CN114171735A - Nickel-manganese-tungsten lithium ion battery positive electrode material and preparation method thereof - Google Patents
Nickel-manganese-tungsten lithium ion battery positive electrode material and preparation method thereof Download PDFInfo
- Publication number
- CN114171735A CN114171735A CN202110286928.0A CN202110286928A CN114171735A CN 114171735 A CN114171735 A CN 114171735A CN 202110286928 A CN202110286928 A CN 202110286928A CN 114171735 A CN114171735 A CN 114171735A
- Authority
- CN
- China
- Prior art keywords
- nickel
- manganese
- tungsten
- ion battery
- lithium ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 67
- MLRVVBYMRQXIFO-UHFFFAOYSA-N [W].[Mn].[Ni].[Li] Chemical compound [W].[Mn].[Ni].[Li] MLRVVBYMRQXIFO-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000007774 positive electrode material Substances 0.000 title claims description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 86
- 239000011572 manganese Substances 0.000 claims abstract description 67
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 63
- JYGSTJWDZZCBSS-UHFFFAOYSA-N [W].[Mn].[Ni] Chemical compound [W].[Mn].[Ni] JYGSTJWDZZCBSS-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000010405 anode material Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000498 ball milling Methods 0.000 claims abstract description 32
- 239000002243 precursor Substances 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 27
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 20
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 16
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 15
- 238000004729 solvothermal method Methods 0.000 claims abstract description 13
- 239000010937 tungsten Substances 0.000 claims abstract description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 8
- 239000012716 precipitator Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 238000004321 preservation Methods 0.000 claims abstract description 5
- 238000001556 precipitation Methods 0.000 claims description 37
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- 238000005303 weighing Methods 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- 239000011812 mixed powder Substances 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 14
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 9
- 239000001099 ammonium carbonate Substances 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 235000013877 carbamide Nutrition 0.000 claims description 7
- 229940071125 manganese acetate Drugs 0.000 claims description 7
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 7
- 229940078494 nickel acetate Drugs 0.000 claims description 7
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 7
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229940099596 manganese sulfate Drugs 0.000 claims description 5
- 235000007079 manganese sulphate Nutrition 0.000 claims description 5
- 239000011702 manganese sulphate Substances 0.000 claims description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- 235000017550 sodium carbonate Nutrition 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- PXXRROSTRSLPET-UHFFFAOYSA-J C(C)(=O)[O-].[W+4].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-] Chemical compound C(C)(=O)[O-].[W+4].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-] PXXRROSTRSLPET-UHFFFAOYSA-J 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 4
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 claims description 4
- 229910013100 LiNix Inorganic materials 0.000 claims description 3
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 3
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 229910013716 LiNi Inorganic materials 0.000 abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 15
- 239000000243 solution Substances 0.000 description 68
- 239000000463 material Substances 0.000 description 57
- 239000007788 liquid Substances 0.000 description 24
- 239000010406 cathode material Substances 0.000 description 17
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 239000011888 foil Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 235000012501 ammonium carbonate Nutrition 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- -1 oxygen ions Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- 241000255789 Bombyx mori Species 0.000 description 1
- 229910002983 Li2MnO3 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 229910006525 α-NaFeO2 Inorganic materials 0.000 description 1
- 229910006596 α−NaFeO2 Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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 anode materials, and particularly relates to a nickel-manganese-tungsten lithium ion battery anode material and a preparation method thereofxMnyWzO2The anode material is prepared by sequentially carrying out solvothermal reaction and high-temperature solid-phase reaction; the solvent thermal reaction is to carry out solvent thermal reaction on a nickel source, a manganese source and a tungsten source compound in a water solvent containing a precipitator to prepare nickel-manganese-tungsten precursor powder; the high-temperature solid-phase reaction is that nickel-manganese-tungsten precursor powder and a lithium source compound are subjected to ball milling and mixing, and then are subjected to temperature rise sintering and heat preservation sintering in an oxygen atmosphere, so that the nickel-manganese-tungsten lithium ion battery anode material LiNi prepared by the method isxMnyWzO2Has excellent electrochemical activityStructural stability, safety performance.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to a nickel-manganese-tungsten lithium ion battery anode material and a preparation method thereof.
Background
As the demand of large-scale equipment such as electric vehicles and energy storage systems for lithium ion batteries is increasing, lithium ion positive electrode materials with high specific capacity or high working voltage have received wide attention as alternative positive electrode materials. Energy density largely determines the large-scale industrial application of electric vehicles (driving range) or energy storage systems (calendar life), so achieving high energy density of batteries remains a challenging problem.
The anode material of lithium ion battery used in electric automobile is layered Li [ Ni ]xCoy(Al/Mn)1-x-y]O2(Al ═ NCA or Mn ═ NCM) oxide materials, both positive electrode materials being derived from layered LiNiO2The NCM and NCA cathode materials with the Ni content of more than 80 percent can promote the formation of an electroless electrochemically active rock salt phase due to the increase of the Ni content, an inactive rock salt structure NiO phase is formed on the surface of the NCM or NCA, the migration of a nickel layer in transition metal to a lithium layer is accelerated at high cut-off voltage, the residual alkali on the surface of the material is increased, the cation shuffling is accelerated, a side reaction between an electrode and an electrolyte is caused, the conversion to the inactive rock salt phase is accelerated, and the cathode materials with the theoretical capacity of 270mAh/g are widely applied and successfully commercialized due to high capacity and low costThe dynamic performance is deteriorated; when charging and discharging are performed at a high voltage, Ni and Co are oxidized into high valence and then oxygen ions are oxidized to cause O2The release of gas and irreversible structural changes further exacerbate the mechanical disruption of the crystal structure. Therefore, the inherent instability of the positive electrode directly reduces the capacity retention rate and the thermal stability of the material, and the oxygen precipitation phenomenon of the material is aggravated, so that the battery has the defects of rapid capacity fading, poor thermal stability, reduced electrochemical performance and the like.
