ternary lithium ion battery anode material provided by the first aspect of the invention.
Example 1
(1) 450g of ternary cathode material (LiNi)0.83Co0.12Mn0.05O2) Poured into 900mL of deionized water, and during stirring, a total volume of 3000mL of PEI (Mw: 100000) adding the above solution, stirring for 30min, adding 500mL ammonium phosphomolybdate [ (NH) with concentration of 100mg/mL4)3PMo12O40]Solutions (PMo for short)12) Continuously stirring for 30min, transferring the mixed solution to a filter press for filter pressing, performing solid-liquid separation to obtain a filter cake, transferring the filter cake to the inside of an oven for drying, removing residual moisture, and marking the dried material as a material A;
(2) and uniformly dispersing all the obtained material A in a sagger, then placing the sagger in a muffle furnace filled with oxygen atmosphere for calcining at the temperature of 450 ℃ for 8 hours, taking out the material after natural cooling, sieving and removing iron to obtain the polyoxide-coated ternary lithium ion battery anode material.
Example 2
(1) 500g of Ni-Co-Mn hydroxide ternary material precursor Ni is weighed0.90Co0.05Mn0.05(OH)2240g of lithium hydroxide (LiOH. H)2O), 1.5g of nano-zirconium dioxide (ZrO)2) Transferring the mixture into a high-speed mixer to mix at the rotating speed of 1000rpm for 1h, taking out the mixture after mixing, transferring the mixture into a muffle furnace to calcine the mixture, sintering the mixture for 12h at the temperature of 700 ℃ in an oxygen atmosphere, and taking out the material after sintering to obtain a ternary cathode material;
(2) pouring 450g of ternary cathode material into 500mL of deionized water, gradually adding 500mL of PEI (Mw: 500000) solution with the total volume of 100mg/mL into the solution while stirring, continuing to stir for 30min, and adding 100mL of ammonium silicomolybdate [ (NH) with the concentration of 50mg/mL into the solution4)4SiMo12O40]Solution (SiMo for short)12) Continuously stirring for 30min, transferring the mixed solution to a filter press for filter pressing, performing solid-liquid separation to obtain a filter cake, transferring the filter cake to the inside of an oven for drying, removing residual moisture, and marking the dried material as a material A;
(3) and uniformly dispersing all the obtained material A in a sagger, then placing the sagger in a muffle furnace filled with oxygen atmosphere for calcining at the temperature of 550 ℃ for 6 hours, naturally cooling, taking out the material, sieving and removing iron to obtain the polyoxide-coated ternary lithium ion battery anode material.
Example 3
(1) 500g of Ni-Co-Mn hydroxide ternary material precursor Ni is weighed0.90Co0.05Mn0.05(OH)2240g of lithium hydroxide (LiOH. H)2O), 1.5g of nano-zirconium dioxide (ZrO)2) Transferring the mixture into a high-speed mixer to mix at the rotating speed of 1000rpm for 1h, taking out the mixture after mixing, transferring the mixture into a muffle furnace to calcine the mixture, sintering the mixture for 12h at the temperature of 700 ℃ in an oxygen atmosphere, and taking out the material after sintering to obtain a ternary cathode material;
(2) 450g of ternary cathode material is poured into 500mL of deionized water, and during stirring, a total volume of 1000mL of PEI (M) with a concentration of 200mg/mL is gradually addedw: 500000) was added to the above solution, and after stirring for another 30min, ammonium silicomolybdate [ (NH) was added to the solution in a volume of 500mL and a concentration of 50mg/mL4)4SiMo12O40]Solution (SiMo for short)12) Continuously stirring for 30min, transferring the mixed solution to a filter press for filter pressing, performing solid-liquid separation to obtain a filter cake, transferring the filter cake to the inside of an oven for drying, removing residual moisture, and marking the dried material as a material A;
(3) and uniformly dispersing all the obtained material A in a sagger, then placing the sagger in a muffle furnace filled with oxygen atmosphere for calcining at the temperature of 600 ℃ for 6 hours, taking out the material after natural cooling, sieving and removing iron to obtain the polyoxide-coated ternary lithium ion battery anode material.
