CN116779871B - Lithium lanthanum zirconate coated and modified cathode material, preparation method thereof and lithium ion battery - Google Patents
Lithium lanthanum zirconate coated and modified cathode material, preparation method thereof and lithium ion battery Download PDFInfo
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- RJEIKIOYHOOKDL-UHFFFAOYSA-N [Li].[La] Chemical compound [Li].[La] RJEIKIOYHOOKDL-UHFFFAOYSA-N 0.000 title claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 9
- 239000010406 cathode material Substances 0.000 title description 8
- 239000013096 zirconium-based metal-organic framework Substances 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 239000007774 positive electrode material Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000010405 anode material Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000011247 coating layer Substances 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 11
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 9
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 8
- 239000002105 nanoparticle Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 56
- 238000003756 stirring Methods 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 12
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000008139 complexing agent Substances 0.000 claims description 8
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 239000007790 solid phase Substances 0.000 claims description 7
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 150000002603 lanthanum Chemical class 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- -1 zirconium ions Chemical class 0.000 claims description 5
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 150000003754 zirconium Chemical class 0.000 claims description 4
- 229910013716 LiNi Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 3
- 239000012621 metal-organic framework Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 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
- 239000007788 liquid Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 10
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 3
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 238000006138 lithiation reaction Methods 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 44
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 18
- 235000019441 ethanol Nutrition 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000725 suspension Substances 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 6
- 229910052746 lanthanum Inorganic materials 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000011572 manganese Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- FYNXQOUDSWHQQD-UHFFFAOYSA-N tantalum(5+) pentanitrate Chemical compound [Ta+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYNXQOUDSWHQQD-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910017273 Ni0.8Mn0.1Co0.1(OH)2 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- LDPWMGUFXYRDRG-UHFFFAOYSA-I niobium(5+) pentaacetate Chemical compound [Nb+5].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O LDPWMGUFXYRDRG-UHFFFAOYSA-I 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 239000005341 toughened glass Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910016783 Ni0.5Mn0.5(OH)2 Inorganic materials 0.000 description 1
- 229910017095 Ni0.6Mn0.2Co0.2 Inorganic materials 0.000 description 1
- 229910017223 Ni0.8Co0.1Mn0.1(OH)2 Inorganic materials 0.000 description 1
- 229910017288 Ni0.8Mn0.2(OH)2 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 description 1
- 229910000331 cadmium sulfate Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NXKAMHRHVYEHER-UHFFFAOYSA-J hafnium(4+);disulfate Chemical compound [Hf+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O NXKAMHRHVYEHER-UHFFFAOYSA-J 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 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
Abstract
The invention belongs to the technical field of lithium ion battery materials, and discloses a coated and modified lithium ion battery positive electrode material, which comprises a matrix and a coating layer positioned on the surface of the matrix, wherein the coating layer is lanthanum lithium zirconate doped with at least one metal element in Ta, hf, cd, cu, Y, nb, and the coating layer is nano particles. The Zr-MOF is synthesized by a liquid phase method, the Zr-MOF is coated on the surface of the precursor by electrostatic adsorption, doped metal ions are further adsorbed on the surface of the Zr-MOF by means of physical adsorption of the Zr-MOF, and finally the anode material doped with metal elements is prepared by combining a gel method with a lithiation sintering method, so that the preparation method is simple, the flow is short, and no toxic and harmful substances are generated in the preparation process.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to coating modification of a positive electrode material.
Background
The lithium ion battery anode material generally contains transition metal elements such as nickel, cobalt, manganese and the like. The transition metal elements form solid solution, and atoms can be mixed and arranged in any proportion. Nickel rise increases battery capacity, but high nickel materials reduce battery cycle life and stability. Modification of the high nickel positive electrode material is a major means of maintaining battery capacity while improving cycle life and stability of the battery.