Patent CN109921007A discloses a high-nickel lithium-rich cathode material, its preparation method and application, the chemical formula of the high-nickel lithium-rich cathode material is Li1+z(Ni0.5+xMn0.5-x-yMy)1-zO2Or Li1+z(Ni0.5+x-yMn0.5-xMy)1-zO2Although the patent mentions that "the VIB transition metal element can present a higher oxidation state positive 6 valence, particularly molybdenum and tungsten, and can generate a strong interaction with oxygen ions, so that the structure can be maintained relatively stable," compared with other transition metal elements, the high nickel lithium-rich cathode material has the advantages of easier activation of more redox pairs, contribution to more capacity, structural stability enhancement and the like, and further has more excellent electrochemical performance ", the high nickel lithium-rich cathode material in the patent scheme is Li2MnO3And LiM' O2The solid solution is an alloy phase with solute atoms dissolved in solvent crystal lattices and still kept in a solvent type, the material with the structure has the problems of poor multiplying power and cycle performance, voltage attenuation and the like, particularly, the voltage in the cycle process is seriously attenuated, the lithium ion charging and discharging mechanism is complex, and meanwhile, the upper limit of the voltage of the material is as high as 4.8V (depending on Li)2MnO3The activation contribution capacity under high voltage), and the electrolyte matched with the activation contribution capacity needs to be a high-voltage electrolyte, so that the universality is not high. In addition, the raw materials used in the method are nitrates, the products produced in the preparation process can cause environmental pollution, and certain complexing agents added in the use have great harm to human bodies, so the method cannot be used for industrial production.
Therefore, in order to solve the problems, the invention provides a positive electrode material LiNi which can be used for preparing a positive electrode of a lithium ion batteryxMnyWzO2The preparation method solves the problems of non-ideal electrochemical performance caused by cation mixed-row and unstable crystal structure, poor safety performance of the battery and the like.
Disclosure of Invention
The invention provides a nickel-manganese-tungsten lithium ion battery anode material and a preparation method thereof, aiming at the defects of the prior art.
The method is realized by the following technical scheme:
a positive electrode material of Ni-Mn-W Li-ion battery has a chemical formula of LiNixMnyWzO2The molar ratio of the nickel source to the manganese source to the tungsten source is x: y: z, wherein x is more than or equal to 0.8 and less than or equal to 1, y is more than or equal to 0.01 and less than or equal to 0.2, z is more than or equal to 0.01 and less than or equal to 0.2, and x + y + z is 1.
The preparation method of the nickel-manganese-tungsten lithium ion battery anode material comprises the following steps of sequentially carrying out solvothermal reaction and high-temperature solid-phase reaction on the anode material; the solvent thermal reaction is to carry out solvent thermal reaction on a nickel source, a manganese source and a tungsten source compound in a water solvent containing a precipitator to prepare nickel-manganese-tungsten precursor powder; the high-temperature solid-phase reaction is to perform ball milling and mixing on nickel-manganese-tungsten precursor powder and a lithium source compound, and then perform heating sintering and heat preservation sintering in an oxygen atmosphere.
The nickel source is any one of nickel hydroxide, nickel sulfate, nickel acetate, nickel nitrate, nickel oxalate and nickel chloride.
The manganese source is any one of manganese hydroxide, manganese sulfate, manganese acetate, manganese nitrate, manganese oxalate and manganese chloride.
The tungsten source is any one of ammonium metatungstate, sodium tungstate, tungsten acetate, tungsten oxide and tungsten chloride.
The precipitant is any one of sodium carbonate, ammonium bicarbonate, oxalic acid and urea.
The lithium source is any one of lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate and lithium oxalate.
The dosage of the precipitant is as follows according to molar ratio: (Ni + Mn + W) ═ 1-5: 1.
the solvothermal reaction is carried out at 100-300 ℃ for 5-20 h.
And (3) heating and sintering, wherein the heating rate is 1-20 ℃/min, and the sintering temperature is 700-1000 ℃.
And (3) performing heat preservation sintering, wherein the heat preservation time is 5-20 h.
A preparation method of a nickel-manganese-tungsten lithium ion battery anode material comprises the following steps:
the first step is as follows: solvothermal reaction
(1) Weighing a nickel source, a manganese source and a tungsten source, dissolving the nickel source, the manganese source and the tungsten source by using deionized water, and mixing and stirring uniformly to form a solution A; weighing a precipitator, dissolving the precipitator with deionized water, and mixing and stirring uniformly to form a solution B; dropwise adding the solution B into the solution A to form a mixed reaction solution;
(2) pouring the mixed reaction solution into a liner of a reaction kettle to carry out high-temperature hydrothermal reaction to prepare reaction precipitation solution;
(3) repeatedly washing the reaction precipitate with deionized water by a centrifugal machine under the condition that the centrifugal rotating speed is 1000-10000 r/min, and drying at 50-100 ℃ to obtain nickel-manganese-tungsten precursor powder;
the second step is that: high temperature solid phase reaction
(4) Ball-milling the nickel-manganese-tungsten precursor powder and a lithium source for 3-10 hours at the ball-milling speed of 300-800 r/min to obtain mixed powder;
(5) and (3) placing the mixed powder in a high-temperature atmosphere tube furnace, heating and sintering to 700-1000 ℃ in an oxygen atmosphere, and then preserving heat for 5-20 hours at the temperature to obtain the nickel-manganese-tungsten lithium ion battery anode material.
In the step (4), the dosage of the lithium source is 1.0-1.20 of Li/(Ni + Mn + W) in terms of molar ratio.
And (4) performing ball milling, wherein the adopted medium is any one of zirconium dioxide balls and agate balls.