Example 4
(1) 500g of Ni-Co-Al hydroxide ternary material precursor Ni is weighed0.88Co0.09Al0.03(OH)2240g of lithium hydroxide (LiOH. H)2O), 1.5g of nano-zirconium dioxide (ZrO)2) Transferring the mixture into a high-speed mixer to mix at the rotating speed of 1000rpm for 1h, taking out the mixture after mixing, transferring the mixture into a muffle furnace to calcine the mixture, sintering the mixture for 12h at the temperature of 720 ℃ in an oxygen atmosphere, and taking out the material after sintering to obtain a ternary cathode material;
(2) 450g of ternary cathode material was poured into 500mL of deionized water, and during stirring, a total volume of 500mL of 50mg/mL PEI (M) was gradually addedw: 500000) solution is added into the above solution, and stirring is continued for 30min, and then ammonium phosphotungstate [ (NH) is added into the solution with a volume of 200mL and a concentration of 10mg/mL4)3PW12O40]Solution (PW for short)12) Continuously stirring for 30min, transferring the mixed solution to a filter press for filter pressing, performing solid-liquid separation to obtain a filter cake, transferring the filter cake to the inside of an oven for drying, removing residual moisture, and marking the dried material as a material A;
(3) and uniformly dispersing all the obtained material A in a sagger, then placing the sagger in a muffle furnace filled with oxygen atmosphere for calcining at the temperature of 550 ℃ for 6 hours, naturally cooling, taking out the material, sieving and removing iron to obtain the polyoxide-coated ternary lithium ion battery anode material.
Example 5
(1) 500g of Ni-Co-Al hydroxide ternary material precursor Ni is weighed0.88Co0.09Al0.03(OH)2260g of lithium hydroxide (LiOH. H)2O), 10g of nano-titanium dioxide (TiO)2) Transferring the mixture into a high-speed mixer to mix at the rotating speed of 1000rpm for 1h, taking out the mixture after mixing, transferring the mixture into a muffle furnace to calcine the mixture, sintering the mixture for 12h at the temperature of 700 ℃ in an oxygen atmosphere, and taking out the material after sintering to obtain a ternary cathode material;
(2) pouring 450g of ternary cathode material into 800mL of deionized water, gradually adding 250mL of PEI (Mw: 1000000) solution with the total volume of 20mg/mL into the solution while stirring, continuing to stir for 30min, and adding 50mL of ammonium silicomolybdate [ (NH) with the concentration of 10mg/mL into the solution4)4SiMo12O40]Solution (SiMo for short)12) Continuously stirring for 30min, transferring the mixed solution to a filter press for filter pressing, performing solid-liquid separation to obtain a filter cake, transferring the filter cake to the inside of an oven for drying, removing residual moisture, and marking the dried material as a material A;
(3) and uniformly dispersing all the obtained material A in a sagger, then placing the sagger in a muffle furnace filled with oxygen atmosphere for calcining at the temperature of 600 ℃ for 4 hours, naturally cooling, taking out the material, sieving and removing iron to obtain the polyoxide-coated ternary lithium ion battery anode material.
Comparative example 1
Comparative example 1 differs from example 2 only in that no PEI was added to comparative example 1.
Comparative example 2
Comparative example 2 differs from example 2 only in that 4000mL of PEI (Mw: 500000) at a concentration of 300mg/mL was added in comparative example 1.
Comparative example 3
Comparative example 3 is different from example 2 in that the sintering temperature after coating in comparative example 3 is 300 ℃.
Comparative example 4
Comparative example 4 is different from example 2 in that the sintering temperature after coating in comparative example 3 is 900 ℃.
Test group
The polyoxide-coated ternary lithium ion battery positive electrode materials obtained in examples 1-5 and comparative examples 1-4, acetylene black and PVDF are mixed according to a ratio of 94:4:2, NMP is used as a solvent, the mixture is uniformly mixed and then coated on an aluminum foil, a 2032 button cell is manufactured to be subjected to electrochemical performance testing, the testing voltage range is 2.8-4.3V, the first week is charging and discharging according to 0.1C/0.1C, then 1C/1C cycle testing is carried out for 50 weeks, and the testing results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the positive electrode materials obtained in the embodiments 1 to 5 of the present invention all have good capacity and cycle capacity retention rate.
Compared with other dry coating methods, the preparation method of the polyoxide-coated ternary lithium ion battery anode material has the following advantages:
firstly, the coating layer is more uniform and compact, multiple oxide nano-levels can be uniformly distributed on the surface of the anode material, and an uncoated bare interface of the anode material is avoided to the maximum extent, so that the interface stability of the anode material can be greatly improved, and the cycle stability and the safety performance of the material are improved to the maximum extent;
secondly, the thickness of the coating is controllable, and the adsorption quantity of polyoxometallate ions can be effectively adjusted by adjusting the concentration and the content of PEI and POM, so that the coating quantity of the final sintered product is controlled;
the washing and coating processes of the ternary cathode material can be simultaneously realized by a one-step method, the process flow is shortened, the operation is convenient, and the method is suitable for batch preparation and industrial production;
the coating raw material is single, multi-element uniform coating can be realized simultaneously only by one coating raw material, and the interface stability and the ionic conductivity of the material are greatly improved through the synergistic effect among different oxide coating layers.
Compared with the conventional wet coating, the method has the following advantages:
firstly, the traditional wet coating is realized only by electrostatic adsorption of ions on the surface of a coating agent and a positive electrode material in the washing process, so that the coating amount is less, and the final coating efficiency is not high; according to the invention, the PEI is firstly utilized to aminate the interface of the anode material, so that the Zeta potential value of the surface layer is changed from negative to positive, thereby providing effective guarantee for the subsequent combination of polyoxometallate anions, greatly improving the anion-cation reaction combination efficiency between the PEI and the anode material, and enabling the coating amount to be adjustable and controllable;
secondly, the PEI and the coating agent solution are alkalescent as a whole, so that the damage (H) of the surface layer structure of the anode material in the water washing process can be effectively relieved+/Li+Exchange).
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (10)
1. A preparation method of a multi-oxide coated ternary lithium ion battery positive electrode material is characterized by comprising the following steps:
uniformly mixing a ternary positive electrode material, deionized water and a polyethyleneimine solution, then adding a polyoxometallate solution, uniformly stirring, and performing filter pressing and drying to obtain a material A;
calcining the material A in an oxygen atmosphere, and then cooling, sieving and removing iron to obtain a polyoxide-coated ternary lithium ion battery anode material;
the general structural formula of the polyoxometallate is (NH)4)nXM12O40Or (NH)4)nX2M18O62N is one of 3, 4, 5 or 6X is one of P, Si, Ge, As, B, Co or Cu, and M is one of Mo, W, V, Nb or Ta.
2. The method for preparing the polyoxide-coated ternary lithium ion battery positive electrode material according to claim 1, wherein the mass ratio of the ternary positive electrode material to deionized water is 1: (1-5).
3. The preparation method of the polyoxide-coated ternary lithium ion battery cathode material according to claim 1, wherein the molecular weight Mw of the polyethyleneimine is 100000-1000000, and the mass ratio of the finally added polyethyleneimine to the ternary cathode material is (0.01-2): 1.
4. the preparation method of the polyoxide-coated ternary lithium ion battery positive electrode material according to claim 1, wherein the mass ratio of the finally added polyoxometallate to the ternary positive electrode material is (0.001-0.12): 1.
5. the method for preparing the polyoxide-coated ternary lithium ion battery positive electrode material according to claim 1, wherein the stirring time after the addition of the polyethyleneimine is 10-90 min, and the stirring time after the addition of the polyoxometallate is 20-120 min.
6. The preparation method of the polyoxide-coated ternary lithium ion battery positive electrode material according to claim 1, wherein the drying temperature is 80-120 ℃, and the drying time is 5-20 h.
7. The preparation method of the polyoxide-coated ternary lithium ion battery positive electrode material according to claim 1, wherein the calcining temperature is 400-800 ℃, and the calcining time is 3-15 h.
8. The method for preparing the polyoxide-coated ternary lithium ion battery positive electrode material according to claim 1, wherein the ternary positive electrode material is a doped ternary positive electrode material.
9. The method of claim 8, wherein the doping element is one or more of Zr, Fe, Sm, Pr, Ga, Zn, Y, Mg, Al, Cr, Ca, Na, Ti, Cu, K, Sr, and Mo.
10. The positive electrode material of the ternary lithium ion battery coated with the polyoxide is prepared by the preparation method of the positive electrode material of the ternary lithium ion battery coated with the polyoxide according to any one of claims 1 to 9.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113968593A (en) * | 2021-09-30 | 2022-01-25 | 广东邦普循环科技有限公司 | Method for recovering and treating ternary material micro powder and application thereof |
| CN114772574A (en) * | 2022-05-31 | 2022-07-22 | 蜂巢能源科技股份有限公司 | Method for doping cathode material by using heteropoly acid and/or heteropoly acid salt, cathode material and application |
| CN114976005A (en) * | 2022-06-02 | 2022-08-30 | 中南大学 | Preparation method of in-situ growth polyoxometallate modified lithium ion battery positive electrode material |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004265849A (en) * | 2002-12-17 | 2004-09-24 | Yuasa Corp | Nonaqueous electrolyte battery |
| JP2008115060A (en) * | 2006-11-07 | 2008-05-22 | Catalysts & Chem Ind Co Ltd | Method for producing water dispersion containing chain silica-based fine particle group, water dispersion of chain silica-based fine particle group, and organic solvent dispersion thereof |
