CN103606674A - Surface-modified lithium cobaltate material and preparation method thereof - Google Patents
Surface-modified lithium cobaltate material and preparation method thereof Download PDFInfo
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- CN103606674A CN103606674A CN201310594556.3A CN201310594556A CN103606674A CN 103606674 A CN103606674 A CN 103606674A CN 201310594556 A CN201310594556 A CN 201310594556A CN 103606674 A CN103606674 A CN 103606674A
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- element compound
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- oxide
- acid lithium
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- 239000000463 material Substances 0.000 title claims abstract description 118
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 150000002641 lithium Chemical class 0.000 title abstract 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 134
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 133
- 239000003792 electrolyte Substances 0.000 claims abstract description 45
- 239000007771 core particle Substances 0.000 claims abstract description 31
- 238000000576 coating method Methods 0.000 claims abstract description 24
- 239000011248 coating agent Substances 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims description 199
- 239000002184 metal Substances 0.000 claims description 189
- 229910017052 cobalt Inorganic materials 0.000 claims description 133
- 239000010941 cobalt Substances 0.000 claims description 133
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 133
- 239000002253 acid Substances 0.000 claims description 120
- 150000001875 compounds Chemical class 0.000 claims description 117
- 150000004703 alkoxides Chemical class 0.000 claims description 54
- -1 ester salt Chemical class 0.000 claims description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- 229910044991 metal oxide Inorganic materials 0.000 claims description 47
- 150000004706 metal oxides Chemical class 0.000 claims description 47
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 46
- 150000004692 metal hydroxides Chemical class 0.000 claims description 46
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 40
- 159000000021 acetate salts Chemical class 0.000 claims description 40
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 40
- 238000011282 treatment Methods 0.000 claims description 37
- 230000004048 modification Effects 0.000 claims description 35
- 238000012986 modification Methods 0.000 claims description 35
- 239000010936 titanium Substances 0.000 claims description 32
- 239000011777 magnesium Substances 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- DJZIBVUGARDLOC-UHFFFAOYSA-N [Ni]=O.[Co]=O.[Li] Chemical compound [Ni]=O.[Co]=O.[Li] DJZIBVUGARDLOC-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 claims description 13
- 229940011182 cobalt acetate Drugs 0.000 claims description 12
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 12
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000010405 anode material Substances 0.000 claims description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 9
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 8
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 7
- 239000002245 particle Substances 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
- 238000005245 sintering Methods 0.000 claims description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 4
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 claims description 4
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 claims description 4
- 238000002407 reforming Methods 0.000 claims description 4
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 3
- 241001676573 Minium Species 0.000 claims description 3
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 21
- 239000011247 coating layer Substances 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 10
- 150000003839 salts Chemical class 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 4
- 101100459320 Caenorhabditis elegans myo-2 gene Proteins 0.000 abstract 1
- 229910018680 LixCo Inorganic materials 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 230000001351 cycling effect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 14
- 235000019441 ethanol Nutrition 0.000 description 13
- 239000011572 manganese Substances 0.000 description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 10
- 239000004411 aluminium Substances 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 239000011701 zinc Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000011575 calcium Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- SXSVTGQIXJXKJR-UHFFFAOYSA-N [Mg].[Ti] Chemical compound [Mg].[Ti] SXSVTGQIXJXKJR-UHFFFAOYSA-N 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000013467 fragmentation Methods 0.000 description 6
- 238000006062 fragmentation reaction Methods 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 238000003801 milling Methods 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000001976 improved effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229940071125 manganese acetate Drugs 0.000 description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 3
- 229940078494 nickel acetate Drugs 0.000 description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 229910001051 Magnalium Inorganic materials 0.000 description 2
- PMULXWIGWVQPHP-UHFFFAOYSA-N butan-1-ol;tin Chemical compound [Sn].CCCCO PMULXWIGWVQPHP-UHFFFAOYSA-N 0.000 description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 2
- 239000001639 calcium acetate Substances 0.000 description 2
- 229960005147 calcium acetate Drugs 0.000 description 2
- 235000011092 calcium acetate Nutrition 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- NNSIWZRTNZEWMS-UHFFFAOYSA-N cobalt titanium Chemical compound [Ti].[Co] NNSIWZRTNZEWMS-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052726 zirconium 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
- H01M4/52—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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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 discloses a surface-modified lithium cobaltate material and a preparation method thereof. The lithium cobaltate material comprises a core particle and a surface-modified layer coating the core particle, wherein the core particle is a lithium cobaltate-based positive material with a structural formula as follows: LixCo(1-y)MyO2, wherein x is greater than 1 and not greater than 1.2, y is not less than 0 and not greater than 0.1, M is a doping element; the surface-modified layer comprises a Li<+1> conducting layer and an electrolyte isolating layer; the core particle is coated by the Li<+1> conducting layer and the electrolyte isolating layer in sequence. According to the invention, by sufficiently utilizing dynamic characteristic that different substances react with residual Li salt on the surface of the lithium cobaltate, and characteristic of final reaction product performance, the lithium cobaltate material with double coating layers is prepared. The material is high in comprehensive performances, has high discharge capacity, high cycling stability and the like. The preparation method disclosed by the invention is simple in process and easily realizes industrial production.
Description
Technical field
The invention belongs to lithium ion battery electrode material field, be specifically related to cobalt acid lithium material of a kind of surface modification treatment and preparation method thereof.