Has the advantages that:
the nickel manganese tungsten lithium ion battery anode material LiNi prepared by the method of the inventionxMnyWzO2Has excellent electricityChemical activity, structural stability and safety performance are shown as follows:
the invention adopts a solvothermal reaction method to synthesize a nickel-manganese-tungsten precursor, so that precursor particles are formed by stacking nanoscale one-time sheets, and then a high-temperature solid-phase method is combined to synthesize a nanosheet structure with a loose surface (the thickness of the sheet layer is in the nanoscale), and the synthesized electrode material has nanoscale primary particles and is uniform in appearance, size and distribution, the structure is favorable for the contact of the material and electrolyte, meanwhile, the lithium ion transmission path in the electrochemical reaction process is greatly shortened, and the excellent electrochemical activity of the material is realized. The method has simple process, effectively reduces energy consumption and material loss, and is favorable for industrial preparation of materials.
More importantly: in the sintering process of the nickel-manganese-tungsten precursor and the lithium source, the lithium tungstate can react with residual lithium, so that the residual alkali amount on the surface of the material is reduced, and the electrochemical performance of the material is improved; the subsequent water washing treatment process of the material is avoided while the alkalinity of the material is reduced, so that the material synthesis step is optimized, the material preparation process is simplified, and the engineering application is facilitated.
Secondly, compared with a Nickel Manganese Cobalt (NMC) lithium ion battery material, the nickel manganese tungsten lithium ion battery anode material LiNi prepared by the methodxMnyWzO2The material has excellent cycle performance and rate performance; the key of the action mechanism is as follows: the synergistic effect of the three transition metals of Ni, Mn and W stabilizes the crystal structure of the material, reduces the mixed discharge of nickel and lithium, improves the conductivity of the material and reduces the polarization phenomenon of the material; the combined material has W-O bonds with stronger bond energy, improves the thermal stability of the material under high cut-off voltage, weakens the oxygen release capacity, and weakens the irreversible structural change, so the nickel-manganese-tungsten lithium ion battery anode material of the invention not only improves the oxygen precipitation phenomenon of the traditional material, but also improves the thermal stability of the material, thereby achieving the purpose of improving the safety performance of the lithium ion battery from the aspects of tungsten source crystal lattice stability and bond energy improvement.
Thirdly, the nickel manganese tungsten lithium ion prepared by the inventionThe battery anode material is applied to the lithium ion battery, can effectively improve the safety performance of the battery, and the thermal decomposition temperature of NMC is 212 ℃, while the nickel-manganese-tungsten lithium ion battery anode material LiNi in the inventionxMnyWzO2The decomposition temperature of the nickel manganese tungsten lithium ion battery is about 223 ℃, the thermal decomposition temperature of the battery under high cut-off voltage is improved, and meanwhile, the nickel manganese tungsten lithium ion battery anode material LiNixMnyWzO2The heat released under high cut-off voltage is far less than that of the NMC anode, which shows that the NMW anode material has excellent mechanical and chemical stability, inhibits the oxygen precipitation of the material and weakens O2Release of gases and irreversible structural changes.
Drawings
FIG. 1 is an XRD contrast spectrum of the positive electrode material and the nickel-manganese-cobalt material of the nickel-manganese-tungsten lithium ion battery prepared in example 1;
FIG. 2 is a SEM comparison of the positive electrode material and the nickel-manganese-cobalt material of the nickel-manganese-tungsten lithium ion battery prepared in example 1;
fig. 3 is an EDS spectrum of the cathode material for a nickel manganese tungsten lithium ion battery prepared in application example 1;
FIG. 4 is a curve of the charging and discharging performance of the nickel-manganese-tungsten and nickel-manganese-cobalt battery assembled in application example 1 in a range of 2.75 to 4.3V;
FIG. 5 shows the cycle performance of the nickel-manganese-tungsten and nickel-manganese-cobalt battery assembled in application example 1 at 0.5C rate in the range of 2.75-4.3V;
fig. 6 is a DSC curve of two materials charged to 4.3V using the nickel manganese tungsten and nickel manganese cobalt batteries assembled in example 1.
Detailed Description
The following is a detailed description of the embodiments of the present invention, but the present invention is not limited to these embodiments, and any modifications or substitutions in the basic spirit of the embodiments are included in the scope of the present invention as claimed in the claims.
Example 1
A preparation method of a nickel-manganese-tungsten lithium ion battery anode material comprises the following steps:
(1) weighing nickel acetate, manganese acetate and tungsten acetate according to the molar ratio of Ni, Mn and W being 0.85, 0.14 and 0.01, mixing and dissolving the nickel acetate, the manganese acetate and the tungsten acetate by using deionized water, and stirring the mixture uniformly to form a solution A; with (Ni + Mn + W): urea 1: 3.5, weighing urea according to the molar ratio, dissolving the urea in deionized water, and uniformly stirring to form a solution B; gradually dripping the solution B into the solution A to form a mixed reaction solution;
(2) pouring the mixed reaction solution into a liner of a reaction kettle, placing the reaction kettle in an oven, preserving heat for 8 hours at 180 ℃, and carrying out thermal reaction on a solvent to obtain a reaction precipitation solution;
(3) after the reaction precipitation liquid is cooled, washing the reaction precipitation liquid by deionized water through a centrifugal machine at the rotating speed of 3000r/min, and drying the precipitation liquid after repeated washing reaction at 80 ℃ through a blast drying oven to obtain nickel-manganese-tungsten precursor powder;
(4) weighing and mixing nickel-manganese-tungsten precursor powder and lithium carbonate according to the molar ratio of Li/(Ni + Mn + W) to 1.05, and performing ball milling for 5 hours at the ball milling speed of 500r/min to obtain mixed powder; wherein the ball milling medium is agate balls;
