CN109755512A - A kind of nickelic long-life multielement positive electrode and preparation method thereof - Google Patents
A kind of nickelic long-life multielement positive electrode and preparation method thereof Download PDFInfo
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- CN109755512A CN109755512A CN201811585902.0A CN201811585902A CN109755512A CN 109755512 A CN109755512 A CN 109755512A CN 201811585902 A CN201811585902 A CN 201811585902A CN 109755512 A CN109755512 A CN 109755512A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 44
- 239000011159 matrix material Substances 0.000 claims abstract description 35
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 28
- 230000008569 process Effects 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 8
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 6
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 3
- 229910052796 boron Inorganic materials 0.000 claims abstract description 3
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 3
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 33
- 229910001416 lithium ion Inorganic materials 0.000 claims description 33
- 239000011572 manganese Substances 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
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- 230000000694 effects Effects 0.000 claims description 15
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- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 238000005253 cladding Methods 0.000 claims description 13
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 claims description 12
- 239000002105 nanoparticle Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 11
- 239000012266 salt solution Substances 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 238000012216 screening Methods 0.000 claims description 8
- 239000010405 anode material Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 229910003002 lithium salt Inorganic materials 0.000 claims description 5
- 159000000002 lithium salts Chemical class 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
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- 238000010790 dilution Methods 0.000 claims description 4
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000010348 incorporation Methods 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 2
- 229910009178 Li1.3Al0.3Ti1.7(PO4)3 Inorganic materials 0.000 claims description 2
- 229910009274 Li1.4Al0.4Ti1.6 (PO4)3 Inorganic materials 0.000 claims description 2
- 229910009511 Li1.5Al0.5Ge1.5(PO4)3 Inorganic materials 0.000 claims description 2
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910009866 Ti5O12 Inorganic materials 0.000 claims description 2
- 229910010252 TiO3 Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 238000003701 mechanical milling Methods 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
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- 230000000052 comparative effect Effects 0.000 description 36
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 18
- 239000011244 liquid electrolyte Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 229910052744 lithium Inorganic materials 0.000 description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 9
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 9
- 229910052808 lithium carbonate Inorganic materials 0.000 description 9
- PNEFIWYZWIQKEK-UHFFFAOYSA-N carbonic acid;lithium Chemical compound [Li].OC(O)=O PNEFIWYZWIQKEK-UHFFFAOYSA-N 0.000 description 8
- 238000004448 titration Methods 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 238000002848 electrochemical method Methods 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 239000002131 composite material Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000010416 ion conductor Substances 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 4
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
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- 229910052751 metal Inorganic materials 0.000 description 4
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000003570 air Substances 0.000 description 3
- 239000005030 aluminium foil Substances 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 229940099596 manganese sulfate Drugs 0.000 description 3
- 239000011702 manganese sulphate Substances 0.000 description 3
- 235000007079 manganese sulphate Nutrition 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- 239000000320 mechanical mixture Substances 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910017246 Ni0.8Co0.1Mn0.1 Inorganic materials 0.000 description 2
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- 229920006362 Teflon® Polymers 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
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- 239000012065 filter cake Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 208000032953 Device battery issue Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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 present invention provides a kind of nickelic long-life multielement positive electrode and preparation method thereof, and it is Li that the positive electrode, which is by chemical formula,1+a[(Ni1‑2xCoxMnx)1‑yMy]1‑zM′zO2Matrix and be coated on the solid electrolyte Li on described matrix surfaceuM″vM″′γM″″βM″″′αOwComposition, wherein M and M ' is at least one of La, Cr, Mo, Ca, Fe, Hf, Ti, Zn, Y, Zr, Si, W, Nb, Sm, V, Mg, B, Al element, and M ", M " ', M " ", M " " ' are at least one of Zr, Ti, Cr, Al, Si, Mn, Sn, W, Nb, P, La, Ta, Ge, Ga, Y, Sc element；Solid electrolyte coats 0.01~5% that total amount is matrix mole.Positive electrode of the invention energy density with higher and cyclical stability, can be used for lithium-ion-power cell.The preparation method simple process and low cost of the material is suitable for large-scale production.
Description
Technical field
The present invention relates to a kind of nickelic long-life multielement positive electrode and preparation methods, belong to lithium ion battery technology neck
Domain.
Background technique
In recent years, with new-energy automobile industry grow rapidly, market for the energy density of power battery, safety,
More stringent requirements are proposed for the performances such as fast charging and discharging and cycle life.Power type lithium-ion battery anode material is also by mangaic acid
Lithium, LiFePO4 develop to the direction of nickelic multicomponent material.Nickelic multicomponent material really have specific capacity is high, cost of material compared with
Low advantage, but with the raising of nickel content, cycle life, high rate performance and security performance can also deteriorate accordingly.Therefore,
It needs to be modified polynary positive pole material by the techniques such as adulterating, coating, to adapt to the application demand of industrialization.Numerous
Commonplace way is by the method for collosol and gel or mechanical mixture in multicomponent material matrix surface shape in cladding process
At one layer of oxide cladding layers, the problems such as to alleviate the side reaction between positive electrode and electrolyte, transition metal dissolution.But it is general
Logical oxide cladding layers be difficult solve the median surface impedance of positive electrode charge and discharge process it is big, lithium ion transport access denial etc. is asked
Topic, therefore the high rate performance and cycle life of polynary positive pole material can not be effectively improved.In contrast, inorganic solid electrolyte material
Material is due to stable structure and has lithium ion tunnel, can be used as excellent positive electrode covering.
Chinese patent CN108682819A discloses a kind of positive electrode directly coated with solid electrolyte and its technique
Method.Positive electrode, solid electrolyte and carbon material are carried out by mechanical mixture by high speed mixer in patent and annealed, is obtained
The positive electrode of solid electrolyte and carbon material compound coating, the material have more preferably multiplying power spy relative to uncoated material
Property and cycle performance.But this cladding mode for directlying adopt mechanical mixture it is difficult to ensure that solid electrolyte in positive electrode table
Face is uniformly distributed, and is easy to cause the surface of high-nickel material to form the by-products such as lithium carbonate in mixed process, leads to sample
Specific discharge capacity decline, at the same time, the annealing process in the patent is carried out in tube furnace in nitrogen atmosphere, because
This high process cost is not suitable for industrialization production.