The lithium lanthanum zirconate is a garnet-like solid electrolyte, has good chemical stability, and can be used as a coating material to modify the anode material so as to effectively improve the performance of the anode material. Patent document with publication number of CN109461917A discloses a preparation method of a lanthanum zirconate in-situ coated high-nickel ternary cathode material, wherein the high-nickel ternary cathode material is added into an anhydrous organic solvent, then a lanthanum source is added and stirred to obtain a black suspension a; adding a zirconium source into an anhydrous organic solvent, and stirring to obtain a solution b, wherein the molar ratio of zirconium element in the zirconium source to lanthanum element in the lanthanum source is 1:1; adding the suspension a into the solution b, stirring, performing ultrasonic treatment, and aging to obtain gel; evaporating the obtained gel to dryness to obtain xerogel powder; grinding the xerogel powder and roasting to obtain the product. The coating obtained by the method is uneven, thicker and poorer in performance. Patent document with publication number of CN114068894A discloses a preparation method of a lanthanum lithium zirconate coated ternary cathode material, which adopts a coprecipitation method to prepare a ternary precursor of coated lanthanum lithium zirconate, then mixing lithium for sintering, and simultaneously reacting the lanthanum lithium zirconate and the ternary precursor with a lithium source to form the lanthanum lithium zirconate coated ternary material. However, the variable factors are too many in the process of preparing the lanthanum lithium zirconate by coprecipitation reaction, the regulation and control are not easy, the morphology and structure of the synthesized lanthanum lithium zirconate are also greatly different, and the performances of the final lanthanum lithium zirconate coated ternary material are inconsistent.
Disclosure of Invention
Aiming at the problems in the background technology, the invention aims to provide a metal-doped lanthanum lithium zirconate coated and modified lithium ion battery anode material and a preparation method thereof.
In order to achieve the above object, the present invention provides the following specific technical solutions.
Firstly, the invention provides a coating modified lithium ion battery anode material, which comprises a matrix and a coating layer positioned on the surface of the matrix, wherein the chemical expression of the matrix is LiNi m Mn n Co 1-m-n O 2 Wherein m is more than or equal to 0.5 and less than or equal to 0.8,0.1, n is more than or equal to 0.5; the coating layer is lithium lanthanum zirconate doped with at least one metal element in Ta, hf, cd, cu, Y, nb, and the coating layer is nano particles.
Secondly, the invention provides a preparation method of the coating modified lithium ion battery anode material, which comprises the following steps:
step S1, dissolving zirconium salt in deionized water or an organic solvent I to form a solution A; dissolving an organic complexing agent in deionized water or an organic solvent II to form a solution B; mixing the solution A and the solution B, stirring, reacting, separating solid from liquid after the reaction is finished, washing, and drying the solid phase to obtain Zr-MOF;
step S2, precursor Ni m Mn n Co 1-m-n (OH) 2 Dispersing in an organic solvent III, adding Zr-MOF obtained in the step S1, then adding lanthanum salt and at least one salt of the doped metal element Ta, hf, cd, cu, Y, nb, heating and stirring to form gel, drying the gel, mixing with a lithium source, and calcining to obtain the coated modified lithium ion battery anode material.
In a further preferred embodiment, the zirconium salt is at least one of zirconium nitrate, zirconium acetate, zirconium sulfate; the organic complexing agent is at least one of trimesic acid, isophthalic acid and phthalic acid; the organic solvent I and the organic solvent II are at least one of ethanol, methanol, glycol, acetone and N, N-dimethylformamide; the organic solvent III is at least one of ethanol, methanol and glycol.
In a further preferred embodiment, the concentration of zirconium ions in the solution A is from 0.1 to 2mol/L; the concentration of the organic complexing agent in the solution B is 0.1-1mol/L.
In a further preferred embodiment, in step S1, the amount of solution a and solution B mixed is 1, according to the ratio of the molar amount of zirconium element to the molar amount of organic complexing agent: 5-10.
In a further preferred scheme, the lanthanum salt is at least one of lanthanum nitrate and lanthanum acetate; the metal-doped salt is at least one of nitrate, acetate and sulfate.
In a further preferred embodiment, in step S2, the precursor, zr-MOF, lanthanum salt, salt of at least one metal element of the doping metal Ta, hf, cd, cu, Y, nb, and the molar ratio of the amount of lithium in the lithium source is 1:0.04-0.12:0.06-0.18:0.01-0.03:1.1-1.3.
In a further preferred embodiment, in step S2, the heating temperature is 50 to 80 ℃.
In a further preferred scheme, in the step S2, the drying temperature is 100-140 ℃, and the drying time is 12-36 h.
In a further preferred scheme, in the step S2, the calcination temperature is 800-1100 ℃, the calcination atmosphere is oxygen or air, and the calcination time is 8-20 h.
Based on the same inventive concept, the invention provides a lithium ion battery, which comprises the coating modified lithium ion battery anode material.
The technical scheme provided by the invention has the following obvious beneficial effects:
the coating layer provided by the invention is nano particles and doped with at least one metal element in Ta, hf, cd, cu, Y, nb, so that the rapid transmission of lithium ions can be promoted, the conductivity of the material can be greatly improved, and the first coulomb efficiency of the battery can be effectively improved.
According to the preparation method, firstly, zr-MOF is synthesized through a liquid phase method, the surface of a precursor is coated with the Zr-MOF through electrostatic adsorption, doped metal ions are further adsorbed on the surface of the Zr-MOF through physical adsorption of the Zr-MOF, and finally, the anode material doped with metal elements is prepared through a gel method and a lithiation sintering method, so that the preparation method is simple, the flow is short, and no toxic and harmful substances are generated in the preparation process.
Drawings
Fig. 1 is an XRD pattern of the coating obtained in example 1.
Fig. 2 is an SEM image of the positive electrode material obtained in example 2.
Fig. 3 is an HRTEM image of the positive electrode material obtained in example 1.
Fig. 4 is a TEM image of the positive electrode material obtained in comparative example 2-2.
Fig. 5 is an SEM image of the positive electrode material obtained in comparative examples 2 to 3.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1
(1) 4mmol of zirconium nitrate was dissolved in 40ml of ethanol to form solution A. 20mmol of isophthalic acid was dissolved in 60ml of ethanol to form solution B. And uniformly mixing the solution A and the solution B, stirring and reacting for 6 hours, and centrifugally washing and drying the reaction product to obtain the Zr-MOF.
(2) To 100ml of ethanol, 4mmol of Zr-MOF in the step (1) was added, and after stirring for 1 hour, 6mmol of lanthanum nitrate, 0.8mmol of tantalum nitrate, and 0.2mmol of copper nitrate were added, and after heating at 60℃for 4 hours, stirring was performed to form a gel, and after drying at 120℃for 12 hours, a coating was obtained.
Fig. 1 is an XRD pattern of the coating obtained in example 1, from which it can be seen that the phases are lithium lanthanum zirconate doped with copper and tantalum.
Example 2
(1) 4mmol of zirconium nitrate was dissolved in 40ml of ethanol to form solution A. 20mmol of isophthalic acid was dissolved in 60ml of ethanol to form solution B. And uniformly mixing the solution A and the solution B, stirring and reacting for 6 hours, and centrifugally washing and drying the reaction product to obtain the Zr-MOF.
(2) 0.1mol of ternary precursor Ni 0.8 Mn 0.1 Co 0.1 (OH) 2 Dispersing in 100ml ethanol, adding 4mmol of Zr-MOF in step (1), stirring for 1h, adsorbing Zr-MOF on the surface of ternary precursor by electrostatic attraction, adding 6mmol of lanthanum nitrate, 0.8mmol of tantalum nitrate and 0.2mmol of copper nitrate, heating at 60deg.C for 4h, stirring to form gel, drying at 120deg.C for 12h, mixing with 0.115mol of lithium hydroxide in solid phase,calcining at 850 ℃ for 12 hours to obtain the positive electrode material.
Fig. 2 is an SEM image of the positive electrode material obtained in example 1, and it can be seen from the image that the prepared positive electrode material is in the shape of micrometer sphere, and has uniform size distribution and 8-10 micrometers.
Fig. 3 is an HRTEM diagram of the positive electrode material obtained in example 1, and it can be seen that the outer layer is a nanoparticle coating layer, the inner layer is the positive electrode material, the coating layer is uniform, and the nanoparticle sizes are uniform. As can be seen from the combination of FIG. 1 and lattice fringe analysis, the outer layer is a coating.
Comparative example 2-1
Comparative example 2-1 is different from example 2 in that: the coating layer is not doped with metal elements.
(1) 4mmol of zirconium nitrate was dissolved in 40ml of ethanol to form solution A. 20mmol of isophthalic acid was dissolved in 60ml of ethanol to form solution B. Uniformly mixing the solution A and the solution B, stirring and reacting for 6 hours, and centrifugally washing and drying a reaction product to obtain Zr-MOF;
(2) 0.1mol of ternary precursor Ni 0.8 Mn 0.1 Co 0.1 (OH) 2 Dispersing in 100ml of ethanol, adding 4mmol of Zr-MOF in the step (1), stirring for 1h, adsorbing the Zr-MOF on the surface of the ternary precursor by virtue of electrostatic attraction, then adding 6mmol of lanthanum nitrate, heating at 60 ℃ for 4h, stirring to form gel, drying at 120 ℃ for 12h, then carrying out solid-phase mixing with 0.115mol of lithium hydroxide, and calcining at 850 ℃ for 12h to obtain the cathode material.
Comparative examples 2 to 2
Comparative example 2-2 a lithium lanthanum zirconate coated cathode material was prepared according to example 1 of patent document CN114068894 a:
step 1, zirconium sulfate and lanthanum sulfate are mixed according to a mole ratio Zr: la=2: 3 preparing a solution with the total metal ion concentration of 15.0mmol/L, adding 2000L of the mixed solution as a base solution into a reaction kettle, adding 478kg of Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 Adding the ternary precursor into the base solution, and uniformly mixing to obtain a mixed suspension; wherein the mass ratio of the ternary precursor to the zirconium ions in the mixed suspension is 1:0.02, and the ternary precursor and lanthanum ions are dissociatedThe mass ratio of the seeds is 1:0.03, and the concentration of the ternary precursor in the mixed suspension is 239g/L;
step 2, pumping a precipitant solution into the reaction kettle, performing coprecipitation reaction for 3 hours at 25 ℃, and aging for 1 hour to obtain a ternary precursor wrapping a lithium lanthanum zirconate precursor; wherein the precipitant solution is ammonia water; the concentration of the precipitant solution is 4.57mol/L, and the feeding amount of the precipitant solution is 30L/h;
step 3, washing, drying, sieving, removing iron from the ternary precursor coated with the lithium lanthanum zirconate precursor, mixing with a lithium source, and preserving heat for 12 hours at 850 ℃ to obtain the lithium lanthanum zirconate coated LiNi 0.8 Co 0.1 Mn 0.1 O 2 A ternary material; wherein the lithium source is lithium hydroxide; the molar ratio of lithium source to precursor was 1.15:1.
fig. 4 is a TEM image of the positive electrode material obtained in comparative example 2-2, which is a micron-sized polymer particle with nanoparticles of different sizes distributed on the surface.
Comparative examples 2 to 3
Comparative examples 2-3 were carried out according to example 1 of patent document CN109461917 a:
(1) Weighing 10.0000g of LiNi 0.8 Co 0.1 Mn 0.1 O 2 Adding the powder into absolute ethyl alcohol, adding 0.1513g of lanthanum nitrate (hexahydrate), and stirring at a stirring rate of 80 rpm for 30min to obtain black suspension a;
(2) 0.1574g of tetrabutyl zirconate (mass fraction is 85%) is dispersed in 40mL of absolute ethanol and stirred for 30min at a stirring rate of 80 revolutions per minute to form a transparent and uniform solution b;
(3) Adding the suspension a into the solution b, stirring for 3 hours at a stirring speed of 80 revolutions per minute, performing ultrasonic treatment for 3 hours under ultrasonic power of 80W, and aging for 12 hours to obtain gel;
(4) Evaporating the gel at 80 ℃ to obtain xerogel powder;
(5) Grinding the xerogel powder for 30min, and roasting for 12h at 400 ℃ in air atmosphere to form LiNi with lanthanum zirconate coated on the surface 0.8 Co 0.1 Mn 0.1 O 2 And a positive electrode material.