(5) the mixed powder is calcined for 7 hours at a high temperature which is increased to 750 ℃ in oxygen at a heating rate of 2 ℃/min by a high-temperature atmosphere tube furnace to obtain the cathode material LiNi of the nickel-manganese-tungsten lithium ion battery0.85Mn0.14W0.01O2。
Example 2
A preparation method of a nickel-manganese-tungsten lithium ion battery anode material comprises the following steps:
(1) weighing nickel sulfate, manganese sulfate and tungsten oxide according to the molar ratio of Ni to Mn to W of 0.90 to 0.03 to 0.07, mixing and dissolving the nickel sulfate, manganese sulfate and tungsten oxide by using deionized water, and stirring the mixture uniformly to form a solution A; with (Ni + Mn + W): ammonium bicarbonate 1: 2.5, dissolving ammonium bicarbonate in deionized water, stirring uniformly to form a solution B, and gradually dropping the solution B into the solution A to form a mixed reaction solution;
(2) pouring the mixed reaction solution into a liner of a reaction kettle, placing the reaction kettle in an oven, preserving heat for 10 hours at 150 ℃, and carrying out thermal reaction on a solvent to obtain a reaction precipitation solution;
(3) after the reaction precipitation liquid is cooled, washing the reaction precipitation liquid by deionized water through a centrifugal machine at the rotating speed of 5000r/min, and drying the precipitation liquid after repeated washing reaction at the temperature of 60 ℃ through a blast drying oven to obtain nickel-manganese-tungsten precursor powder;
(4) weighing and mixing nickel-manganese-tungsten precursor powder and lithium hydroxide according to the molar ratio of Li/(Ni + Mn + W) to 1.10, and performing ball milling for 8 hours at the ball milling speed of 450r/min to obtain mixed powder; wherein the ball milling medium is zirconium dioxide balls;
(5) the mixed powder is calcined for 15 hours at a high temperature which is increased to 700 ℃ in oxygen at a heating rate of 10 ℃/min by a high-temperature atmosphere tube furnace, and the cathode material LiNi of the nickel-manganese-tungsten lithium ion battery is obtained0.90Mn0.03W0.07O2。
Example 3
A preparation method of a nickel-manganese-tungsten lithium ion battery anode material comprises the following steps:
(1) weighing nickel acetate, manganese acetate and ammonium tungstate according to the molar ratio of Ni to Mn to W of 0.88 to 0.10 to 0.02, mixing and dissolving the nickel acetate, the manganese acetate and the ammonium tungstate with deionized water, stirring the mixture uniformly to form a solution A, and mixing the solution A with the weight ratio of (Ni + Mn + W): oxalic acid is 1: 1, dissolving oxalic acid in deionized water, stirring uniformly to form a solution B, and gradually dropping the solution B into the solution A to form a mixed reaction solution;
(2) pouring the mixed reaction solution into a liner of a reaction kettle, placing the reaction kettle in an oven, preserving heat for 5 hours at 200 ℃, and carrying out solvothermal reaction to obtain a reaction precipitation solution;
(3) after the reaction precipitation liquid is cooled, washing the reaction precipitation liquid by deionized water through a centrifugal machine at the rotating speed of 8000r/min, and drying the precipitation liquid after repeated washing reaction at the temperature of 100 ℃ through a blast drying box to obtain nickel-manganese-tungsten precursor powder;
(4) weighing and mixing nickel-manganese-tungsten precursor powder and lithium hydroxide according to the molar ratio of Li/(Ni + Mn + W) being 1.07, and performing ball milling for 10 hours at the ball milling speed of 300r/min to obtain mixed powder; wherein the ball milling medium is zirconium dioxide balls;
(5) the mixed powder is calcined for 12 hours at a high temperature of 800 ℃ in oxygen at a heating rate of 15 ℃/min in a high-temperature atmosphere tube furnace to obtain the cathode material LiNi of the nickel-manganese-tungsten lithium ion battery0.88Mn0.10W0.02O2。
Example 4
A preparation method of a nickel-manganese-tungsten lithium ion battery anode material comprises the following steps:
(1) weighing nickel chloride, manganese chloride and tungsten chloride according to the molar ratio of Ni to Mn to W of 0.82 to 0.08 to 0.10, mixing and dissolving the nickel chloride, the manganese chloride and the tungsten chloride by using deionized water, and stirring the mixture uniformly to form a solution A; with (Ni + Mn + W): sodium carbonate 1: weighing sodium carbonate according to the molar ratio of 1.5, dissolving the sodium carbonate in deionized water, uniformly stirring to form a solution B, and gradually dropping the solution B into the solution A to form a mixed reaction solution;
(2) pouring the mixed reaction solution into a liner of a reaction kettle, placing the reaction kettle in an oven, preserving heat for 18 hours at 120 ℃, and carrying out thermal reaction on a solvent to obtain a reaction precipitation solution;
(3) after the reaction precipitation liquid is cooled, washing the reaction precipitation liquid by deionized water through a centrifugal machine at the rotating speed of 4500r/min, and drying the precipitation liquid after repeated washing reaction at 90 ℃ through a blast drying box to obtain nickel-manganese-tungsten precursor powder;
(4) weighing and mixing nickel-manganese-tungsten precursor powder and lithium nitrate according to the molar ratio of Li/(Ni + Mn + W) to 1.09, and performing ball milling at the ball milling speed of 700r/min for 8 hours to obtain mixed powder; wherein the ball milling medium is zirconium dioxide balls;
(5) the mixed powder is calcined for 5 hours at a high temperature of 900 ℃ in oxygen at a heating rate of 3 ℃/min in a high-temperature atmosphere tubular furnace to obtain the cathode material LiNi of the nickel-manganese-tungsten lithium ion battery0.82Mn0.08W0.10O2。
Example 5
A preparation method of a nickel-manganese-tungsten lithium ion battery anode material comprises the following steps:
(1) weighing starting raw materials such as nickel hydroxide, manganese hydroxide and sodium tungstate according to the molar ratio of Ni to Mn to W of 0.93 to 0.02 to 0.05, mixing and dissolving the starting raw materials by using deionized water, stirring the mixture uniformly to form a solution A, and then mixing the solution A with the molar ratio of (Ni + Mn + W): ammonium carbonate 1: 4, dissolving ammonium carbonate in deionized water, uniformly stirring to form a solution B, and gradually dropping the solution B into the solution A to form a mixed reaction solution;