Chinese patent CN107039634A, which is disclosed, a kind of is deposited in positive electrode surface in situ using collosol and gel/solution
The method for generating fast lithium ion conductor clad.By by the precursor solution and lithium ion battery of fast lithium ion conductor in patent
Positive electrode is uniformly mixed at a certain temperature, obtains the composite positive pole of the fast lithium ion conductor of surface coated inorganic, will be answered
It closes anode after heat treatment, obtains inorganic fast lithium ion conductor covered composite yarn positive electrode.The positive electrode tool of the method preparation
Have a higher specific discharge capacity, but it is described the process is more complicated and cost is prohibitively expensive, be suitable only for small-scale preparation, be not suitable for
In industrialization production；Generated in-situ method is it is difficult to ensure that clad has the pure phase of fast-ionic conductor, and then not can guarantee packet
The uniformity covered；For high-nickel material, this method then will lead to high-nickel material surface and form excessive lithium carbonate, cause
The decline of material discharging specific capacity.
Summary of the invention
For above-mentioned problems of the prior art, the present invention provides a kind of nickelic long-life multielement positive electrode and system
Preparation Method, multicomponent material surface provided by the invention is coated with one layer of nanoscale solid electrolyte, and passes through intermolecular interaction
The carbonic acid lithium content of high-nickel material surface remaining is effectively reduced in power, is substantially reduced interface impedance of the battery in charge and discharge process,
Lithium ion tunnel is constructed, material energy density with higher and cycle life are made.
The present invention also provides the preparation method of above-mentioned polynary positive pole material presoma and material, simple process, process is easy
Stability contorting, production cost is low, is suitable for large-scale industrial production.
To achieve the goals above, the invention adopts the following technical scheme:
Nickelic long-life multielement positive electrode provided by the invention, including matrix and the solid-state for being coated on described matrix surface
Electrolyte clad；The chemical formula of described matrix is Li1+a[(Ni1-2xCoxMnx)1-yMy]1-zM′zO2, wherein -0.5≤a≤0.3,
0.05≤x≤0.3,0≤y≤0.01,0≤z≤0.01, it is Li that the clad, which contains chemical formula,uM″vM″′γM″″βM″″′αOw
Solid electrolyte, wherein 1≤u≤8,0≤v≤3,0≤γ≤2,1≤β≤3,1≤α≤3,2≤w≤12, M and M ' be La,
At least one of Cr, Mo, Ca, Fe, Hf, Ti, Zn, Y, Zr, Si, W, Nb, Sm, V, Mg, B, Al element, M ", M " ', M " ",
M " " ' is at least one of Zr, Ti, Cr, Al, Si, Mn, Sn, W, Nb, P, La, Ta, Ge, Ga, Y, Sc element.
The solid electrolyte clad is densification or un-densified, and the mole of clad accounts for the 0.01~5% of matrix.
The average grain diameter D of the nickelic long-life multielement positive electrode50It is 2~20 μm.
The present invention also provides the preparation methods of above-mentioned nickelic long-life multielement positive electrode, comprising the following steps:
(1) salt solution of nickel, cobalt, manganese and doped chemical is obtained into the mixing salt solution of 1~3mol/L；By hydrogen-oxygen
Change sodium and is dissolved into the aqueous slkali that concentration is 4~10mol/L；The enveloping agent solution for being 2~10mol/L at concentration by ammonia solvent.
Mixing salt solution, aqueous slkali, enveloping agent solution together cocurrent are added in reaction kettle and reacted, is kept stirring in the process,
PH value in reaction and reaction temperature are controlled simultaneously, precursor pulp obtained obtains after separation of solid and liquid, washing, drying, screening
Spherical nickel cobalt manganese hydroxide (Ni1-2xCoxMnx)1-yMy(OH)2；
(2) (the Ni for obtaining step (1)1-2xCoxMnx)1-yMy(OH)2It is uniformly mixed with the oxide of lithium salts, M ', in sky
In gas or oxygen atmosphere, 4~20h is calcined at 600~1000 DEG C, by broken, screening, obtains anode material for lithium ion battery
Matrix Li1+a[(Ni1-2xCoxMnx)1-yMy]1-zM′zO2；
(3) the solid electrolyte powder prepared is put into the ball grinder equipped with liquid medium and carries out mechanical ball mill, shape
At the nano-scale particle colloidal sol with Tyndall effect, after this colloidal sol is diluted by a certain percentage with liquid medium and the anode
Material matrix mixes 5~25min, after mixture is then filtered 5~20min in Suction filtration device, is put into 100~180 DEG C very
0.5-6h is dried in empty baking oven；Or the nano-scale particle colloidal sol with Tyndall effect of formation is put into spraying device,
It is carried out spraying mixing with the positive electrode matrix at a temperature of and dried by certain atmosphere, achievees the effect that uniformly to coat；
Material after above-mentioned drying is finally heat-treated to 2~10h in 100~800 DEG C of temperature ranges, is made and is electrolysed by nanoscale solid state
Matter LiuM″vM″′γM″″βM″″′αOwThe nickel-cobalt-manganese multi positive electrode of cladding.
Preferably, the LiuM″vM″′γM″″βM″″′αOwSolid electrolyte is Li1+δ1Ti2(PO4)3、Li1.1+δ 1Al0.1Ti1.9(PO4)3、Li1.2+δ1Al0.2Ti1.8(PO4)3、Li1.3+δ1Al0.3Ti1.7(PO4)3、Li1.4+δ1Al0.4Ti1.6(PO4)3、
Li1.5+δ1Al0.5Ti1.5(PO4)3、Li1.3+δ1Al0.2Y0.1Ti1.7(PO4)3、Li1.4+δ1Cr0.4Ti1.6(PO4)3、Li1.3+δ 1Al0.2Sc0.1Ti1.7(PO4)3、Li1.3+δ1Al0.2Ge0.1Ti1.7(PO4)3、Li1.3+δ1Al0.3Ge1.7(PO4)3、Li1.5+δ 1Al0.5Ge1.5(PO4)3、Li1.3+δ1Ti2Si0.3P2.7O12、Li0.33+δ1La0.57TiO3、Li6.55+δ2La3Zr2Ge0.15O12、Li7+δ 2La3Zr1.4Nb0.6O12、Li7+δ2La3Zr1.6Ta0.4O12、Li7+δ2La3Zr1.6W0.4O12、Li6.4+δ2La3Zr1.4Ta0.6O12、
Li0.34+δ1La0.51TiO2.94、Li3+δ1La3Te2O12、Li5+δ2La3Bi2O12、Li7+δ2La3Zr2O12、Li4+δ2Ti5O12One of
Or it is several, wherein -0.1≤δ 1≤0.3, -0.5≤δ 2≤0.5.