| JP2010196097A (en) * | 2009-02-24 | 2010-09-09 | Kawamura Inst Of Chem Res | Method for producing structure coated with metal oxide, and structure coated with metal oxide |
| WO2014202888A1 (en) * | 2013-06-17 | 2014-12-24 | IFP Energies Nouvelles | Method for olefin metathesis using a catalyst made from a spherical material having a hierarchised porosity comprising metal oxide particles trapped in a matrix comprising silicon oxide |
| CN105977466A (en) * | 2016-06-30 | 2016-09-28 | 湖南桑顿新能源有限公司 | Conductive oxide coated lithium ion battery tri-element anode material and preparation method thereof |
| JP2018067506A (en) * | 2016-10-21 | 2018-04-26 | 国立大学法人三重大学 | Positive electrode active material for lithium secondary battery, positive electrode of lithium secondary battery, lithium secondary battery, and method of producing positive electrode active material for lithium secondary battery |
| CN109786687A (en) * | 2018-12-17 | 2019-05-21 | 厦门大学 | A kind of preparation method to sacrifice template induced synthesis metal oxide cladding nickel-cobalt-manganese ternary anode material for lithium-ion batteries |
| CN110120515A (en) * | 2019-05-29 | 2019-08-13 | 重庆长安新能源汽车科技有限公司 | A kind of surface modification lithium-ion battery anode material and preparation method thereof |
| WO2019218327A1 (en) * | 2018-05-18 | 2019-11-21 | GM Global Technology Operations LLC | Hybrid lithium ion capacitor battery having a carbon coated separate layer and method of making the same |
| CN110803745A (en) * | 2019-12-16 | 2020-02-18 | 嘉兴市众盛环保科技有限公司 | Polyoxometallate composite particle electrode and preparation method and application thereof |
| CN111430711A (en) * | 2020-03-30 | 2020-07-17 | 新乡天力锂能股份有限公司 | Coated lithium ion battery positive electrode active material and preparation method thereof |
-
2020
- 2020-12-31 CN CN202011632347.XA patent/CN112661205A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004265849A (en) * | 2002-12-17 | 2004-09-24 | Yuasa Corp | Nonaqueous electrolyte battery |
| JP2008115060A (en) * | 2006-11-07 | 2008-05-22 | Catalysts & Chem Ind Co Ltd | Method for producing water dispersion containing chain silica-based fine particle group, water dispersion of chain silica-based fine particle group, and organic solvent dispersion thereof |
| JP2010196097A (en) * | 2009-02-24 | 2010-09-09 | Kawamura Inst Of Chem Res | Method for producing structure coated with metal oxide, and structure coated with metal oxide |
| WO2014202888A1 (en) * | 2013-06-17 | 2014-12-24 | IFP Energies Nouvelles | Method for olefin metathesis using a catalyst made from a spherical material having a hierarchised porosity comprising metal oxide particles trapped in a matrix comprising silicon oxide |
| CN105977466A (en) * | 2016-06-30 | 2016-09-28 | 湖南桑顿新能源有限公司 | Conductive oxide coated lithium ion battery tri-element anode material and preparation method thereof |
| JP2018067506A (en) * | 2016-10-21 | 2018-04-26 | 国立大学法人三重大学 | Positive electrode active material for lithium secondary battery, positive electrode of lithium secondary battery, lithium secondary battery, and method of producing positive electrode active material for lithium secondary battery |
| WO2019218327A1 (en) * | 2018-05-18 | 2019-11-21 | GM Global Technology Operations LLC | Hybrid lithium ion capacitor battery having a carbon coated separate layer and method of making the same |
| CN109786687A (en) * | 2018-12-17 | 2019-05-21 | 厦门大学 | A kind of preparation method to sacrifice template induced synthesis metal oxide cladding nickel-cobalt-manganese ternary anode material for lithium-ion batteries |
| CN110120515A (en) * | 2019-05-29 | 2019-08-13 | 重庆长安新能源汽车科技有限公司 | A kind of surface modification lithium-ion battery anode material and preparation method thereof |
| CN110803745A (en) * | 2019-12-16 | 2020-02-18 | 嘉兴市众盛环保科技有限公司 | Polyoxometallate composite particle electrode and preparation method and application thereof |
| CN111430711A (en) * | 2020-03-30 | 2020-07-17 | 新乡天力锂能股份有限公司 | Coated lithium ion battery positive electrode active material and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113968593A (en) * | 2021-09-30 | 2022-01-25 | 广东邦普循环科技有限公司 | Method for recovering and treating ternary material micro powder and application thereof |
| CN114772574A (en) * | 2022-05-31 | 2022-07-22 | 蜂巢能源科技股份有限公司 | Method for doping cathode material by using heteropoly acid and/or heteropoly acid salt, cathode material and application |
| CN114772574B (en) * | 2022-05-31 | 2023-12-05 | 蜂巢能源科技股份有限公司 | Method for doping positive electrode material by using heteropolyacid and/or heteropolyacid salt, positive electrode material and application |
| CN114976005A (en) * | 2022-06-02 | 2022-08-30 | 中南大学 | Preparation method of in-situ growth polyoxometallate modified lithium ion battery positive electrode material |
| CN114976005B (en) * | 2022-06-02 | 2024-01-30 | 中南大学 | Preparation method of in-situ growth polyoxometallate modified lithium ion battery anode material |
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