(2) pouring the mixed reaction solution into a liner of a reaction kettle, placing the reaction kettle in an oven, preserving heat for 6 hours at 220 ℃, and carrying out solvothermal reaction to obtain a reaction precipitation solution;
(3) after the reaction precipitation liquid is cooled, washing the reaction precipitation liquid by deionized water through a centrifugal machine at the rotating speed of 8500r/min, and drying the precipitation liquid after repeated washing reaction at 50 ℃ through a blast drying oven to obtain nickel-manganese-tungsten precursor powder;
(4) weighing and mixing nickel-manganese-tungsten precursor powder and lithium carbonate according to the molar ratio of Li/(Ni + Mn + W) to 1.16, and performing ball milling for 8 hours at the ball milling speed of 550r/min to obtain mixed powder; wherein the ball milling medium is agate balls;
(5) the mixed powder is calcined for 10 hours at a high temperature of 830 ℃ in oxygen at a heating rate of 5 ℃/min in a high-temperature atmosphere tube furnace to obtain the cathode material LiNi of the nickel-manganese-tungsten lithium ion battery0.93Mn0.02W0.05O2。
Example 6
A preparation method of a nickel-manganese-tungsten lithium ion battery anode material comprises the following steps:
(1) weighing nickel oxalate, manganese oxalate and tungsten oxide according to the molar ratio of Ni to Mn to W of 0.82 to 0.03 to 0.15, mixing and dissolving the nickel oxalate, the manganese oxalate and the tungsten oxide by using deionized water, stirring the mixture uniformly to form a solution A, and then mixing the solution A with the weight ratio of (Ni + Mn + W): oxalic acid is 1: 1, dissolving oxalic acid in deionized water, stirring uniformly to form a solution B, and gradually dropping the solution B into the solution A to form a mixed reaction solution;
(2) pouring the mixed reaction solution into a liner of a reaction kettle, placing the reaction kettle in an oven, preserving heat for 10 hours at 170 ℃, and carrying out solvothermal reaction to obtain a reaction precipitation solution;
(3) after the reaction precipitation liquid is cooled, washing the reaction precipitation liquid by deionized water through a centrifugal machine at the rotating speed of 2500r/min, and drying the precipitation liquid after repeated washing reaction at 85 ℃ through a blast drying oven to obtain nickel-manganese-tungsten precursor powder;
(4) weighing and mixing nickel-manganese-tungsten precursor powder and lithium oxalate according to the molar ratio of Li/(Ni + Mn + W) being 1.20, and performing ball milling for 10 hours at the ball milling speed of 350r/min to obtain mixed powder; wherein the ball milling medium is zirconium dioxide balls;
(5) the mixed powder is calcined for 6 hours at a high temperature of 950 ℃ in oxygen at a heating rate of 2 ℃/min in a high-temperature atmosphere tubular furnace to obtain the cathode material LiNi of the nickel-manganese-tungsten lithium ion battery0.82Mn0.03W0.15O2。
Example 7
A preparation method of a nickel-manganese-tungsten lithium ion battery anode material comprises the following steps:
(1) weighing starting raw materials such as nickel acetate, manganese acetate and tungsten oxide according to the molar ratio of Ni to Mn to W of 0.87 to 0.08 to 0.05, mixing and dissolving the starting raw materials by using deionized water, stirring the mixture uniformly to form a solution A, and then mixing the solution A with the weight ratio of (Ni + Mn + W): urea 1: 5, dissolving the urea in deionized water, uniformly stirring to form a solution B, and gradually dropping the solution B into the solution A to form a mixed reaction solution;
(2) pouring the mixed reaction solution into a liner of a reaction kettle, placing the reaction kettle in an oven, preserving heat for 15 hours at 200 ℃, and carrying out solvothermal reaction to obtain a reaction precipitation solution;
(3) after the reaction precipitation liquid is cooled, washing the reaction precipitation liquid by deionized water through a centrifugal machine at the rotating speed of 6000r/min, and drying the precipitation liquid after repeated washing reaction at 70 ℃ through a blast drying oven to obtain nickel-manganese-tungsten precursor powder;
(4) weighing and mixing nickel-manganese-tungsten precursor powder and lithium carbonate according to the molar ratio of Li/(Ni + Mn + W) to 1.04, and performing ball milling for 6 hours at the ball milling speed of 450r/min to obtain mixed powder; wherein the ball milling medium is zirconium dioxide balls;
(5) the powder is calcined for 18 hours at a high temperature of 730 ℃ in oxygen at a heating rate of 20 ℃/min in a high-temperature atmosphere tubular furnace to obtain the cathode material LiNi of the nickel-manganese-tungsten lithium ion battery0.87Mn0.08W0.05O2。
Example 8
A preparation method of a nickel-manganese-tungsten lithium ion battery anode material comprises the following steps:
(1) weighing starting raw materials such as nickel sulfate, manganese sulfate and ammonium tungstate according to the molar ratio of Ni to Mn to W of 0.96 to 0.02, mixing and dissolving the starting raw materials by using deionized water, stirring the mixture uniformly to form a solution A, and then mixing the solution A with the weight percentages of (Ni + Mn + W): ammonium carbonate 1: 2, weighing ammonium carbonate according to the molar ratio, dissolving the ammonium carbonate in deionized water, uniformly stirring to form a solution B, and gradually dropping the solution B into the solution A to form a mixed reaction solution;
(2) pouring the mixed reaction solution into a liner of a reaction kettle, placing the reaction kettle in an oven, preserving heat for 12 hours at 160 ℃, and carrying out solvothermal reaction to obtain a reaction precipitation solution;
(3) after the reaction precipitation liquid is cooled, washing the reaction precipitation liquid by deionized water through a centrifugal machine at the rotating speed of 3000r/min, and drying the precipitation liquid after repeated washing reaction at 65 ℃ through a blast drying oven to obtain nickel-manganese-tungsten precursor powder;
(4) weighing and mixing nickel-manganese-tungsten precursor powder and lithium carbonate according to the molar ratio of Li/(Ni + Mn + W) to 1.10, and performing ball milling for 5 hours at the ball milling speed of 580r/min to obtain mixed powder, wherein the ball milling medium is agate balls;