It is further preferred that the LiuM″vM″′γM″″βM″″′αOwSolid electrolyte is Li1.3Al0.3Ti1.7(PO4)3、
Li1.4Al0.4Ti1.6(PO4)3、Li1.4Cr0.4Ti1.6(PO4)3、Li7La3Zr2O12、Li1.5Al0.5Ge1.5(PO4)3、
Li6.4La3Zr1.4Ta0.6O12、Li7La3Zr1.4Nb0.6O12、Li7La3Zr1.6Ta0.4O12、Li7La3Zr1.6W0.4O12、
Li1.3Ti2Si0.3P2.7O12One of or it is a variety of.
Preferably, step (1) the reaction pH range is 10~13, and temperature is 50~70 DEG C.
Preferably, step (2) and (3) described lithium salts are one or both of lithium carbonate, lithium hydroxide.
Preferably, the additional amount of step (2) described lithium salts be Li/ (Ni+Co+Mn+M+M ') molar ratio=0.95~
1.3。
Preferably, the preparation method of step (3) described solid electrolyte is one of solid phase method, sol-gal process.
Preferably, liquid medium used in step (3) described mechanical milling process is pure water, methanol, ethyl alcohol, propyl alcohol, second
Glycol, isopropanol, benzyl alcohol, acetone, benzene, toluene, methyl ether, ether, acetic acid, dimethylbenzene, tetrahydrofuran, dimethyl carbonate, N-
One or more of methyl pyrrolidone, propene carbonate, N,N-dimethylformamide, acetonitrile, glycol dimethyl ether.
Preferably, the weight ratio after step (3) the colloidal sol dilution with positive electrode is 1:4~1:0.5.
Preferably, the incorporation time after the dilution of colloidal sol described in step (3) with positive electrode matrix is 5~35min.
Preferably, the atmosphere for mixing and drying by spraying described in step (3) is one of dry air, nitrogen, argon gas
Or several gaseous mixture.
Preferably, the temperature of drying described in step (3) is 60~180 DEG C.
Preferably, the moisture content of gained filter cake is 10%~15% after filtering described in step (3).
Preferably, step (3) heat-treating atmosphere is air or oxygen, and heat treatment temperature is 200~600 DEG C, the time
For 2~10h.
Present invention has the advantage that
(1) the nickelic long-life multielement positive electrode that the present invention obtains has preferable structure steady in charge and discharge process
Qualitative, cycle performance is excellent.
(2) the obtained nickelic long-life multielement positive electrode of the present invention, surface coated nanoscale solid state electrolyte without
Object phase need to be re-formed by heat treatment process, therefore required heat treatment temperature is lower.
(3) preparation method of nickelic long-life multielement positive electrode of the present invention, passes through the ball milling shape in liquid medium
At nanoscale solid state electrolyte can be uniformly adsorbed on just by the peptizaiton of liquid medium or the method for spray drying
Pole material matrix surface, to reach preferable covered effect.
(4) preparation method of nickelic long-life multielement positive electrode of the present invention is taken using intermolecular adsorption capacity
Technique simple to operation achievees the purpose that high-nickel material surface carbonic acid lithium content is effectively reduced, and leads in subsequent processes
Control drying course and heat-treating atmosphere are crossed, alleviates the generation again of surface lithium carbonate, significantly improves the specific discharge capacity of material.
(5) the nickelic long-life multielement positive electrode that the present invention obtains, by cladding solid electrolyte effectively polynary
Positive electrode surface constructs lithium ion transport channel, reduces the interface impedance of positive electrode, while alleviating charge and discharge
Side reaction of the positive electrode surface with electrolyte in journey, hence it is evident that improve the multiplying power and cycle performance of positive electrode.
(6) preparation method simple process of the present invention, pollution-free；Doped chemical and clad incorporation way are simple, and dosage is few,
Heat treatment temperature is lower, is suitble to industrialization production.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment
Attached drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for this
For the those of ordinary skill in field, without creative efforts, it can also be obtained according to these attached drawings other
Attached drawing.
Fig. 1 is the scanning electron microscope (SEM) photograph of polynary positive pole material matrix prepared by comparative example 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of nickelic long-life multielement positive electrode prepared by embodiment 1.
Fig. 3 is bent for the charge and discharge of comparative example 1 and the lithium ion battery containing liquid electrolyte of the preparation of embodiment 1 at 0.1C
Line chart.
Electric discharge of the Fig. 4 for comparative example 1 and the lithium ion battery containing liquid electrolyte of the preparation of embodiment 1 under different multiplying
Specific volume spirogram.
Cycle performance figure of the lithium ion battery containing liquid electrolyte prepared by Fig. 5 comparative example 1 and embodiment 1 at 1C.
Charging and discharging curve figure of the Fig. 6 for comparative example 2 and the solid electrolyte lithium battery of the preparation of embodiment 2 at 0.2C.
Cycle performance figure of the Fig. 7 for comparative example 2 and the solid electrolyte lithium battery of the preparation of embodiment 2 at 0.2C.
Specific embodiment
With reference to the attached drawing in the embodiment of the present invention, technical solution in the embodiment of the present invention carries out clear, complete
Ground description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on this
The embodiment of invention, every other implementation obtained by those of ordinary skill in the art without making creative efforts
Example, belongs to protection scope of the present invention.