Background technology
The production technology of cobalt acid lithium material is simple, there is high, the applicable high current charge-discharge of voltage platform, specific energy advantages of higher simultaneously, therefore in lithium rechargeable battery commercialization, start just to have adopted cobalt acid lithium as its positive electrode, meanwhile, cobalt acid lithium is also current topmost commercial lithium-ion batteries positive electrode.Although it has plurality of advantages as positive electrode, the anti-over-charging ability of this material, when charge cutoff voltage is greater than 4.2V, Li
+a large amount of de-embeddings can occur, cause cobalt acid lithium surface to form oxygen defect, finally cause surface texture unstable, the specific discharge capacity of material is decay rapidly.
For improving above-mentioned defect, in recent years, about the doping of cobalt acid lithium and coated patent and document, there are a large amount of reports, for example, cobalt acid lithium is carried out to Chinese patent " cathode material precursors of the homogeneous nanoparticle core doping " (Granted publication number: CN101897061B) and to cobalt acid lithium carry out Zr of Ti element doping, the Chinese patent of the element dopings such as P " lithium ion secondary battery anode material zirconium, phosphor adulterated cobalt acid lithium and preparation method thereof " (Granted publication number: CN100495775C) and to cobalt acid lithium material carry out the coated Chinese patent application of Al " preparation method of the anode material for lithium-ion batteries of surface clad oxide " (application publication number: CN101950803A) etc.The result of study of above-mentioned report shows, by playing to the doping of cobalt acid lithium and coated modification etc. the structure of stablizing cobalt acid lithium material, and suppress the effects such as side reaction between cobalt acid lithium and electrolyte, based on above-mentioned result of study, current battery manufacturer has developed the even lithium ion battery of 4.35V of 4.3V, but still can not meet the more especially requirement of cycle performance of properties of sample under high voltage (>=4.4V) condition, because above-mentioned doping, coating technology does not produce the impact of essence on the structural stability of material, 4.4V or more under high voltage the specific discharge capacity of material there will be the phenomenon of quick decay, simultaneously, by above doping, coating technology can't improve the specific discharge capacity of material and efficiency etc. first, therefore, aspect electrical property, also there is larger defect in it, this has also reduced the energy density of lithium ion battery to a great extent.
Summary of the invention
For overcoming above-mentioned defect, we carry out special modification to the surface of cobalt acid lithium material, because be the monocrystalline cobalt acid lithium of 15～20 microns for a large amount of particle diameters that use in commercialization, are subject to Li
+the impact of transmission path, the degree that in particle, the cobalt of diverse location acid lithium overcharges is different.The cobalt acid lithium of surface part the most easily overcharges because Li+ transmission path is the shortest, the cobalt acid lithium structure in this region is also the most easily destroyed, therefore the cobalt acid lithium that, has a special surface of stability structure should be the design direction that has the cobalt acid lithium material of high specific discharge capacity and high voltage (>=4.4V) concurrently.
An object of the present invention is to provide a kind of cobalt acid lithium material of surface modification treatment, described cobalt acid lithium material not only can improve its cycle performance under high voltage (>=4.4V) more, and can also improve the specific discharge capacity of material under high voltage (>=4.4V).
Concrete technical scheme is as follows:
A cobalt acid lithium material for surface modification treatment, is characterized in that, comprises the surface reforming layer of core particle and coated described core particle, and described core particle is cobalt acid lithium base anode material, and its structural formula is: Li
xco
1-ym
yo
2, 1 < x≤1.2,0≤y≤0.1, M is doped chemical; Described surface reforming layer comprises Li
+conducting shell and electrolyte separator, described core particle is successively by described Li
+conducting shell and described electrolyte separator are coated.
Further, described doped chemical M comprises one or more in Mg, Ti, Al.
Further, described Li
+conducting shell comprises one or more in Co element compound, Mn element compound, Ni element compound, lithium nickel cobalt dioxide predecessor, nickle cobalt lithium manganate predecessor, described Li
+in conducting shell, in metallic element and described core particle, the mol ratio of Co element is 0.1%～10%.
Further, above-mentioned Li
+in conducting shell, described Co element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Co element, preferably contains metal oxide and the metal hydroxides of Co element; Described Mn element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Mn element, preferably contains metal oxide and the metal hydroxides of Mn element; Described Ni element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Ni element, preferably contains metal oxide and the metal hydroxides of Ni element; Described lithium nickel cobalt dioxide predecessor is the oxide of lithium nickel cobalt dioxide, one or more in hydroxide; Described nickle cobalt lithium manganate predecessor is one or more in nickle cobalt lithium manganate oxide, hydroxide, and the size of described Co element compound, described Mn element compound, described Ni element compound, described lithium nickel cobalt dioxide predecessor, described nickle cobalt lithium manganate predecessor is nanoscale.
Further, described electrolyte separator comprises one or more in Mg element compound, Ti element compound, Al element compound, Zr element compound, Sn element compound, Zn element compound, Ca element compound, it is of a size of 20～500 nanometers, and in described electrolyte separator, the mass ratio of metallic element and described core particle is 0.01%～1%.
Further, in above-mentioned electrolyte separator, described Mg element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Mg element, preferably metal alkoxide, metal ester salt; Described Ti element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Ti element, preferably metal alkoxide, metal ester salt; Described Al element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Al element, preferably metal alkoxide, metal ester salt; Described Zr element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Zr element, preferably metal alkoxide, metal ester salt; Described Sn element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Sn element, preferably metal alkoxide, metal ester salt; Described Zn element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Zn element, preferably metal alkoxide, metal ester salt; Described Ca element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Ca element, preferably metal alkoxide, metal ester salt.