(5) the mixed powder is calcined for 8 hours at a high temperature of 780 ℃ in oxygen at a heating rate of 3 ℃/min by a high-temperature atmosphere tube furnace to obtain the cathode material LiNi of the nickel-manganese-tungsten lithium ion battery0.96Mn0.02W0.02O2。
Application example 1
The cathode material LiNi of the nickel-manganese-tungsten lithium ion battery synthesized in the example 10.85Mn0.14W0.01O2According to the mass ratio of 90% to 5% to 2.5% of (NMW), polyvinylidene fluoride, conductive carbon black and carbon nano tubes, firstly adding N-methyl pyrrolidone as a solvent to be completely dissolved with the polyvinylidene fluoride, then adding the rest substances and uniformly stirring to obtain uniform slurry. Coating the aluminum foil with the thickness of 18 mu m on an aluminum foil, transferring the aluminum foil to a drying oven to be dried at the temperature of 80 ℃, cutting the aluminum foil into positive active electrode wafers with the diameter of 16mm by a sheet punching machine, weighing the slices, transferring the slices to a vacuum drying oven to carry out vacuum drying at the temperature of 80 ℃, and then transferring the slices to a glove box for standby. The assembled half-cell takes a metal lithium sheet as a negative electrode, and 1mol/L LiPF6The electrolyte solution is/EC + PC + DMC (volume ratio is 1: 1: 1), the diaphragm is Celgard 2325, and the CR2025 button half cell is assembled in an argon glove box. The assembled battery is tested for charge and discharge performance on a nova battery test system. While LiNi was obtained in the same manner as in example 10.85Mn0.14Co0.01O2(NMC) material, adopting the above embodiment to assemble NMC anode material, and synchronously completing the electrochemical performance test steps of NMC and NMW battery;
the nickel manganese tungsten lithium ion in example 1 was usedCell positive electrode material LiNi0.85Mn0.14W0.01O2And LiNi0.85Mn0.14Co0.01O2The phase structure, the morphology characteristics and the electrochemical performance are characterized and tested, and XRD patterns of the two materials in figure 1 show classical alpha-NaFeO2The novel positive electrode material of the nickel-manganese-tungsten lithium ion battery has the same layered structure as lithium nickelate, and the peak intensity ratio I (003)/I (104) of the NMC material is obviously smaller than that of the NMW material, so that the cation mixed arrangement degree of the NMW material is lower, and the ordering degree of the material structure is higher; the splitting degree of the two pairs of splitting peaks (006)/(102) and (108)/(110) means the integrity of the layered crystal structure of the material, the more obvious the splitting is, the more perfect the layered structure of the material is shown, from the two pairs of splitting peaks in the XRD pattern, the splitting peaks of the NMW material (006)/(102) and (108)/(110) are more obvious, while the splitting peaks of the NMC material are blurred and gradually combined into one peak, which shows that the crystallinity of the NMW positive electrode material is higher, and the layered structure is more perfect;
the SEM graph of FIG. 2 shows that both the NMC and the NMW material present lamellar primary particles, and form a silkworm pupa-shaped secondary morphology after sintering, the length is about 15-20 μm, the integral morphology of the NMC and the NMW material is not obviously different, but from the aspect of magnification, the surface lamellar of the NMW material particle is obvious, the surface gap of the particle is clear, which is more beneficial to the infiltration of electrolyte, the surface lamellar of the NMC material tends to be fuzzy, the primary particles are connected more densely, which may influence the migration of lithium ions;
FIG. 3 is an EDS diagram of an NMW material, the right image represents the distribution of Ni, Mn and W elements respectively, and it can be seen from the diagram that the elements are uniformly distributed on the surface of the material particles;
the electrochemical performance test result of fig. 4 shows that the positive electrode material of the NMW lithium ion battery is more beneficial to the de-intercalation of lithium ions in the charging and discharging processes, and therefore shows a higher specific discharge capacity than the NMC material, when the positive electrode material is charged and discharged at a rate of 0.5C within a voltage range of 2.75-4.3V, the specific discharge capacity of the NMC material is 189.3mAh/g, and the specific discharge capacity of the NMW material is 193.7 mAh/g;
fig. 5 is a cycle performance curve of two materials circulating for 100 weeks at a rate of 0.5C within a voltage range of 2.75-4.3V, the capacity retention rate of the NMC positive electrode material after 100 weeks of circulation is 84.85%, and the capacity retention rate of the MNW material reaches 91.51%, which shows excellent cycle stability, mainly because the synergistic effect of three transition metals of Ni, Mn, and W stabilizes the crystal structure of the material, reduces the nickel-lithium mixed arrangement, has stronger bond energy in combination with the W-O bond in the MNW positive electrode material, strengthens the crystal structure of the layered positive electrode material, improves the structural stability of the material, inhibits the rapid attenuation of the material capacity, and realizes the excellent electrochemical performance of the material;
FIG. 6 is a DSC-TG curve of an NMC material and an NMW material at 0-1000 ℃, respectively, and a Differential Scanning Calorimetry (DSC) of a positive electrode (4.3V) in a charging state characterizes the thermal stability of the nickel-manganese-tungsten positive electrode material; the charged nickel-manganese-cobalt positive electrode shows a larger exothermic reaction peak at 212 ℃, which is 11 ℃ lower than that of the nickel-manganese-tungsten positive electrode (the thermal decomposition temperature of the nickel-manganese-tungsten positive electrode material is 223 ℃). The heat released by the nickel-manganese-tungsten anode material in the exothermic reaction process is far less than that of a nickel-manganese-cobalt anode, so that microcracks are inhibited, secondary particles are prevented from being permeated by electrolyte, the contact with the electrolyte is greatly reduced, the thermal stability of the nickel-manganese-tungsten anode material is improved, the safety performance of the anode material is improved, and the nickel-manganese-tungsten anode material has excellent electrochemical stability.