Comparative example 1
Step 1: nickel sulfate, cobaltous sulfate, manganese sulfate are dissolved to obtain 2.5mol/ according to the ratio of metal molar ratio 8:1:1
Sodium hydroxide is dissolved into the aqueous slkali that concentration is 6mol/L by the mixing salt solution of L, at concentration is 6mol/L by ammonia solvent
Enveloping agent solution.Mixing salt solution, aqueous slkali, enveloping agent solution together cocurrent are added in reaction kettle and reacted, process
It is constant to be kept stirring revolving speed 125rpm, control pH is 11.9~12.1, and temperature is 65 DEG C, when reaction completion, keeps temperature, stirring
Revolving speed is constant, continues to stir 20min, is then separated by solid-liquid separation nickel cobalt manganese hydroxide slurry obtained, washs, filter cake
It is sieved after 120 DEG C of drying 4h, obtains spherical nickel cobalt manganese hydroxide materials.
Step 2: the spherical nickel cobalt manganese hydroxide materials that step 1 obtains are uniformly mixed with lithium hydroxide, wherein hydrogen
Lithia is added according to molar ratio Li/ (Ni+Co+Mn)=1.05.In oxygen atmosphere, 800 DEG C of sintering 15h, by broken, sieve
Point, obtain anode material for lithium ion battery matrix Li.05Ni0.8Co0.1Mn0.1O2.Titration test is carried out by potentiometric titrimeter
The surface carbonic acid lithium content for obtaining sample at this time is 6300ppm.
Positive electrode sample assembly obtained above is subjected to electrochemical Characterization at the lithium ion battery containing liquid electrolyte.
Specific steps are as follows: by polynary positive pole material, acetylene black and polyvinylidene fluoride (PVDF) according to mass ratio 95%:2.5%:
2.5% is mixed, and is diameter 12mm, thickness with the pressure punch forming of 100Mpa coated on aluminium foil and drying and processing is carried out
Then anode pole piece is put into 120 DEG C of drying 12h in vacuum drying box by 120 μm of anode pole piece.Cathode is using diameter
17mm, with a thickness of the Li sheet metal of 1mm；The polyethylene porous membrane that diaphragm uses with a thickness of 25 μm；Electrolyte uses 1mol/L's
LiPF6, ethylene carbonate (EC) and diethyl carbonate (DEC) equivalent mixed liquor.By anode pole piece, diaphragm, cathode pole piece and
Electrolyte is assembled into 2025 type button cells in the Ar gas glove box that water content and oxygen content are respectively less than 5ppm.By above-mentioned button
Battery carries out the cycle performance of charge and discharge cycles 80 times investigation materials at 3.0~4.3V, 1C, 45 DEG C；In 3.0~4.3V,
The current density of 0.1C, 0.2C, 0.5C, 1C, 2C respectively recycle the high rate performance of 1 investigation material.
As shown in Figure 1, the single crystal grain that the polynary positive pole material of this comparative example preparation is 2~3 μm of diameter, surface remaining
There is a small amount of sample fine powder.
As shown in figure 3, the polynary positive pole material of this comparative example preparation is assembled into the lithium ion battery containing liquid electrolyte and exists
Specific discharge capacity is 199.6mAh/g under 3.0~4.3V, 0.1C.
As shown in figure 4, the polynary positive pole material of this comparative example preparation is assembled into the lithium ion battery containing liquid electrolyte and exists
Specific discharge capacity is respectively 194.4,186.6,178.2,168.0mAh/g under 3.0~4.3V, 0.2C, 0.5C, 1C, 2C multiplying power.
As shown in figure 5, the polynary positive pole material of this comparative example preparation is assembled into the lithium ion battery containing liquid electrolyte and exists
3.0~4.3V, 1C, recycle 100 weeks at 45 DEG C after capacity retention ratio be 89.6%.
Comparative example 2
Step 1: nickel sulfate, cobaltous sulfate, manganese sulfate are dissolved to obtain 2mol/L according to the ratio of metal molar ratio 3:1:1
Mixing salt solution, by sodium hydroxide be dissolved into concentration be 8mol/L aqueous slkali；It at concentration is 6mol/L by ammonia solvent
Enveloping agent solution.100L mixing salt solution, aqueous slkali, enveloping agent solution together cocurrent are added in reaction kettle and reacted,
It is constant that process is kept stirring revolving speed 120rpm, and control pH is 11.5~11.7, and temperature is 60 DEG C, when reaction is completed, keep temperature,
Speed of agitator is constant, continues to stir 20min, is then separated by solid-liquid separation nickel cobalt manganese hydroxide slurry obtained, washs, filters
It is sieved after 105 DEG C of drying 5h of cake, obtains nickel cobalt manganese hydroxide.
Step 2: the nickel cobalt manganese hydroxide that step 1 obtains is uniformly mixed with lithium carbonate, wherein lithium carbonate is according to rubbing
You than mixture is calcined 12 hours at 870 DEG C after Li/ (Ni+Co+Mn)=1.17, obtained after broken, screening it is polynary just
Pole material matrix Li1.17Ni0.6Co0.2Mn0.2O2.Titration test, which is carried out, by potentiometric titrimeter obtains the surface carbon of sample at this time
Sour lithium content is 2347ppm.
By positive electrode sample assembly obtained above at solid state lithium battery.Specific steps are as follows: by PEO and LiTFSI (object
The amount ratio EO:Li=12 of matter) it is dissolved in acetonitrile, after stirring 12 hours, obtained slurry is cast in Teflon mould
In, PEO dielectric film is placed in press after hot pressing 5min after being dried in vacuo 10 hours in 50 DEG C of baking oven and is taken out, is washed into straight
The wafer type PEO dielectric film of diameter 19mm.By polynary positive pole material obtained above, conductive black, PVDF, LiTFSI according to matter
Amount is mixed than 90:3:5:2, and suitable NMP is added, scratches on aluminium foil after mixing evenly, dry in 120 DEG C of convection ovens
1h is washed into the anode pole piece that diameter is 11mm；Using lithium metal as cathode, by the anode pole piece of preparation and PEO dielectric film in water
Content and oxygen content, which are respectively less than in the Ar gas glove box of 5ppm, is assembled into 2025 type button cells.By above-mentioned button cell 3.0
~4.3V, 0.2C, charge-discharge test is carried out at 60 DEG C.
As shown in fig. 6, the polynary positive pole material of this comparative example preparation is assembled into solid state lithium battery in 3.0~4.3V, 0.2C
Lower specific discharge capacity is 116.3mAh/g.
As shown in fig. 7, the polynary positive pole material of this comparative example preparation is assembled into solid state lithium battery in 3.0~4.3V, 0.2C
Under be recycled to the 9th week and battery failure occur, cycle performance is poor.
Embodiment 1
Step 1 and step 2 are consistent with 1 preparation step of comparative example.
Step 3: by 0.8g solid electrolyte powder Li1.34Al0.3Ti1.7(PO4)3Be put into the ball grinder equipped with pure water into
Row mechanical ball mill forms the nano-scale particle colloidal sol with Tyndall effect, same 100g after this colloidal sol is diluted to 30g with pure water
The positive electrode matrix that step 2 obtains mixes 10min with the speed of 200r/min, then takes out mixture in suction funnel
Be put into 180 DEG C of vacuum drying ovens after filter 18min and dry 2.5h, drying material is heat-treated 3h in 600 DEG C of temperature ranges, be made by
Nanoscale solid state electrolyte Li1.34Al0.3Ti1.7(PO4)3The nickel-cobalt-manganese multi positive electrode of cladding.It is carried out by potentiometric titrimeter
The surface carbonic acid lithium content that titration test obtains sample at this time is 1590ppm.
Positive electrode sample assembly obtained above is subjected to electrochemical Characterization at the lithium ion battery containing liquid electrolyte.
Specific assembling steps and characterizing method are consistent with the method in comparative example 1, and details are not described herein again.
As shown in Fig. 2, the single crystal grain that polynary positive pole material manufactured in the present embodiment is 2~3 μm of diameter, surface is compared
Uniformly it is coated with the solid electrolyte particle of nano-grade size.
Exist as shown in figure 3, polynary positive pole material manufactured in the present embodiment is assembled into the lithium ion battery containing liquid electrolyte
Specific discharge capacity is 208.1mAh/g under 3.0~4.3V, 0.1C, and the positive electrode prepared than comparative example 1 improves 8.5mAh/g.
Exist as shown in figure 4, polynary positive pole material manufactured in the present embodiment is assembled into the lithium ion battery containing liquid electrolyte
Specific discharge capacity is above the positive electrode of the preparation of comparative example 1 under 3.0~4.3V, 0.2C, 1C, 2C multiplying power, wherein under 2C multiplying power
Specific discharge capacity reaches 183.4mAh/g, is higher by 15.4mAh/g than comparative example 1.
Exist as shown in figure 5, polynary positive pole material manufactured in the present embodiment is assembled into the lithium ion battery containing liquid electrolyte
3.0~4.3V, 1C, recycle 80 weeks at 45 DEG C after capacity retention ratio be 93.5%.
Embodiment 2
Step 1 and step 2 are consistent with 2 preparation step of comparative example.
Step 3: by the Li of 0.3g1.47Al0.4Ti1.6(PO4)3Powder, which is put into the ball grinder equipped with ethyl alcohol, carries out mechanical ball
Mill forms the nano-scale particle colloidal sol with Tyndall effect, obtains after this colloidal sol is diluted to 50g with ethyl alcohol with 100g step 2
The positive electrode matrix arrived mixes 15min with the speed of 150r/min, after mixture is then filtered 20min in suction funnel
It is put into 85 DEG C of vacuum drying ovens and dries 4h, by drying material in 400 DEG C of heat treatment 5h, be made by nanoscale Li1.47Al0.4Ti1.6
(PO4)3The polynary positive pole material of cladding.It carries out titration test by potentiometric titrimeter and obtains the surface lithium carbonate of sample at this time containing
Amount is 1180ppm.
By positive electrode sample assembly obtained above at solid state lithium battery.Specific assembling steps and characterizing method and comparison
Method in example 2 is consistent, and details are not described herein again.
As shown in fig. 6, polynary positive pole material manufactured in the present embodiment is assembled into solid state lithium battery in 3.0~4.3V, 0.2C
Lower specific discharge capacity is 166.7mAh/g, improves 50.4mAh/g than comparative example 2.
As shown in fig. 7, polynary positive pole material manufactured in the present embodiment is assembled into solid state lithium battery in 3.0~4.3V, 0.2C
Under be recycled to the 10th week specific discharge capacity and be maintained at 160.5mAh/g, recycle conservation rate and cycle life with comparative example 2 compared with greatly
It is big to improve.
Embodiment 3
Step 1: nickel sulfate, cobaltous sulfate, manganese sulfate are dissolved to obtain 1.5mol/ according to the ratio of metal molar ratio 2:1:1
Aluminum sulfate and sodium hydroxide are obtained aluminium ion concentration 0.2mol/L according to molar ratio 1:10 mixed preparing by the mixing salt solution of L
Aluminum solutions；Sodium hydroxide is dissolved into the aqueous slkali that concentration is 5mol/L；The complexing for being 2mol/L at concentration by ammonia solvent
Agent solution.Mixing salt solution, aluminum solutions, aqueous slkali, enveloping agent solution together cocurrent are added in reaction kettle and reacted, mistake
It is constant that journey is kept stirring revolving speed 115rpm, and control pH is 11.8~12.0, and temperature is 55 DEG C, when reaction is completed, keeps temperature, stirs
It is constant to mix revolving speed, continues to stir 20min, then nickel cobalt manganese aluminium hydroxide slurry obtained is separated by solid-liquid separation, is washed, filter
It is sieved after 110 DEG C of drying 3h of cake, obtains the spherical nickel cobalt manganese hydroxide materials of aluminium element Uniform Doped.
Step 2: the spherical nickel cobalt manganese hydroxide materials for the aluminium element Uniform Doped that step 1 obtains are mixed with lithium carbonate
It closes uniformly, wherein lithium carbonate is added according to molar ratio Li/ (Ni+Co+Mn+Al)=0.97.In air atmosphere, 900 DEG C of sintering
8h obtains anode material for lithium ion battery matrix Li by broken, screening0.97(Ni0.5Co0.25Mn0.25)0.995Al0.005O2。
It carries out titration test to obtain the surface carbonic acid lithium content of sample at this time being 1340ppm by potentiometric titrimeter.
Step 3: by the Li of 1.0g7.2La3Zr2O12Powder is put into the ball grinder equipped with N-Methyl pyrrolidone the machine that carries out
Tool ball milling forms the nano-scale particle colloidal sol with Tyndall effect, this colloidal sol is diluted to 100g with N-Methyl pyrrolidone
The positive electrode matrix obtained afterwards with 100g step 2 mixes 17min with the speed of 100r/min, is then filtering mixture
It is put into 140 DEG C of vacuum drying ovens after suction filtration 14min in funnel and dries 3h, by drying material in 500 DEG C of heat treatment 4h, be made by nanometer
Grade Li7.2La3Zr2O12The nickel-cobalt-manganese multi positive electrode of cladding.Titration test, which is carried out, by potentiometric titrimeter obtains sample at this time
Surface carbonic acid lithium content be 530ppm.
Positive electrode sample assembly obtained above is subjected to electrochemical Characterization at the lithium ion battery containing liquid electrolyte.
Specific assembling steps and characterizing method are consistent with the method in comparative example 1, and details are not described herein again.Electrochemical property test shows,
The sample that the present embodiment is prepared specific discharge capacity at 3.0~4.3V, 0.1C is 164.1mAh/g, sample 3.0~
Capacity retention ratio reaches 96.2% after recycling 80 weeks under 4.3V, 1C, 45 DEG C of multiplying powers.
Embodiment 4
Step 1 and step 2 are consistent with 2 preparation step of comparative example.
Step 3: by the Li of 0.35g7.15La3Zr2O12Powder, which is put into the ball grinder equipped with pure water, carries out mechanical ball mill, shape
At the nano-scale particle colloidal sol with Tyndall effect, obtained after this colloidal sol is diluted to 50g with pure water with 100g step 2
Positive electrode matrix mixes 15min with the speed of 150r/min, is put into after mixture is then filtered 20min in suction funnel
4h is dried in 100 DEG C of vacuum drying ovens, by drying material in 350 DEG C of heat treatment 6h, is made by nanoscale Li7.15La3Zr2O12Cladding
Polynary positive pole material.It carries out titration test to obtain the surface carbonic acid lithium content of sample at this time being 1275ppm by potentiometric titrimeter.
By positive electrode sample assembly obtained above at solid state lithium battery.Specific steps are as follows: obtain PEO, step 3
Nanoscale Li7.15La3Zr2O12Colloidal sol and LiTFSI (the mass ratio of the material EO:Li=12, mass ratio EO:Li7.15La3Zr2O12=
It 15:1) is dissolved in pure water, after stirring 16 hours, obtained slurry is cast in Teflon mould, in 55 DEG C of baking
Composite electrolyte membrane is placed in press after hot pressing 10min after being dried in vacuo 10 hours in case and is taken out, the circle of diameter 19mm is washed into
Piece type composite electrolyte membrane.By polynary positive pole material obtained above, conductive black, PVDF, LiTFSI according to mass ratio 90:3:
5:2 mixing, is added suitable NMP, scratches on aluminium foil after mixing evenly, and dry 1h, is washed into diameter in 120 DEG C of convection ovens
For the anode pole piece of 11mm；Using lithium metal as cathode, the anode pole piece of preparation and composite electrolyte membrane are contained in water content and oxygen
Amount is respectively less than in the Ar gas glove box of 5ppm and is assembled into 2025 type button cells.By above-mentioned button cell 3.0~4.3V,
0.2C, charge-discharge test is carried out at 60 DEG C.Test result shows that polynary positive pole material manufactured in the present embodiment is assembled into solid-state lithium
Battery specific discharge capacity at 3.0~4.3V, 0.2C is 170.2mAh/g, improves 55.9mAh/g than comparative example 2.Battery follows
Ring to the 10th week specific discharge capacity is maintained at 166.3mAh/g, recycles conservation rate and cycle life significantly mentions compared with comparative example 2
It is high.
Embodiment 5
Step 1 is consistent with 1 preparation step of comparative example.
Step 2: the nickel cobalt manganese hydroxide materials that step 1 is obtained and nano oxidized magnesium dust, nano oxidized zirconium powder
End is mixed according to the ratio of molar ratio (Ni+Co+Mn): Mg:Zr=99:0.4:0.6.Above-mentioned mixture is mixed with lithium hydroxide again
It closes uniformly, wherein lithium hydroxide is added according to molar ratio Li/ (Ni+Co+Mn+Mg+Zr)=1.03.In oxygen atmosphere, 750 DEG C
It is sintered 16h, by broken, screening, obtains anode material for lithium ion battery matrix Li1.03(Ni0.8Co0.1Mn0.1)0.99Mg0.004Zr0.006O2。
Step 3: by 0.5g solid electrolyte powder Li1.33Al0.3Ti1.7(PO4)3Be put into the ball grinder equipped with acetonitrile into
Row mechanical ball mill forms the nano-scale particle colloidal sol with Tyndall effect, by same 100g after this colloidal sol dilution in acetonitrile to 30g
The positive electrode matrix that step 2 obtains mixes 10min with the speed of 180r/min, then takes out mixture in suction funnel
It is put into 70 DEG C of vacuum drying ovens after filter 10min and dries 3h, drying material is heat-treated 8h in 400 DEG C of temperature ranges, be made by receiving
Meter level solid electrolyte Li1.33Al0.3Ti1.7(PO4)3The polynary positive pole material of cladding.
Positive electrode sample assembly obtained above is subjected to electrochemical Characterization at the lithium ion battery containing liquid electrolyte.
Specific assembling steps and characterizing method are consistent with the method in comparative example 1, and details are not described herein again.
Electrochemical property test shows, the sample that the present embodiment is prepared specific discharge capacity at 3.0~4.3V, 0.1C
For 206.3mAh/g, the positive electrode prepared than comparative example 1 improves 6.7mAh/g.In 3.0~4.3V, 1C, recycle at 45 DEG C
Capacity retention ratio is 93.4% after 80 weeks.
Embodiment 6
Step 1 and step 2 are consistent with 2 preparation step of comparative example.
Step 3: by the Li of 0.45g1.32Al0.2Y0.1Ti1.7(PO4)3Powder is put into the ball grinder equipped with ethylene glycol and carries out
Mechanical ball mill forms the nano-scale particle colloidal sol with Tyndall effect, this colloidal sol spent glycol is diluted to after 10g and is put into spray
The positive electrode matrix obtained in mist drying equipment with 100g step 2 is spray-dried 20min at nitrogen atmosphere, 150 DEG C, so
The material after spray drying is made in 450 DEG C of heat treatment 5h by nanoscale Li afterwards1.32Al0.2Y0.1Ti1.7(PO4)3What is coated is more
First positive electrode.
Positive electrode sample assembly obtained above is subjected to electrochemical Characterization at the lithium ion battery containing liquid electrolyte.
Specific assembling steps and characterizing method are consistent with the method in comparative example 1, and details are not described herein again.
Electrochemical property test shows, the sample that the present embodiment is prepared specific discharge capacity at 3.0~4.3V, 0.1C
For 182.4mAh/g.In 3.0~4.3V, 1C, recycle 80 weeks at 45 DEG C after capacity retention ratio be 94.3%.
Embodiment 7
Step 1 and step 2 are consistent with 5 preparation step one, two of embodiment.
Step 3: respectively by solid electrolyte powder Li1.4Cr0.4Ti1.6(PO4)3And Li1.305Ti2Si0.3P2.7O12Respectively
0.3g, which is put into the ball grinder equipped with pure water, carries out mechanical ball mill, forms the nano-scale particle colloidal sol with Tyndall effect, will
Two kinds of colloidal sols mix after being diluted to 50g with pure water respectively and the positive electrode matrix that obtains with 100g step 2 is with 170r/min's
Speed mixes 13min, then filters to be put into 125 DEG C of vacuum drying ovens after 14min in suction funnel by mixture and dries 4h, general
Drying material is heat-treated 5h in 350 DEG C of temperature ranges, is made by nanoscale solid state electrolyte Li1.4Cr0.4Ti1.6(PO4)3With
Li1.305Ti2Si0.3P2.7O12The polynary positive pole material of compound coating.Titration test, which is carried out, by potentiometric titrimeter obtains sample at this time
The surface carbonic acid lithium content of product is 1550ppm.
Positive electrode sample assembly obtained above is subjected to electrochemical Characterization at the lithium ion battery containing liquid electrolyte.
Specific assembling steps and characterizing method are consistent with the method in comparative example 1, and details are not described herein again.
Electrochemical property test shows, the sample that the present embodiment is prepared specific discharge capacity at 3.0~4.3V, 0.1C
For 204.1mAh/g, the positive electrode prepared than comparative example 1 improves 4.5mAh/g.In 3.0~4.3V, 1C, recycle at 45 DEG C
Capacity retention ratio is 93.2% after 80 weeks.
Embodiment 8
Step 1 is consistent with 1 preparation step of comparative example.
Step 2: the nickel cobalt manganese hydroxide materials that step 1 is obtained and nano lanthanum oxide powder are according to molar ratio (Ni+
Co+Mn): the ratio mixing of La=99.8:0.2.Above-mentioned mixture is uniformly mixed with lithium hydroxide again, wherein lithium hydroxide is pressed
According in molar ratio Li/ (Ni+Co+Mn+La)=1.2 oxygen atmosphere, 750 DEG C of sintering 13h obtain lithium ion by broken, screening
Positive electrode for battery material matrix Li1.2(Ni0.8Co0.1Mn0.1)0.998La0.002O2。
Step 3: respectively by solid electrolyte powder Li1.42Al0.4Ge1.6(PO4)3And Li6.5La3Zr1.4Ta0.6O12Respectively
0.3g, which is put into the ball grinder equipped with isopropanol, carries out mechanical ball mill, forms the nano-scale particle colloidal sol with Tyndall effect,
By two kinds of colloidal sols respectively with mixing after isopropanol to 40g and the positive electrode matrix obtained with 100g step 2 is with 175r/
The speed of min mixes 14min, then filters to be put into 145 DEG C of vacuum drying ovens after 13min in suction funnel by mixture and dry
Drying material is heat-treated 6h in 350 DEG C of temperature ranges by 4h, is made by nanoscale solid state electrolyte Li1.47Al0.4Ge1.6(PO4)3
And Li6.5La3Zr1.4Ta0.6O12The polynary positive pole material of compound coating.
Positive electrode sample assembly obtained above is subjected to electrochemical Characterization at the lithium ion battery containing liquid electrolyte.
Specific assembling steps and characterizing method are consistent with the method in comparative example 1, and details are not described herein again.
Electrochemical property test shows, the sample that the present embodiment is prepared specific discharge capacity at 3.0~4.3V, 0.1C
For 205.5mAh/g, the positive electrode prepared than comparative example 1 improves 5.9mAh/g.In 3.0~4.3V, 1C, recycle at 45 DEG C
Capacity retention ratio is 93.1% after 80 weeks.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Within the technical scope of the present disclosure, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Subject to enclosing.
Claims (10)
1. a kind of nickelic long-life multielement positive electrode, it is characterised in that including matrix and the solid-state for being coated on described matrix surface
Electrolyte clad；The chemical formula of described matrix is Li1+a[(Ni1-2xCoxMnx)1-yMy]1-zM′zO2, wherein -0.5≤a≤0.3,
0.05≤x≤0.3,0≤y≤0.01,0≤z≤0.01, it is Li that the clad, which contains chemical formula,uM″vM″′γM″″βM″″′αOw
Solid electrolyte, wherein 1≤u≤8,0≤v≤3,0≤γ≤2,1≤β≤3,1≤α≤3,2≤w≤12, M and M ' be La,
At least one of Cr, Mo, Ca, Fe, Hf, Ti, Zn, Y, Zr, Si, W, Nb, Sm, V, Mg, B, Al element, M ", M " ', M " ",
M " " ' is at least one of Zr, Ti, Cr, Al, Si, Mn, Sn, W, Nb, P, La, Ta, Ge, Ga, Y, Sc element.
2. nickelic long-life multielement positive electrode according to claim 1, it is characterised in that the solid electrolyte cladding
For layer to be fine and close or un-densified, the mole of clad accounts for the 0.01~5% of matrix；Nickelic long-life multielement positive electrode is averaged
Partial size D50It is 2~20 μm.
3. a kind of preparation method of nickelic long-life multielement positive electrode, it is characterised in that the following steps are included:
(1) salt solution of nickel, cobalt, manganese and doped chemical is obtained into the mixing salt solution of 1~3mol/L；By sodium hydroxide
It is dissolved into the aqueous slkali that concentration is 4~10mol/L；The enveloping agent solution for being 2~10mol/L at concentration by ammonia solvent；It will mix
Closing salting liquid, aqueous slkali, enveloping agent solution, cocurrent is added in reaction kettle and is reacted together, is kept stirring in the process, simultaneously
Control pH value in reaction and reaction temperature, precursor pulp obtained obtain spherical shape after separation of solid and liquid, washing, drying, screening
Nickel cobalt manganese hydroxide (Ni1-2xCoxMnx)1-yMy(OH)2；
(2) (the Ni for obtaining step (1)1-2xCoxMnx)1-yMy(OH)2Be uniformly mixed with the oxide of lithium salts, M ', in air or
In oxygen atmosphere, 4~20h is calcined at 600~1000 DEG C, by broken, screening, obtains anode material for lithium ion battery matrix
Li1+a[(Ni1-2xCoxMnx)1-yMy]1-zM′zO2；
(3) the solid electrolyte powder prepared is put into the ball grinder equipped with liquid medium and carries out mechanical ball mill, form tool
There is the nano-scale particle colloidal sol of Tyndall effect, after this colloidal sol is diluted by a certain percentage with liquid medium and the positive electrode
Matrix mixes 5~25min, after mixture is then filtered 5~20min in Suction filtration device, is put into 100~180 DEG C of vacuum and dries
0.5-6h is dried in case；Or the nano-scale particle colloidal sol with Tyndall effect of formation is put into spraying device, certain
It is carried out spraying mixing with the positive electrode matrix at a temperature of and dried by atmosphere, achievees the effect that uniformly to coat；Finally
Material after above-mentioned drying is heat-treated 2~10h in 100~800 DEG C of temperature ranges, is made by nanoscale solid state electrolyte
LiuM″vM″′γM″″βM″″′αOwThe nickel-cobalt-manganese multi positive electrode of cladding.
4. the preparation method of nickelic long-life multielement positive electrode according to claim 3, it is characterised in that the LiuM″vM″′γM″″βM″″′αOwSolid electrolyte is Li1+δ1Ti2(PO4)3、Li1.1+δ1Al0.1Ti1.9(PO4)3、Li1.2+δ1Al0.2Ti1.8
(PO4)3、Li1.3+δ1Al0.3Ti1.7(PO4)3、Li1.4+δ1Al0.4Ti1.6(PO4)3、Li1.5+δ1Al0.5Ti1.5(PO4)3、Li1.3+δ 1Al0.2Y0.1Ti1.7(PO4)3、Li1.4+δ1Cr0.4Ti1.6(PO4)3、Li1.3+δ1Al0.2Sc0.1Ti1.7(PO4)3、Li1.3+δ 1Al0.2Ge0.1Ti1.7(PO4)3、Li1.3+δ1Al0.3Ge1.7(PO4)3、Li1.5+δ1Al0.5Ge1.5(PO4)3、Li1.3+δ 1Ti2Si0.3P2.7O12、Li0.33+δ1La0.57TiO3、Li6.55+δ2La3Zr2Ge0.15O12、Li7+δ2La3Zr1.4Nb0.6O12、Li7+δ 2La3Zr1.6Ta0.4O12、Li7+δ2La3Zr1.6W0.4O12、Li6.4+δ2La3Zr1.4Ta0.6O12、Li0.34+δ1La0.51TiO2.94、Li3+δ 1La3Te2O12、Li5+δ2La3Bi2O12、Li7+δ2La3Zr2O12、Li4+δ2Ti5O12One or more of, wherein -0.1≤δ 1≤
0.3, -0.5≤δ 2≤0.5.
5. the preparation method of nickelic long-life multielement positive electrode according to claim 4, it is characterised in that the LiuM″vM″′γM″″βM″″′αOwSolid electrolyte is Li1.3Al0.3Ti1.7(PO4)3、Li1.4Al0.4Ti1.6(PO4)3、Li1.4Cr0.4Ti1.6
(PO4)3、Li7La3Zr2O12、Li1.5Al0.5Ge1.5(PO4)3、Li6.4La3Zr1.4Ta0.6O12、Li7La3Zr1.4Nb0.6O12、
Li7La3Zr1.6Ta0.4O12、Li7La3Zr1.6W0.4O12、Li1.3Ti2Si0.3P2.7O12One of or it is a variety of.
6. the preparation method of nickelic long-life multielement positive electrode according to claim 3, it is characterised in that step (1) institute
Stating reaction pH range is 10~13, and temperature is 50~70 DEG C.
7. the preparation method of nickelic long-life multielement positive electrode according to claim 3, it is characterised in that step (2) institute
The additional amount for stating lithium salts is molar ratio=0.95~1.3 of Li/ (Ni+Co+Mn+M+M ').
8. the preparation method of nickelic long-life multielement positive electrode according to claim 3, it is characterised in that in step (3)
Liquid medium used in the mechanical milling process is pure water, methanol, ethyl alcohol, propyl alcohol, ethylene glycol, isopropanol, benzyl alcohol, third
Ketone, benzene, toluene, methyl ether, ether, acetic acid, dimethylbenzene, tetrahydrofuran, dimethyl carbonate, N-Methyl pyrrolidone, propylene carbonate
One or more of ester, N,N-dimethylformamide, acetonitrile, glycol dimethyl ether.
9. the preparation method of nickelic long-life multielement positive electrode according to claim 3, it is characterised in that step (3) institute
Stating the weight ratio after colloidal sol dilutes with positive electrode is 1:4~1:0.5.
10. the preparation method of nickelic long-life multielement positive electrode according to claim 3, it is characterised in that step (3)
Described in colloidal sol dilution after with positive electrode matrix incorporation time be 5~35min.
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