Fig. 5 is an SEM image of the cathode material obtained in comparative examples 2-3, the material was in the shape of micrometer spheres, and white particles with larger sizes were obviously distributed on the surface of the material, indicating that the surface coating layer was unevenly distributed.
Example 3
(1) 12mmol of zirconium acetate was dissolved in 12ml of methanol to form solution A. 96mmol of trimesic acid was dissolved in 96ml of ethylene glycol to form solution B. Uniformly mixing the solution A and the solution B, stirring and reacting for 8 hours, and centrifugally washing and drying a reaction product to obtain Zr-MOF;
(2) 0.1mol of ternary precursor Ni 0.6 Mn 0.2 Co 0.2 (OH) 2 Dispersing in 100ml of ethanol, adding 12mmol of Zr-MOF in the step (1), stirring for 1h, adsorbing the Zr-MOF on the surface of the ternary precursor by virtue of electrostatic attraction, then adding 18mmol of lanthanum nitrate, 1mmol of hafnium sulfate and 2mmol of niobium acetate, heating at 60 ℃ for 4h, stirring to form gel, drying at 100 ℃ for 36h, then carrying out solid-phase mixing with 0.13mol of lithium hydroxide, and calcining at 800 ℃ for 20h to obtain the positive electrode material.
Example 4
(1) 8mmol of zirconium acetate was dissolved in 4ml of acetone to form solution A. 80mmol of phthalic acid was dissolved in 160ml of ethanol to form solution B. Uniformly mixing the solution A and the solution B, stirring and reacting for 6 hours, and centrifugally washing and drying a reaction product to obtain Zr-MOF;
(2) 0.1mol of precursor Ni 0.8 Mn 0.2 (OH) 2 Dispersing in 100ml of ethanol, adding 8mmol of Zr-MOF in the step (1), stirring for 1h, adsorbing the Zr-MOF on the surface of the ternary precursor by virtue of electrostatic attraction, then adding 10mmol of lanthanum acetate, 1mmol of cadmium sulfate, 0.5mmol of yttrium nitrate and 0.5mmol of niobium acetate, heating at 60 ℃ for 4h, stirring to form gel, drying at 140 ℃ for 12h, mixing with 0.11mol of lithium hydroxide in a solid phase, and calcining at 1100 ℃ for 8h to obtain the anode material.
Example 5
(1) 8mmol of zirconium nitrate was dissolved in 20ml of ethanol to form solution A. 60mmol of isophthalic acid were dissolved in 600ml of N, N-dimethylformamide to form solution B. Uniformly mixing the solution A and the solution B, stirring and reacting for 6 hours, and centrifugally washing and drying a reaction product to obtain Zr-MOF;
(2) 0.1mol of precursor Ni 0.5 Mn 0.5 (OH) 2 Dispersing in 100ml of ethanol, adding 8mmol of Zr-MOF in the step (1), stirring for 1h, adsorbing the Zr-MOF on the surface of the ternary precursor by virtue of electrostatic attraction, then adding 8mmol of lanthanum nitrate, 0.8mmol of tantalum nitrate and 0.4mmol of copper nitrate, heating at 60 ℃ for 4h, stirring to form gel, drying at 120 ℃ for 12h, then carrying out solid-phase mixing with 0.115mol of lithium hydroxide, and calcining at 1000 ℃ for 16h to obtain the anode material.
The positive electrode materials obtained in examples 2-5 and comparative examples 2-1 to 2-3 were mixed with Acetylene Black (AB) as a conductive agent and polyvinylidene fluoride (PVDF) as a binder in a mass ratio of 8:1:1, and N-methylpyrrolidone (NMP) as a solvent, and the mixture was stirred in a small beaker at a rotational speed of 800r/min for 2 hours to obtain a slurry. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, horizontally placing the current collector aluminum foil on toughened glass, transferring the toughened glass into a vacuum drying oven at 85 ℃ for drying for 4 hours, preparing a pole piece with the diameter of 12mm by using a punching sheet, then drying the pole piece at 105 ℃ for 4 hours in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content being lower than 0.1ppm and filled with argon atmosphere for 4 hours to reduce the water absorbed by the pole piece in the transferring process, and then assembling the CR2032 button cell in the glove box. The battery uses a pure metal lithium sheet with a diameter of 16mm and a thickness of 0.5mm as a negative electrode, and a porous polyethylene film with a diameter of 18mm and a model Celgard2300 as a separator.
After the battery is assembled and aged for 12 hours, the charge and discharge tests with different potentials are carried out. After 3 cycles of activation at 3-4.3V voltage and 0.1C magnification, the cycle was again 200 cycles at 2C. The results are shown in Table 1.
TABLE 1
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. The preparation method of the coating modified lithium ion battery anode material is characterized by comprising the following steps of:
step S1, dissolving zirconium salt in deionized water or an organic solvent I to form a solution A; dissolving an organic complexing agent in deionized water or an organic solvent II to form a solution B; mixing the solution A and the solution B, stirring, reacting, separating solid from liquid after the reaction is finished, washing, and drying the solid phase to obtain Zr-MOF;
step S2, precursor Ni m Mn n Co 1-m-n (OH) 2 Dispersing in an organic solvent III, adding Zr-MOF obtained in the step S1, then adding lanthanum salt and at least one salt of the doped metal element Ta, hf, cd, cu, Y, nb, heating and stirring to form gel, drying the gel, mixing with a lithium source, and calcining to obtain the coated modified lithium ion battery anode material;
the coated and modified lithium ion battery anode material comprises a matrix and a coating layer positioned on the surface of the matrix, wherein the chemical expression of the matrix is LiNi m Mn n Co 1-m-n O 2 Wherein m is more than or equal to 0.5 and less than or equal to 0.8,0.1, n is more than or equal to 0.5; the coating layer is lithium lanthanum zirconate doped with at least one metal element in Ta, hf, cd, cu, Y, nb, and the coating layer is nano particles.
2. The method according to claim 1, wherein the zirconium salt is at least one of zirconium nitrate, zirconium acetate, zirconium sulfate; the organic complexing agent is at least one of trimesic acid, isophthalic acid and phthalic acid; the organic solvent I and the organic solvent II are at least one of ethanol, methanol, glycol, acetone and N, N-dimethylformamide; the organic solvent III is at least one of ethanol, methanol and glycol; the lanthanum salt is at least one of lanthanum nitrate and lanthanum acetate; the metal-doped salt is at least one of nitrate, acetate and sulfate.
3. The preparation method according to claim 1 or 2, wherein the concentration of zirconium ions in the solution a is 0.1 to 2mol/L; the concentration of the organic complexing agent in the solution B is 0.1-1mol/L.
4. The preparation method according to claim 1 or 2, wherein in step S1, the amount of the solution a and the solution B to be mixed is 1 in terms of the molar ratio of the zirconium element to the organic complexing agent: 5-10.
5. The method of claim 1, wherein in step S2, the molar ratio of the precursor, zr-MOF, lanthanum salt, salt of at least one metal element of the doping metal Ta, hf, cd, cu, Y, nb, lithium in the lithium source is 1:0.04-0.12:0.06-0.18:0.01-0.03:1.1-1.3.
6. The method according to claim 1, wherein in step S2, the heating is performed at a temperature of 50 to 80 ℃.
7. The method according to claim 1, wherein in step S2, the drying temperature is 100 to 140 ℃.
8. The method according to claim 1, wherein in the step S2, the calcination temperature is 800-1100 ℃, and the calcination atmosphere is an oxygen or air atmosphere.
9. A lithium ion battery, characterized by comprising the positive electrode material of the lithium ion battery prepared by the preparation method of any one of claims 1-8.
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