Application example 2
The cathode material LiNi of the nickel-manganese-tungsten lithium ion battery synthesized in the example 20.90Mn0.03W0.07O2The polyvinylidene fluoride, the conductive carbon black and the carbon nano tube are added with N-methyl pyrrolidone as a solvent to be completely dissolved with the polyvinylidene fluoride according to the mass ratio of 90 percent to 5 percent to 2.5 percent, and then the rest substances are added to be uniformly stirred to obtain uniform slurry. Coating the aluminum foil with the thickness of 18 mu m on an aluminum foil, transferring the aluminum foil to a drying oven to be dried at the temperature of 80 ℃, cutting the aluminum foil into positive active electrode wafers with the diameter of 16mm by a sheet punching machine, weighing the slices, transferring the slices to a vacuum drying oven to carry out vacuum drying at the temperature of 80 ℃, and then transferring the slices to a glove box for standby. The assembled half-cell takes a metal lithium sheet as a negative electrode, and 1mol/L LiPF6The electrolyte solution is/EC + PC + DMC (volume ratio is 1: 1: 1), the diaphragm is Celgard 2325, and the CR2025 button half cell is assembled in an argon glove box. The assembled battery is tested for charge and discharge performance on a nova battery test system.
From the results of electrochemical tests, the electrochemical test method is characterized by LiNi0.90Mn0.03W0.07O2The specific discharge capacity of a battery prepared from the lithium ion battery anode material at a rate of 0.5C within a voltage range of 2.75-4.3V is 204.5mAh/g, the capacity retention rate of the battery after 100 cycles is 88.98%, and the battery has good electrochemical activity and electrochemical stability, which indicates that the nickel-manganese-tungsten material has relatively excellent structural stability and safety.
Claims (10)
1. The nickel-manganese-tungsten lithium ion battery anode material is characterized in that the chemical formula of the nickel-manganese-tungsten lithium ion battery anode material is LiNixMnyWzO2The molar ratio of the nickel source to the manganese source to the tungsten source is x: y: z, wherein x is more than or equal to 0.8 and less than or equal to 1, y is more than or equal to 0.01 and less than or equal to 0.2, z is more than or equal to 0.01 and less than or equal to 0.2, and x + y + z is 1.
2. The positive electrode material of the nickel-manganese-tungsten lithium ion battery of claim 1, which is prepared by the solvothermal reaction and the high-temperature solid-phase reaction in sequence; the solvent thermal reaction is to carry out solvent thermal reaction on a nickel source, a manganese source and a tungsten source compound in a water solvent containing a precipitator to prepare nickel-manganese-tungsten precursor powder; the high-temperature solid-phase reaction is to perform ball milling and mixing on nickel-manganese-tungsten precursor powder and a lithium source compound, and then perform heating sintering and heat preservation sintering in an oxygen atmosphere.
3. The positive electrode material of the nickel-manganese-tungsten lithium ion battery as claimed in claim 2, wherein the nickel source is any one of nickel hydroxide, nickel sulfate, nickel acetate, nickel nitrate, nickel oxalate and nickel chloride.
4. The positive electrode material of the nickel-manganese-tungsten lithium ion battery as claimed in claim 2, wherein the manganese source is any one of manganese hydroxide, manganese sulfate, manganese acetate, manganese nitrate, manganese oxalate and manganese chloride.
5. The positive electrode material of the nickel-manganese-tungsten lithium ion battery according to claim 2, wherein the tungsten source is any one of ammonium metatungstate, sodium tungstate, tungsten acetate, tungsten oxide and tungsten chloride.
6. The positive electrode material of the nickel-manganese-tungsten lithium ion battery as claimed in claim 2, wherein the precipitant is any one of sodium carbonate, ammonium bicarbonate, oxalic acid and urea.
7. The positive electrode material of the nickel manganese tungsten lithium ion battery as claimed in claim 2, wherein the lithium source is any one of lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate and lithium oxalate.
8. The positive electrode material of the nickel-manganese-tungsten lithium ion battery of claim 1, wherein the solvothermal reaction is carried out at 100-300 ℃ for 5-20 h.
9. The positive electrode material of the nickel-manganese-tungsten lithium ion battery according to claim 1, wherein the temperature rise sintering is performed at a temperature rise rate of 1-20 ℃/min and a sintering temperature of 700-1000 ℃.
10. The preparation method of the nickel-manganese-tungsten lithium ion battery positive electrode material as claimed in claim 1 or 2, characterized by comprising the following steps:
the first step is as follows: solvothermal reaction
(1) Weighing a nickel source, a manganese source and a tungsten source, dissolving the nickel source, the manganese source and the tungsten source by using deionized water, and mixing and stirring uniformly to form a solution A; weighing a precipitator, dissolving the precipitator with deionized water, and mixing and stirring uniformly to form a solution B; dropwise adding the solution B into the solution A to form a mixed reaction solution;
(2) pouring the mixed reaction solution into a liner of a reaction kettle to carry out high-temperature hydrothermal reaction to prepare reaction precipitation solution;
(3) repeatedly washing the reaction precipitate with deionized water by a centrifugal machine under the condition that the centrifugal rotating speed is 1000-10000 r/min, and drying at 50-100 ℃ to obtain nickel-manganese-tungsten precursor powder;
the second step is that: high temperature solid phase reaction
(4) Ball-milling the nickel-manganese-tungsten precursor powder and a lithium source for 3-10 hours at the ball-milling speed of 300-800 r/min to obtain mixed powder;
(5) and (3) placing the mixed powder in a high-temperature atmosphere tube furnace, heating and sintering to 700-1000 ℃ in an oxygen atmosphere, and preserving heat for 5-20 hours at the temperature to obtain the nickel-manganese-tungsten lithium ion battery anode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110286928.0A CN114171735A (en) | 2021-03-17 | 2021-03-17 | Nickel-manganese-tungsten lithium ion battery positive electrode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110286928.0A CN114171735A (en) | 2021-03-17 | 2021-03-17 | Nickel-manganese-tungsten lithium ion battery positive electrode material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114171735A true CN114171735A (en) | 2022-03-11 |