Another object of the present invention is to provide a kind of preparation method of cobalt acid lithium material of above-mentioned surface modification treatment, comprises the steps:
(1) by Li element compound, Co element compound and containing the compound of doped metallic elements M, according to mol ratio, be Li:(Co+M)=(1～1.2): 1 mixes;
(2) mixed raw material is placed in to baking furnace, roasting in air atmosphere, sintering temperature is 600～1100 ℃, preferably, between 900～1050 ℃, roasting time is 4～20 hours, obtains monocrystalline cobalt acid lithium;
(3) described monocrystalline cobalt acid lithium is pulverized, obtained described core particle, it is monocrystal particle, its average grain diameter D
50be 6～20 microns, preferably 12～20 microns;
(4) by Li
+the coated material of conducting shell joins in ethanol or deionized water, wherein the mass ratio of coated material and ethanol or deionized water is 1:5～1:100, stir 0.5～4 hour, after stirring completes, the cobalt acid lithium obtaining in step (3) is joined in above-mentioned mixed liquor, and at 100～300 ℃, dry 2～6 hours, final, Li
+the coated material of conducting shell has evenly been coated in the core particle surface described in step (3), and the thickness of coating is 20～500 nanometers, described Li
+in the coated material of conducting shell, in metallic element and described core particle, the mol ratio of Co element is 0.1%～10%;
(5) the coated material of electrolyte separator is joined in ethanol or deionized water, wherein the mass ratio of coated material and ethanol or deionized water is 1:5～1:100, stir 0.5～4 hour, after stirring completes, the cobalt acid lithium material obtaining in step (4) is joined in above-mentioned mixed liquor, and at 100～300 ℃, dry 2～6 hours, finally, the coated material of electrolyte separator has evenly been coated in the surface of the cobalt acid lithium material described in step (4), the thickness applying is 20～500 nanometers, in the coated material of described electrolyte separator, the mass ratio of metallic element and described core particle is 0.01%～1%,
(6) the described core particle in step (5) is carried out to sintering under normal pressure and air atmosphere, first 300～500 ℃ of preliminary treatment 3～15 hours, then 500～1000 ℃ of heat treatments 3～15 hours.
Further, compound containing doped chemical M described in step (1) is one or more in Mg element compound, Ti element compound, Al element compound, preferably Mg is element compound doped, Mg element compound and Ti element compound mixing and doping and Mg element compound and Al element compound mixing and doping, described Mg element compound refers to one or more in magnesium oxide, magnesium hydroxide, magnesium carbonate; Described Ti element compound refers to one or more in titanium dioxide, butyl titanate; Described Al element compound refers to one or more in minium, aluminium hydroxide, aluminium isopropoxide.
Further, described in step (1), the compound of Li element comprises one or more in lithium carbonate, lithium hydroxide, lithium acetate.
Further, described in step (1), the compound of Co element comprises one or more in cobaltosic oxide, cobalt hydroxide, cobalt carbonate, cobalt acetate.
Further, Li described in step (4)
+the coated material of conducting shell refers to one or more in Co element compound, Mn element compound, Ni element compound, lithium nickel cobalt dioxide predecessor, nickle cobalt lithium manganate predecessor, described Co element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Co element, preferably contains metal oxide and the metal hydroxides of Co element; Described Mn element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Mn element, preferably contains metal oxide and the metal hydroxides of Mn element; Described Ni element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Ni element, preferably contains metal oxide and the metal hydroxides of Ni element; Described lithium nickel cobalt dioxide predecessor is the oxide of lithium nickel cobalt dioxide, one or more in hydroxide; Described nickle cobalt lithium manganate predecessor is one or more in nickle cobalt lithium manganate oxide, hydroxide.
Further, the coated material of electrolyte separator described in step (5) refers to one or more in Mg element compound, Ti element compound, Al element compound, Zr element compound, Sn element compound, Zn element compound, Ca element compound, described Mg element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Mg element, preferably metal alkoxide, metal ester salt; Described Ti element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Ti element, preferably metal alkoxide, metal ester salt; Described Al element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Al element, preferably metal alkoxide, metal ester salt; Described Zr element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Zr element, preferably metal alkoxide, metal ester salt; Described Sn element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Sn element, preferably metal alkoxide, metal ester salt; Described Zn element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Zn element, preferably metal alkoxide, metal ester salt; Described Ca element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Ca element, preferably metal alkoxide, metal ester salt.
The present invention has carried out special surface modification to cobalt acid lithium surface, has prepared the cobalt acid lithium material with two-coat surface texture that meets high specific discharge capacity and the requirement of high voltage (>=4.4V) cycle performance.This modifying process takes full advantage of kinetic character that the remaining Li salt in different material and cobalt acid lithium surface reacts and the feature of final reacting product performance.
First, aspect kinetics feature, internal layer coating (Co, the compound of the elements such as Mn) dynamics reacting with the remaining Li salt in cobalt acid lithium surface will be much larger than outer coating (Al, Mg, the compound of the elements such as Ti) dynamics reacting with the remaining Li salt in cobalt acid lithium surface, affected by this, internal layer coating just can react with the remaining Li salt on cobalt acid lithium surface at lower temperature (300 ℃～500 ℃), outer field coating needs higher temperature (500 ℃ of >) to react, utilize this feature, the sintering schedule that we take for first carrying out preliminary treatment 3～15 hours under cryogenic conditions (300 ℃～500 ℃), be elevated to again higher temperature (500 ℃ of >) heat treatment 3～15 hours, like this, at low temperature pretreatment stage, the coated material of internal layer can consume the Li on cobalt acid lithium surface, form inner Li
+conducting shell, after rising heat treatment temperature, because remaining Li is at Li
+in conducting shell, to stablize the form of chemical bond, exist, outer field coating cannot react with remaining Li again, can only form the electrolyte separators such as metal oxide, and like this, finally just having obtained internal layer is Li
+conduction coating layer, the outer two-coat for electrolyte isolation coating layer.
Secondly, at Li
+the product characteristic of property aspect of the coated material of conduction coating layer and the remaining Li salt of the coated material of electrolyte separator and cobalt acid lithium surface, Li
+co in the coated material of conduction coating layer, first procatarxis such as Mn has electro-chemical activity, the cobalt acid lithium generating in this coating layer forming process, LiMn2O4s etc. have contribution to specific discharge capacity, make its specific discharge capacity and first efficiency etc. also had greatly and improved, fully stablized the surface texture of cobalt acid lithium simultaneously, finally making its comprehensive electrochemical have greatly improves, and electrolyte is isolated the Al in coating layer, although the elements such as Mg also can consume the remaining Li salt on cobalt acid lithium surface, but because above element does not all have electro-chemical activity, after the remaining Li reactant salt on they and cobalt acid lithium surface, can not be improved effect to the chemical property of material, on the contrary, during the remaining Li reactant salt on a large amount of above elements and the sour lithium of cobalt surface, also can cause discharge capacity, the significantly reduction of efficiency first, chemical property to material damages, therefore, double-coated in the present invention takes full advantage of the advantage of each coating layer, in the two-coat forming, outside electrolyte separator can reduce the generation of side reaction between cobalt acid lithium surface and electrolyte, inner Li
+conducting shell has effectively improved the comprehensive electrochemical of material.
Two-coat in the present invention had both possessed the effect of the isolated electrolyte that normal packet coating plays, and had also overcome Li in normal packet coating
+conducting power is poor, interfacial structure is unstable, to the specific discharge capacity of material without the defect such as improving, coating function is single, at above Li
+under the comprehensive function of conducting shell and electrolyte separator, the cycle performance of material has had greatly improvement, under button cell 4.5V condition, still has good cycle performance.
In sum, advantage of the present invention is as follows:
1. the cobalt of surface modification treatment provided by the invention acid lithium material, is making full use of Li
+on the different characteristics basis of the coated material of conducting shell and the remaining Li reactant salt of the coated material of electrolyte isolation and cobalt acid lithium surface, by specific sintering schedule, obtained carrying out the lithium cobaltate cathode material that special surface modification has double-coated layer, the electrolyte separator of above double-coated layer peripheral has the effects such as side reaction of isolated electrolyte, minimizing and electrolyte that traditional coating layer possesses.
2. the more important thing is, the cobalt acid lithium material of surface modification treatment provided by the invention has inner Li
+conductive coatings, this Li
+conductive coatings makes the comprehensive electrochemical of material have greatly raising, has fully stablized the surface texture of cobalt acid lithium, at above-mentioned inner Li
+under the acting in conjunction of the two-coat of conductive coatings and outside electrolyte barrier coat; material can meet full battery 4.4V or the more requirement under high voltage, and this is that the technical approach such as general doping, coated and size particles mixing are inaccessiable to the improvement institute of material cycle performance.
3. the cobalt of surface modification treatment provided by the present invention acid lithium material is at high temperature (45 ℃), high voltage (4.5V) and high magnification (1.0C) etc. comparatively under exacting terms, and its cycle performance keeps better, and within 100 weeks, capability retention approximately 92.5%.
4. operating process of the present invention is easy, and the cost of raw material is lower, is easy to realize suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the cobalt acid lithium material of the surface modification treatment for preparing of the embodiment of the present invention 3.
The SEM figure of 1000 times of the cobalt acid lithium materials of the surface modification treatment that Fig. 2 a) prepares for the embodiment of the present invention 3.
The SEM figure of 3000 times of the cobalt acid lithium materials of surface modification treatment Fig. 2 b) preparing for the embodiment of the present invention 3.
Fig. 3 is the TEM figure of the cobalt acid lithium material of the surface modification treatment for preparing of the embodiment of the present invention 3.
Fig. 4 is the cycle performance figure of the cobalt acid lithium material of the surface modification treatment for preparing of the embodiment of the present invention 3.
Embodiment
Embodiment 1
The present embodiment is a kind of preparation method of cobalt acid lithium material of surface modification treatment, comprises the steps:
(1) ratio that is 1.20:0.98:0.02 in molar ratio in lithium, cobalt, magnesium is mixed lithium carbonate, cobaltosic oxide and cobalt acetate, magnesium oxide with dry method mode ball milling; After having mixed, above-mentioned material is placed in to baking furnace under air atmosphere roasting and normal pressure, with 600 ℃ of roastings, within 13 hours, obtains mixing the monocrystalline cobalt acid lithium of magnesium; The material that roasting completes carries out airflow milling fragmentation again and sieves after coarse crushing, finally obtains cobalt acid lithium material to be covered, its average grain diameter D
50it is 6 microns.
(2) nickel acetate is joined in ethanol, wherein the mass ratio of nickel acetate and ethanol is 1:100, stir 4 hours, the cobalt acid lithium obtaining in step (1) is joined in above-mentioned mixed liquor, and at 300 ℃, dry 2 hours, tentatively complete the ground floor of cobalt acid lithium is coated, the thickness of coating is about 20 nanometers, and wherein the mol ratio of the Co element in the Ni element in nickel acetate and cobalt acid lithium is 0.1%.
(3) butyl titanate is joined in ionized water, wherein the mass ratio of butyl titanate and ionized water is 1:5, stir 0.5 hour, after stirring completes, the cobalt acid lithium material of mixing magnesium obtaining in step (2) is joined in above-mentioned mixed liquor, and dry 2 hours at 300 ℃, tentatively complete the second layer of cobalt acid lithium coated, the thickness applying is about 20 nanometers, and in above-mentioned aluminium colloidal sol, the mass ratio of Al element and cobalt acid lithium is 0.01%.
(4) by the product after drying in step (3) under air atmosphere and normal pressure in baking furnace first 500 ℃ of preliminary treatment 3 hours, then 900 ℃ of heat treatments 5 hours, above-mentioned material is sieved after cooling, finally can obtain Li
+conducting shell and electrolyte separator double-coated and there is the cobalt acid lithium base high-voltage anode material of low remaining Li content.
The present embodiment is a kind of preparation method of cobalt acid lithium material of surface modification treatment, and concrete steps are as follows:
(1) ratio that is 1.07:0.98:0.01:0.01 in molar ratio in lithium, cobalt, titanium, aluminium is mixed lithium hydroxide, cobalt hydroxide, butyl titanate, aluminium oxide with dry method mode ball milling; After having mixed, above-mentioned material is placed in to baking furnace under air atmosphere roasting and normal pressure, with 1000 ℃ of roastings 13 hours, obtain mixing the monocrystalline cobalt acid lithium of titanium aluminium, the material that roasting completes carries out airflow milling fragmentation again and sieves after coarse crushing, finally obtain cobalt acid lithium material to be covered, its average grain diameter D
50be about 20 microns.
(2) manganese acetate, cobalt acetate are joined in deionized water, wherein the mass ratio of manganese acetate and cobalt acetate quality sum and deionized water is 1:5, stir 0.5 hour, the cobalt acid lithium that obtains mixing titanium aluminium in step (1) is joined in above-mentioned mixed liquor, and at 100 ℃, dry 6 hours, tentatively complete the ground floor of cobalt acid lithium coated, the thickness applying is about 500 nanometers, and wherein the mol ratio of the cobalt in the manganese in manganese acetate and cobalt acid lithium is 6%, the cobalt in cobalt acetate and the mol ratio of the cobalt in the sour lithium of cobalt be 4%.
(3) nano magnesia is joined in ethanol, wherein the mass ratio of nano magnesia and ethanol is 1:100, stir 4 hours, after stirring completes, the cobalt acid lithium material of mixing titanium aluminium obtaining in step (2) is joined in above-mentioned mixed liquor, and dry 6 hours at 100 ℃, tentatively complete the second layer of cobalt acid lithium coated, the thickness applying is about 500 nanometers, and in coating, the mass ratio of Al element and core particle is 1%.
(4) by the product after drying in step (3) under air atmosphere and normal pressure in baking furnace first 300 ℃ of preliminary treatment 15 hours, then 1000 ℃ of heat treatments 3 hours, above-mentioned material is sieved after cooling, finally can obtain Li
+conducting shell and electrolyte separator double-coated and there is the cobalt acid lithium base high-voltage anode material of low remaining Li content.
Embodiment 3
The present embodiment is a kind of preparation method of cobalt acid lithium material of surface modification treatment, and concrete steps are as follows:
(1) ratio that is 1.06:0.96:0.02:0.02 in molar ratio in lithium, cobalt, magnesium, titanium is mixed lithium carbonate, cobaltosic oxide, magnesium oxide and titanium dioxide with dry method mode ball milling; After having mixed, above-mentioned material is placed in to baking furnace under air atmosphere roasting and normal pressure, with 1015 ℃ of roastings 13 hours; The material that roasting completes carries out airflow milling fragmentation again and sieves after coarse crushing, finally obtains the monocrystalline cobalt acid lithium material of mixing magnesium titanium to be covered, its average grain diameter D
50be about 16 microns.
(2) cobalt acetate is joined in ethanol, wherein the mass ratio of cobalt acetate and ethanol is 1:50, stir 1 hour, the monocrystalline cobalt acid lithium that obtains mixing magnesium titanium in step (1) is joined in above-mentioned mixed liquor, and at 200 ℃, dry 4 hours, tentatively complete the ground floor of cobalt acid lithium is coated, the thickness of coating is about 40 nanometers, and wherein the mol ratio of the cobalt in the cobalt in cobalt acetate and cobalt acid lithium is 4%.
(3) aluminium isopropoxide is joined in ethanol, wherein the mass ratio of aluminium isopropoxide and ethanol is 1:80, stir 3 hours, after stirring completes, the cobalt acid lithium material of mixing magnesium titanium obtaining in step (2) is joined in above-mentioned mixed liquor, and dry 5 hours at 100 ℃, tentatively complete the second layer of cobalt acid lithium coated, the thickness applying is about 70 nanometers, and in coating, the mass ratio of Al element and core particle is 0.05%.
(4) by the product after drying in step (3) under air atmosphere and normal pressure in baking furnace first with 400 ℃ of preliminary treatment 3 hours, after with 800 ℃ of heat treatments 5 hours, above-mentioned material is sieved after cooling, finally can obtain Li
+conducting shell and electrolyte separator double-coated and there is the cobalt acid lithium base high-voltage anode material of low remaining Li content.
Fig. 1 is the phase XRD of the material of the present embodiment, and phase is pure cobalt acid lithium phase as seen from the figure, and after doping, the layer structure of cobalt acid lithium main body is not damaged.
Fig. 2 a) and Fig. 2 b) be the SEM figure that material prepared by the present embodiment amplifies 1000 times and 3000 times under electron microscope, the surface of sample is more mellow and fuller, smooth as seen from the figure, the Surface Modification Effect is obvious, is coated more even.
Fig. 3 is the TEM figure of the present embodiment under transmission electron microscope, and coating layer is double-coated as seen from the figure, and between interior external coating, has obvious line of demarcation.
Fig. 4 is the sample of the present embodiment cycle performance curve chart under the condition of high temperature (45 ℃), high voltage (4.5V) and high magnification (1.0C), and the cycle performance of sample keeps better as seen from the figure, and within 100 weeks, capability retention approximately 92.5%.
Embodiment 4
The present embodiment is a kind of preparation method of cobalt acid lithium material of surface modification treatment, and concrete steps are as follows:
(1) ratio that is 1.01:0.97:0.01:0.01:0.01 in molar ratio in lithium, cobalt, titanium, aluminium, magnesium is mixed lithium acetate, cobalt carbonate, butyl titanate, minium, magnesium oxide with dry method mode ball milling; After having mixed, above-mentioned material is placed in to baking furnace under air atmosphere roasting and normal pressure, with 1100 ℃ of roastings 4 hours; The material that roasting completes carries out airflow milling fragmentation again and sieves after coarse crushing, finally obtains the monocrystalline cobalt acid lithium material of mixing magnesium titanium aluminium to be covered, its average grain diameter D
50it is 10 microns.
(2) by the nanoscale predecessor of the lithium nickel cobalt dioxide of equimolar amounts, nanoscale cobalt acetate, nanoscale manganese oxide, nanoscale nickel hydroxide joins in deionized water, the nanoscale predecessor of lithium nickel cobalt dioxide wherein, nanoscale cobalt acetate, nanoscale manganese oxide, the quality of nanoscale nickel hydroxide and with the mass ratio of deionized water be 1:80, stir 3 hours, the monocrystalline cobalt acid lithium that obtains mixing magnesium titanium aluminium in step (1) is joined in above-mentioned mixed liquor, and at 150 ℃, dry 5 hours, tentatively complete the ground floor of cobalt acid lithium coated, the thickness applying is about 40 nanometers, the nanoscale predecessor of lithium nickel cobalt dioxide wherein, nanoscale cobalt acetate, nanoscale manganese oxide, the ratio of the mole of the cobalt in nanoscale nickel hydroxide in mole sum of metal and cobalt acid lithium is 3.5%.
(3) by equimolar isopropyl alcohol magnalium, calcium acetate, the sub-zinc of sulfuric acid, n-butanol tin, calcium nitrate, magnesium hydroxide and zirconia, butyl titanate joins in deionized water, isopropyl alcohol magnalium wherein, calcium acetate, the sub-zinc of sulfuric acid, n-butanol tin, calcium nitrate, magnesium hydroxide and zirconia, the quality sum of butyl titanate and the mass ratio of deionized water are 1:40, stir 2 hours, after stirring completes, the cobalt acid lithium material of mixing magnesium titanium aluminium obtaining in step (2) is joined in above-mentioned mixed liquor, and at 250 ℃, dry 3 hours, tentatively complete the second layer of cobalt acid lithium coated, the thickness applying is about 70 nanometers, Al element in coating, Ca element, Zn element, Mg element, Zr element, Ti element, the mass ratio of Sn element quality sum and core particle is 1%.
(4) by the product after drying in step (3) under air atmosphere and normal pressure in baking furnace first with 400 ℃ of preliminary treatment 15 hours, after with 500 ℃ of heat treatments 15 hours, above-mentioned material is sieved after cooling, finally can obtain Li
+conducting shell and electrolyte separator double-coated and there is the cobalt acid lithium base high-voltage anode material of low remaining Li content.
Embodiment 5
The present embodiment is a kind of preparation method of cobalt acid lithium material of surface modification treatment, and concrete steps are as follows:
(1) ratio that is 1.08:0.97:0.03 in molar ratio in lithium, cobalt, titanium is mixed lithium carbonate and lithium acetate and lithium hydroxide, cobaltosic oxide and cobalt carbonate, titanium dioxide with dry method mode ball milling; After having mixed, above-mentioned material is placed in to baking furnace under air atmosphere roasting and normal pressure, with 1020 ℃ of roastings 20 hours; The material that roasting completes carries out airflow milling fragmentation again and sieves after coarse crushing, finally obtains doped titanium monocrystalline cobalt acid lithium material to be covered, its average grain diameter D
50it is 15 microns.
(2) the nanoscale predecessor of nickle cobalt lithium manganate is joined in deionized water, wherein the nanoscale predecessor of nickle cobalt lithium manganate and the mass ratio of deionized water are 1:40, stir 2 hours, by obtaining doped titanium monocrystalline cobalt acid lithium in step (1), join in above-mentioned mixed liquor, and at 150 ℃, dry 6 hours, tentatively complete the ground floor of cobalt acid lithium coated, the thickness applying is 40 nanometers, and wherein in nickle cobalt lithium manganate predecessor, the ratio of the mole of the Co element in the mole sum of Ni element, Co element and Mn element and cobalt acid lithium is 4.0%.
(3) aluminium isopropoxide is joined in ethanol, wherein the mass ratio of aluminium isopropoxide and solvent is 1:30, stir 3 hours, after stirring completes, the doped titanium cobalt acid lithium material obtaining in step (2) is joined in above-mentioned mixed liquor, and at 250 ℃, dry 3 hours, tentatively complete the second layer of cobalt acid lithium coatedly, it is 0.05% that coating thick is about the mass ratio of Al element and core particle in 70 nano coatings.
(4) by the product after drying in step (3) under air atmosphere and normal pressure in baking furnace first with 450 ℃ of preliminary treatment 3 hours, after with 800 ℃ of heat treatments 5 hours, above-mentioned material is sieved after cooling, finally can obtain Li
+conducting shell and electrolyte separator double-coated and there is the cobalt acid lithium base high-voltage anode material of low remaining Li content.
Comparative example 1
This comparative example has been cancelled Li
+conduction coating layer, to contrast with the above embodiments 5.The preparation method of the cobalt acid lithium material of this comparative example is as follows:
(1) ratio that is 1.08:0.97:0.03 in molar ratio in lithium, cobalt, titanium is mixed lithium carbonate, cobaltosic oxide and titanium dioxide with dry method mode ball milling, after having mixed, above-mentioned material is placed in to baking furnace with 1020 ℃ of roastings 10 hours, the material that roasting completes carries out airflow milling fragmentation again and sieves after coarse crushing, finally obtain cobalt acid lithium material to be covered, its average grain diameter D
50it is 15 microns.
(2) aluminium isopropoxide is joined in absolute ethyl alcohol, being heated to 100 ℃ dissolves completely to aluminium isopropoxide, the cobalt acid lithium material of the coated cobalt oxide in surface in step (1) is joined in above-mentioned aluminium colloidal sol, stir 1 hour post-drying, in coating, the mass ratio of Al element and core particle is 0.05%.
(3) by the mixture after drying in step step (2) in baking furnace first with 450 ℃ of preliminary treatment 3 hours, after with 800 ℃ of heat treatments 5 hours, above-mentioned material is sieved after cooling.
It should be noted that, above cited be only specific embodiments of the invention, obviously, the invention is not restricted to above embodiment, any to some modifications and changes of this invention, all should fall into claim scope of the present invention within.
The analysis of meta particle diameter and remaining Li content etc.
Inventor has carried out meta particle diameter, pH, LiOH content, Li to above-described embodiment
2cO
3the test of content, as shown in table 1, test result shows, Li
+liOH, the Li of conducting shell and electrolyte separator double-coated sample (embodiment 1～5)
2cO
3content and pH are all starkly lower than the sample (comparative example 1) that only has electrolyte separator coated, also just explanation, Li
+li in conducting shell and electrolyte separator double-coated layer
+conducting shell has played the effect that consumes the cobalt acid lithium remaining Li in surface really.
The physical index of each embodiment of table 1 and chemical index
Electrochemical property
Inventor has carried out 3.0～4.5V to above-described embodiment, 25 ℃ of conditions, and multiplying power is respectively the electrochemical property test of 0.2C, 0.5C, 1.0C, as shown in table 2, and test result shows, under identical multiplying power condition, Li
+the specific discharge capacity of conducting shell and electrolyte separator double-coated sample (embodiment 1～5) is all apparently higher than only having the coated sample of electrolyte separator (comparative example 1), and the ratio of its 1.0C specific discharge capacity and 0.2C specific discharge capacity also will be apparently higher than only having the coated sample of electrolyte separator (comparative example 1).This shows, this special coated mode is obvious to the surface modification effect of cobalt acid lithium, has significantly improved specific discharge capacity and the high rate performance of sample.
Specific discharge capacity (3.0～4.5V) under each embodiment different multiplying condition of table 2
Claims (10)
1. the cobalt of a surface modification treatment acid lithium material, is characterized in that, comprises the surface reforming layer of core particle and coated described core particle, and described core particle is cobalt acid lithium base anode material, and its structural formula is: Li
xco
1-ym
yo
2, 1 ﹤ x≤1.2,0≤y≤0.1, M is doped chemical; Described surface reforming layer comprises Li
+conducting shell and electrolyte separator, described core particle is successively by described Li
+conducting shell and described electrolyte separator are coated.
2. the cobalt of surface modification treatment as claimed in claim 1 acid lithium material, is characterized in that, described doped chemical M comprises one or more in Mg, Ti, Al.
3. the cobalt of surface modification treatment as claimed in claim 1 acid lithium material, is characterized in that described Li
+conducting shell comprises one or more in Co element compound, Mn element compound, Ni element compound, lithium nickel cobalt dioxide predecessor, nickle cobalt lithium manganate predecessor, described Li
+in conducting shell, in metallic element and described core particle, the mol ratio of Co element is 0.1%～10%.
4. the cobalt of surface modification treatment as claimed in claim 3 acid lithium material, is characterized in that, at described Li
+in conducting shell, described Co element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Co element; Described Mn element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Mn element; Described Ni element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Ni element; Described lithium nickel cobalt dioxide predecessor is the oxide of lithium nickel cobalt dioxide, one or more in hydroxide; Described nickle cobalt lithium manganate predecessor is one or more in nickle cobalt lithium manganate oxide, hydroxide, and the size of described Co element compound, described Mn element compound, described Ni element compound, described lithium nickel cobalt dioxide predecessor, described nickle cobalt lithium manganate predecessor is nanoscale.
5. the cobalt of surface modification treatment as claimed in claim 1 acid lithium material, it is characterized in that, described electrolyte separator comprises one or more in Mg element compound, Ti element compound, Al element compound, Zr element compound, Sn element compound, Zn element compound, Ca element compound, it is of a size of 20～500 nanometers, and in described electrolyte separator, the mass ratio of metallic element and described core particle is 0.01%～1%.
6. the cobalt of surface modification treatment as claimed in claim 5 acid lithium material, it is characterized in that, in described electrolyte separator, described Mg element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Mg element; Described Ti element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Ti element; Described Al element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Al element; Described Zr element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Zr element; Described Sn element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Sn element; Described Zn element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Zn element; Described Ca element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Ca element.
7. a preparation method who prepares the cobalt acid lithium material of surface modification treatment as claimed in claim 1, comprises the steps:
(1) by Li element compound, Co element compound and containing the compound of doped metallic elements M, according to mol ratio, be Li:(Co+M)=1～1.2:1 mixes;
(2) mixed raw material is placed in to baking furnace, roasting in air atmosphere, sintering temperature is 600～1100 ℃, roasting time is 4～20 hours, obtains monocrystalline cobalt acid lithium;
(3) described monocrystalline cobalt acid lithium is pulverized, obtained core particle, it is monocrystal particle, its average grain diameter D
50it is 6～20 microns;
(4) by Li
+the coated material of conducting shell joins in ethanol or deionized water, wherein the mass ratio of coated material and ethanol or deionized water is 1:5～1:100, stir 0.5～4 hour, after stirring completes, the cobalt acid lithium obtaining in step (3) is joined in above-mentioned mixed liquor, and at 100～300 ℃, dry 2～6 hours, final, Li
+the coated material of conducting shell has evenly been coated in the core particle surface described in step (3), and the thickness of coating is 20～500 nanometers, described Li
+in the coated material of conducting shell, in metallic element and described core particle, the mol ratio of Co element is 0.1%～10%;
(5) the coated material of electrolyte separator is joined in ethanol or deionized water, wherein the mass ratio of coated material and ethanol or deionized water is 1:5～1:100, stir 0.5～4 hour, after stirring completes, the cobalt acid lithium material obtaining in step (4) is joined in above-mentioned mixed liquor, and at 100～300 ℃, dry 2～6 hours, finally, the coated material of electrolyte separator has evenly been coated in the surface of the cobalt acid lithium material described in step (4), the thickness applying is 20～500 nanometers, in the coated material of described electrolyte separator, the mass ratio of metallic element and described core particle is 0.01%～1%,
(6) the described core particle in step (5) is carried out to sintering under normal pressure and air atmosphere, first 300～500 ℃ of preliminary treatment 3～15 hours, then 500～1000 ℃ of heat treatments 3～15 hours.
8. the preparation method of the cobalt of surface modification treatment as claimed in claim 7 acid lithium material, is characterized in that, described in step (1), Li element compound comprises one or more in lithium carbonate, lithium hydroxide, lithium acetate; Described Co element compound comprises one or more in cobaltosic oxide, cobalt hydroxide, cobalt carbonate, cobalt acetate; The described compound containing doped chemical M is one or more in Mg element compound, Ti element compound, Al element compound; Described Mg element compound refers to one or more in magnesium oxide, magnesium hydroxide, magnesium carbonate; Described Ti element compound refers to one or more in titanium dioxide, butyl titanate; Described Al element compound refers to one or more in minium, aluminium hydroxide, aluminium isopropoxide.
9. the preparation method of the cobalt of surface modification treatment as claimed in claim 7 acid lithium material, is characterized in that Li described in step (4)
+the coated material of conducting shell refers to one or more in Co element compound, Mn element compound, Ni element compound, lithium nickel cobalt dioxide predecessor, nickle cobalt lithium manganate predecessor, and described Co element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Co element; Described Mn element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Mn element; Described Ni element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Ni element; Described lithium nickel cobalt dioxide predecessor is the oxide of lithium nickel cobalt dioxide, one or more in hydroxide; Described nickle cobalt lithium manganate predecessor is one or more in nickle cobalt lithium manganate oxide, hydroxide.
10. the preparation method of the cobalt of surface modification treatment as claimed in claim 7 acid lithium material, it is characterized in that, the coated material of electrolyte separator described in step (5) refers to one or more in Mg element compound, Ti element compound, Al element compound, Zr element compound, Sn element compound, Zn element compound, Ca element compound, and described Mg element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Mg element; Described Ti element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Ti element; Described Al element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Al element; Described Zr element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Zr element; Described Sn element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Sn element; Described Zn element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Zn element; Described Ca element compound refers to one or more in metal oxide, metal hydroxides, metal alkoxide, metal ester salt, metal nitrate, metal sulfate or the metal acetate salt that contains Ca element.
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