Family
ID=80476282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110286928.0A Pending CN114171735A (en) | 2021-03-17 | 2021-03-17 | Nickel-manganese-tungsten lithium ion battery positive electrode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114171735A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070054192A1 (en) * | 2005-09-08 | 2007-03-08 | Sanyo Electric Co., Ltd | Non-aqueous electrolyte secondary battery |
| CN101017914A (en) * | 2006-02-08 | 2007-08-15 | 三洋电机株式会社 | Non-aqueous electrolyte secondary battery |
| CN102723481A (en) * | 2012-07-09 | 2012-10-10 | 华南师范大学 | High-voltage lithium battery cathode material doped with trace amount of tungsten and preparation method thereof |
| CN103081190A (en) * | 2010-09-02 | 2013-05-01 | 住友化学株式会社 | Positive electrode active material |
| CN106169566A (en) * | 2016-08-09 | 2016-11-30 | 长沙理工大学 | A kind of preparation method of stratiform lithium-rich anode material |
| CN109755549A (en) * | 2019-03-11 | 2019-05-14 | 清远佳致新材料研究院有限公司 | Nickel-base anode material and preparation method thereof, lithium ion cell positive, lithium ion battery and application |
| CN109921007A (en) * | 2019-03-15 | 2019-06-21 | 国家纳米科学中心 | A kind of nickelic lithium-rich anode material, and its preparation method and application |
| CN111430683A (en) * | 2020-01-17 | 2020-07-17 | 蜂巢能源科技有限公司 | Cobalt-free cathode material of lithium ion battery, preparation method of cobalt-free cathode material and lithium ion battery |
| CN111498914A (en) * | 2020-04-24 | 2020-08-07 | 四川万邦胜辉新能源科技有限公司 | Nickel-manganese-based positive electrode material precursor and synthesis method of positive electrode material |
-
2021
- 2021-03-17 CN CN202110286928.0A patent/CN114171735A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070054192A1 (en) * | 2005-09-08 | 2007-03-08 | Sanyo Electric Co., Ltd | Non-aqueous electrolyte secondary battery |
| CN101017914A (en) * | 2006-02-08 | 2007-08-15 | 三洋电机株式会社 | Non-aqueous electrolyte secondary battery |
| CN103081190A (en) * | 2010-09-02 | 2013-05-01 | 住友化学株式会社 | Positive electrode active material |
| CN102723481A (en) * | 2012-07-09 | 2012-10-10 | 华南师范大学 | High-voltage lithium battery cathode material doped with trace amount of tungsten and preparation method thereof |
| CN106169566A (en) * | 2016-08-09 | 2016-11-30 | 长沙理工大学 | A kind of preparation method of stratiform lithium-rich anode material |
| CN109755549A (en) * | 2019-03-11 | 2019-05-14 | 清远佳致新材料研究院有限公司 | Nickel-base anode material and preparation method thereof, lithium ion cell positive, lithium ion battery and application |
| CN109921007A (en) * | 2019-03-15 | 2019-06-21 | 国家纳米科学中心 | A kind of nickelic lithium-rich anode material, and its preparation method and application |
| CN111430683A (en) * | 2020-01-17 | 2020-07-17 | 蜂巢能源科技有限公司 | Cobalt-free cathode material of lithium ion battery, preparation method of cobalt-free cathode material and lithium ion battery |
| CN111498914A (en) * | 2020-04-24 | 2020-08-07 | 四川万邦胜辉新能源科技有限公司 | Nickel-manganese-based positive electrode material precursor and synthesis method of positive electrode material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112750999B (en) | Cathode material, preparation method thereof and lithium ion battery | |
| US20210367233A1 (en) | Ternary positive electrode material and preparation method therefor, and lithium-ion battery | |
| JP5712544B2 (en) | Positive electrode active material particle powder, method for producing the same, and nonaqueous electrolyte secondary battery | |
| CN109546123B (en) | Vanadium pentoxide-coated core-shell structure gradient nickel-cobalt-manganese positive electrode material and preparation method thereof | |
| EP1837937B1 (en) | Lithium manganese-based composite oxide and method for preparing the same | |
| CN114790013A (en) | Sodium ion battery positive electrode active material capable of self-supplementing sodium, and preparation method and application thereof | |
| CN111446444B (en) | Lithium-rich manganese-based material and preparation method and application thereof | |
| KR20240013213A (en) | Sodium-containing oxide anode material and its manufacturing method and application, anode plate and its application | |
| JP2023500117A (en) | Cobalt-free cathode material for lithium-ion batteries, its preparation method and lithium-ion batteries | |
| CN106602024B (en) | Surface in-situ modification type lithium-rich material and preparation method thereof | |
| CN106486657B (en) | Surface in-situ coated lithium-rich material and preparation method thereof | |
| CN110556531A (en) | Anode material, preparation method thereof and lithium ion battery containing anode material | |
| CN109888225A (en) | Positive electrode and preparation method thereof and lithium ion battery | |
| CN111180724A (en) | Preparation method of ternary single crystal cathode material | |
| CN112289994B (en) | Coated high-nickel ternary material and preparation method and application thereof | |
| CN115939336A (en) | Positive electrode material of sodium ion battery, positive plate and secondary battery | |
| CN115064670B (en) | Preparation method of doped coated modified sodium nickel manganese oxide positive electrode material | |
| CN114695862A (en) | Fluorine-aluminum co-doped lithium cobaltate cathode material and preparation method thereof | |
| KR20230080395A (en) | Eco-friendly precursors and complex oxide powders and their manufacturing methods and applications | |
| CN101783408A (en) | Cathode material, preparation method thereof and battery using cathode material | |
| GB2619865A (en) | Preparation method for positive electrode material precursor having large channel, and application thereof | |
| CN115732674A (en) | Sodium anode precursor material and preparation method and application thereof | |
| CN112694104B (en) | Prussian blue analogue, preparation method thereof, negative electrode material and application | |
| CN113697869B (en) | Ternary positive electrode material precursor modified by compounding metal phosphide and metal phosphate | |
| JP4055269B2 (en) | Manganese oxide and method for producing the same, lithium manganese composite oxide using manganese oxide, and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |