CN103606674B - Cobalt acid lithium material of a kind of surface modification treatment and preparation method thereof - Google Patents
Cobalt acid lithium material of a kind of surface modification treatment and preparation method thereof Download PDFInfo
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- CN103606674B CN103606674B CN201310594556.3A CN201310594556A CN103606674B CN 103606674 B CN103606674 B CN 103606674B CN 201310594556 A CN201310594556 A CN 201310594556A CN 103606674 B CN103606674 B CN 103606674B
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- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 136
- 239000010941 cobalt Substances 0.000 title claims abstract description 136
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 135
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 132
- 239000002253 acid Substances 0.000 title claims abstract description 121
- 239000000463 material Substances 0.000 title claims abstract description 116
- 238000011282 treatment Methods 0.000 title claims abstract description 36
- 230000004048 modification Effects 0.000 title claims abstract description 34
- 238000012986 modification Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003792 electrolyte Substances 0.000 claims abstract description 44
- 239000007771 core particle Substances 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 13
- 239000010405 anode material Substances 0.000 claims abstract description 10
- 238000002407 reforming Methods 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims description 199
- 239000002184 metal Substances 0.000 claims description 189
- 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
- 238000000576 coating method Methods 0.000 claims description 33
- 239000010936 titanium Substances 0.000 claims description 32
- 239000011248 coating agent Substances 0.000 claims description 30
- 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
- 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
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 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
- 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
- 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
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 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
- 238000005245 sintering 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
- 238000000034 method Methods 0.000 abstract description 11
- 150000003839 salts Chemical class 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 150000001868 cobalt Chemical class 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 15
- 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
- 239000011247 coating layer Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- 239000004411 aluminium Substances 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000011575 calcium Substances 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 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
- 238000003801 milling Methods 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 238000001035 drying Methods 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
- 238000012360 testing method Methods 0.000 description 4
- 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
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-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
- 230000008569 process Effects 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
- 238000013475 authorization Methods 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
- 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
- 238000009831 deintercalation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 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
- 239000002904 solvent Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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
Cobalt acid lithium material that the invention discloses a kind of surface modification treatment and preparation method thereof, this cobalt acid lithium material 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 coated.The present invention makes full use of the feature of kinetic character that different material and cobalt acid lithium surface residual Li salt reacts and final reacting product performance, prepare the cobalt acid lithium material of two-coat, this material high comprehensive performance, has high discharge capacity, high cyclical stability etc.The inventive method technique is simple, is easy to realize suitability for industrialized production.
Description
Technical field
The invention belongs to lithium ion battery electrode material field, cobalt acid lithium material being specifically related to a kind of surface modification treatment and preparation method thereof.
Background technology
The production technology of cobalt acid lithium material is simple, there is voltage platform high, applicable high current charge-discharge, specific energy advantages of higher simultaneously, therefore start just to have employed cobalt acid lithium as its positive electrode in lithium rechargeable battery commercialization, 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 deintercalation can occur, cause cobalt acid lithium surface to form oxygen defect, finally cause surface texture unstable, the specific discharge capacity of material can decay rapidly.
For improving above-mentioned defect, in recent years, a large amount of report is had about the cobalt acid doping of lithium and coated patent and document, such as, Chinese patent " cathode material precursors of homogeneous nanoparticle core doping " (Authorization Notice No.: CN101897061B) of Ti element doping is carried out to cobalt acid lithium and Zr is carried out to cobalt acid lithium, Chinese patent " the lithium ion secondary battery anode material zirconium of the element dopings such as P, phosphor adulterated cobalt acid lithium and preparation method thereof " (Authorization Notice No.: CN100495775C) and cobalt acid lithium material is carried 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 can play the structure of stable cobalt acid lithium material to the cobalt acid doping of lithium and coating modification etc., and suppress the effects such as the side reaction between cobalt acid lithium and electrolyte, based on above-mentioned result of study, current battery manufacturer have developed the 4.3V even lithium ion battery of 4.35V, but the requirement of properties of sample especially cycle performance under still can not meeting more 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 rapid decay, simultaneously, by above doping, coating technology can't improve specific discharge capacity and efficiency etc. first of material, therefore, larger defect is also there is in it in electrical property, this also reduces 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 the particle diameter used a large amount of in commercialization, by Li
+the impact of transmission path, the degree that in particle, the cobalt acid lithium of diverse location overcharges is different.The cobalt acid lithium of surface portion 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 with special surface of stability structure should be the design direction of the cobalt acid lithium material having 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 more high voltage (>=4.4V), 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, comprise 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 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 containing Co element, the metal oxide preferably containing Co element and metal hydroxides; 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 containing Mn element, the metal oxide preferably containing Mn element and metal hydroxides; 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 containing Ni element, the metal oxide preferably containing Ni element and metal hydroxides; Described lithium nickel cobalt dioxide predecessor is one or more in the oxide of lithium nickel cobalt dioxide, 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 containing 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 containing 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 containing 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 containing 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 containing 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 containing 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 containing 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 be Li:(Co+M containing the compound of doped metallic elements M according to mol ratio)=(1 ~ 1.2): 1 mixes;
(2) mixed raw material is placed in baking furnace, roasting in air atmosphere, sintering temperature is 600 ~ 1100 DEG C, and preferably between 900 ~ 1050 DEG C, roasting time is 4 ~ 20 hours, obtains monocrystalline cobalt acid lithium;
(3) pulverized by described monocrystalline cobalt acid lithium, obtain 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 obtained in step (3) acid lithium is joined in above-mentioned mixed liquor, and dry 2 ~ 6 hours at 100 ~ 300 DEG C, finally, 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) coated for electrolyte separator material 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 obtained in step (4) acid lithium material is joined in above-mentioned mixed liquor, and dry 2 ~ 6 hours at 100 ~ 300 DEG C, 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 of coating 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 sintered under normal pressure and air atmosphere, first 300 ~ 500 DEG C of preliminary treatment 3 ~ 15 hours, then 500 ~ 1000 DEG C of heat treatments 3 ~ 15 hours.
Further, be one or more in Mg element compound, Ti element compound, Al element compound containing the compound of doped chemical M described in step (1), preferred 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 containing Co element, the metal oxide preferably containing Co element and metal hydroxides; 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 containing Mn element, the metal oxide preferably containing Mn element and metal hydroxides; 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 containing Ni element, the metal oxide preferably containing Ni element and metal hydroxides; Described lithium nickel cobalt dioxide predecessor is one or more in the oxide of lithium nickel cobalt dioxide, hydroxide; Described nickle cobalt lithium manganate predecessor is one or more in nickle cobalt lithium manganate oxide, hydroxide.
Further, described in step (5), the coated material of electrolyte separator 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 containing 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 containing 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 containing 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 containing 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 containing 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 containing 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 containing 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 meeting high specific discharge capacity and the requirement of high voltage (>=4.4V) cycle performance.This modifying process takes full advantage of the feature of kinetic character that different material and cobalt acid lithium surface residual Li salt reacts and final reacting product performance.
First, in kinetics feature, internal layer coating (Co, the compound of the elements such as Mn) dynamics that reacts with cobalt acid lithium surface residual Li salt will much larger than external sheath thing (Al, Mg, the compound of the elements such as Ti) dynamics that reacts with cobalt acid lithium surface residual Li salt, affect by this, internal layer coating just can react with the remaining Li salt on cobalt acid lithium surface at lower temperature (300 DEG C ~ 500 DEG C), outer field coating then needs higher temperature (> 500 DEG C) to react, utilize this feature, the sintering schedule that we take for first carrying out preliminary treatment 3 ~ 15 hours under cryogenic conditions (300 DEG C ~ 500 DEG C), be elevated to higher temperature (> 500 DEG C) heat treatment 3 ~ 15 hours again, like this, in the Cold pretreatment stage, the Li on cobalt acid lithium surface can consume by the coated material of internal layer, form inner Li
+conducting shell, after raising heat treatment temperature, because remaining Li is at Li
+exist with the form of stable chemical bond in conducting shell, outer field coating then cannot react with remaining Li again, can only form the electrolyte separators such as metal oxide, and like this, finally just obtaining internal layer is Li
+conduction coating layer, the outer two-coat for electrolyte isolation coating layer.
Secondly, at Li
+the product performance characteristics aspect of the conduction coated material of coating layer and the coated material of electrolyte separator and cobalt acid lithium surface residual Li salt, Li
+co in the coated material of conduction coating layer, first procatarxis such as Mn has electro-chemical activity, the cobalt acid lithium generated in this coating layer forming process, LiMn2O4s etc. have contribution to specific discharge capacity, make its specific discharge capacity and first efficiency etc. there has also been and greatly improve, fully stabilize the surface texture of cobalt acid lithium simultaneously, finally make its comprehensive electrochemical have greatly to improve, and the Al in electrolyte isolation 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, effect can not be improved to the chemical property of material after the remaining Li reactant salt on they and cobalt acid lithium surface, on the contrary, also discharge capacity can be caused during the remaining Li reactant salt of a large amount of above elements with the sour lithium surface of cobalt, the significantly reduction of efficiency first, the chemical property of material is damaged, therefore, double-coated in the present invention takes full advantage of the advantage of each coating layer, in the two-coat formed, outside electrolyte separator can reduce the generation of side reaction between cobalt acid lithium surface and electrolyte, inner Li
+conducting shell then effectively improves 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 also overcomed Li in normal packet coating
+conducting power is poor, interfacial structure is unstable, to the specific discharge capacity of material without defects such as improvement, coating function are single, at above Li
+under the comprehensive function of conducting shell and electrolyte separator, the cycle performance of material has had and has greatly improved, and still has good cycle performance under button cell 4.5V condition.
In sum, advantage of the present invention is as follows:
1. the cobalt acid lithium material of surface modification treatment provided by the invention, is making full use of Li
+the coated material of conducting shell and electrolyte are isolated on the different characteristics basis of coated material and cobalt acid lithium surface residual Li reactant salt, by specific sintering schedule, obtain and carry out the lithium cobaltate cathode material that special surface modification has double-coated layer, the electrolyte separator of above double-coated layer peripheral has isolated electrolyte that traditional coating layer possesses, reduce and the effect such as side reaction of electrolyte.
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 to improve, and fully stabilizes 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 External electrolytic liquid barrier coat; material can meet full battery 4.4V or the requirement more under high voltage, and this is that the improvement institutes of technical approach to material circulation performance such as general doping, coated and size particles mixing are inaccessiable.
3. the cobalt acid lithium material of surface modification treatment provided by the present invention is under high temperature (45 DEG C), high voltage (4.5V) and high magnification (1.0C) etc. comparatively exacting terms, and its cycle performance keeps better, 100 weeks capability retentions about 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 that the embodiment of the present invention 3 prepares.
The SEM figure of the cobalt acid lithium material 1000 times of the surface modification treatment that Fig. 2 a) prepares for the embodiment of the present invention 3.
Fig. 2 b) the SEM figure of the cobalt acid lithium material 3000 times of surface modification treatment for 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 that the embodiment of the present invention 3 prepares.
Fig. 4 is the cycle performance figure of the cobalt acid lithium material of the surface modification treatment that the embodiment of the present invention 3 prepares.
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) be that lithium carbonate, cobaltosic oxide and cobalt acetate, magnesium oxide mix with dry method mode ball milling by the ratio of 1.20:0.98:0.02 in molar ratio in lithium, cobalt, magnesium; After having mixed, above-mentioned material is placed in baking furnace under air atmosphere roasting and normal pressure, within 13 hours, obtains with 600 DEG C of roastings the monocrystalline cobalt acid lithium mixing 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 obtained in step (1) acid lithium is joined in above-mentioned mixed liquor, and dry 2 hours at 300 DEG C, tentatively complete the ground floor of cobalt acid lithium coated, the thickness of coating is about 20 nanometers, and the mol ratio of the Co element in the sour lithium of the Ni element wherein in nickel acetate and cobalt 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 mixing magnesium obtained in step (2) is joined in above-mentioned mixed liquor, and dries 2 hours at 300 DEG C, tentatively complete the second layer of cobalt acid lithium coated, the thickness of coating is about 20 nanometers, and in above-mentioned Alumina gel, the mass ratio of Al element and cobalt acid lithium is 0.01%.
(4) product after oven dry in step (3) is first 500 DEG C of preliminary treatment 3 hours in baking furnace under air atmosphere and normal pressure, then 900 DEG C of heat treatments 5 hours, after cooling, above-mentioned material is sieved, 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 2
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) be that lithium hydroxide, cobalt hydroxide, butyl titanate, aluminium oxide mix with dry method mode ball milling by the ratio of 1.07:0.98:0.01:0.01 in molar ratio in lithium, cobalt, titanium, aluminium; After having mixed, above-mentioned material is placed in baking furnace under air atmosphere roasting and normal pressure, with 1000 DEG C of roastings 13 hours, obtain the monocrystalline cobalt acid lithium mixing 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 obtaining mixing titanium aluminium in step (1) is joined in above-mentioned mixed liquor, and dry 6 hours at 100 DEG C, tentatively complete the ground floor of cobalt acid lithium coated, the thickness of coating is about 500 nanometers, and the mol ratio of the cobalt in the manganese wherein in manganese acetate and cobalt acid lithium is 6%, the mol ratio of the cobalt in cobalt acetate and the cobalt in the sour lithium of cobalt is 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 mixing titanium aluminium obtained in step (2) is joined in above-mentioned mixed liquor, and dries 6 hours at 100 DEG C, tentatively complete the second layer of cobalt acid lithium coated, the thickness of coating is about 500 nanometers, and in coating, the mass ratio of Al element and core particle is 1%.
(4) product after oven dry in step (3) is first 300 DEG C of preliminary treatment 15 hours in baking furnace under air atmosphere and normal pressure, then 1000 DEG C of heat treatments 3 hours, after cooling, above-mentioned material is sieved, 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) be that lithium carbonate, cobaltosic oxide, magnesium oxide and titanium dioxide mix with dry method mode ball milling by the ratio of 1.06:0.96:0.02:0.02 in molar ratio in lithium, cobalt, magnesium, titanium; After having mixed, above-mentioned material is placed in baking furnace under air atmosphere roasting and normal pressure, with 1015 DEG C of roastings 13 hours; The material that roasting completes carries out airflow milling fragmentation again and sieves after coarse crushing, finally obtains the to be covered monocrystalline cobalt acid lithium material mixing magnesium titanium, 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 obtaining mixing magnesium titanium in step (1) is joined in above-mentioned mixed liquor, and dry 4 hours at 200 DEG C, tentatively complete the ground floor of cobalt acid lithium coated, the thickness of coating is about 40 nanometers, and the mol ratio of the cobalt in the sour lithium of the cobalt wherein in cobalt acetate and cobalt 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 mixing magnesium titanium obtained in step (2) is joined in above-mentioned mixed liquor, and dries 5 hours at 100 DEG C, tentatively complete the second layer of cobalt acid lithium coated, the thickness of coating 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 DEG C of preliminary treatment 3 hours, after with 800 DEG C of heat treatments 5 hours, after cooling, above-mentioned material is sieved, 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 thing phase XRD of the material of the present embodiment, and thing is pure cobalt acid lithium thing phase mutually 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 an electron microscope, the surface of sample is more mellow and fuller, smooth as seen from the figure, and the Surface Modification Effect is obviously, 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 there is obvious line of demarcation between interior external coating.
Fig. 4 is the cycle performance curve chart of sample under the condition of high temperature (45 DEG C), high voltage (4.5V) and high magnification (1.0C) of the present embodiment, and the cycle performance of sample keeps better as seen from the figure, 100 weeks capability retentions about 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) be that lithium acetate, cobalt carbonate, butyl titanate, minium, magnesium oxide mix with dry method mode ball milling by the ratio of 1.01:0.97:0.01:0.01:0.01 in molar ratio in lithium, cobalt, titanium, aluminium, magnesium; After having mixed, above-mentioned material is placed in baking furnace under air atmosphere roasting and normal pressure, with 1100 DEG C of roastings 4 hours; The material that roasting completes carries out airflow milling fragmentation again and sieves after coarse crushing, finally obtains the to be covered monocrystalline cobalt acid lithium material mixing magnesium titanium aluminium, 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, nanoscale nickel hydroxide joins in deionized water, the wherein nanoscale predecessor of lithium nickel cobalt dioxide, nanoscale cobalt acetate, nanoscale manganese, the quality of nanoscale nickel hydroxide and be 1:80 with the mass ratio of deionized water, stir 3 hours, the monocrystalline cobalt acid lithium obtaining mixing magnesium titanium aluminium in step (1) is joined in above-mentioned mixed liquor, and dry 5 hours at 150 DEG C, tentatively complete the ground floor of cobalt acid lithium coated, the thickness of coating is about 40 nanometers, the wherein nanoscale predecessor of lithium nickel cobalt dioxide, nanoscale cobalt acetate, nanoscale manganese, 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, wherein isopropyl alcohol magnalium, 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 mixing magnesium titanium aluminium obtained in step (2) is joined in above-mentioned mixed liquor, and dry 3 hours at 250 DEG C, tentatively complete the second layer of cobalt acid lithium coated, the thickness of coating 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 DEG C of preliminary treatment 15 hours, after with 500 DEG C of heat treatments 15 hours, after cooling, above-mentioned material is sieved, 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) be that lithium carbonate and lithium acetate and lithium hydroxide, cobaltosic oxide and cobalt carbonate, titanium dioxide mix with dry method mode ball milling by the ratio of 1.08:0.97:0.03 in molar ratio in lithium, cobalt, titanium; After having mixed, above-mentioned material is placed in baking furnace under air atmosphere roasting and normal pressure, with 1020 DEG C 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, join in above-mentioned mixed liquor by obtaining doped titanium monocrystalline cobalt acid lithium in step (1), and dry 6 hours at 150 DEG C, tentatively complete the ground floor of cobalt acid lithium coated, the thickness of coating is 40 nanometers, and wherein in nickle cobalt lithium manganate predecessor, the mole sum of Ni element, Co element and Mn element is 4.0% with the ratio of the mole of the Co element in cobalt acid lithium.
(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 obtained in step (2) is joined in above-mentioned mixed liquor, and dry 3 hours at 250 DEG C, tentatively complete the second layer of cobalt acid lithium coated, the thick mass ratio being about Al element and core particle in 70 nano coatings of coating is 0.05%.
(4) by the product after drying in step (3) under air atmosphere and normal pressure in baking furnace first with 450 DEG C of preliminary treatment 3 hours, after with 800 DEG C of heat treatments 5 hours, after cooling, above-mentioned material is sieved, 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 eliminates 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) be that lithium carbonate, cobaltosic oxide and titanium dioxide mix with dry method mode ball milling by the ratio of 1.08:0.97:0.03 in molar ratio in lithium, cobalt, titanium, after having mixed, above-mentioned material is placed in baking furnace with 1020 DEG C 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, be heated to 100 DEG C dissolve completely to aluminium isopropoxide, join in above-mentioned Alumina gel by the cobalt of Surface coating cobalt oxide in step (1) acid lithium material, 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 DEG C of preliminary treatment 3 hours, after with 800 DEG C of heat treatments 5 hours, after cooling, above-mentioned material is sieved.
It should be noted that, cited be only specific embodiments of the invention above, obviously, the invention is not restricted to above embodiment, any some modifications and changes to this invention all should fall within right of the present invention.
The analysis of median and remaining Li content etc.
Inventor has carried out median, pH, LiOH content, Li to above-described embodiment
2cO
3the test of content, as shown in table 1, test result shows, Li
+liOH, 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) only having electrolyte separator coated, also just illustrate, Li
+li in conducting shell and electrolyte separator double-coated layer
+conducting shell serves the effect consuming cobalt acid lithium surface residual Li 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 DEG C 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, and Li
+the specific discharge capacity of conducting shell and electrolyte separator double-coated sample (embodiment 1 ~ 5) is all apparently higher than the sample only having electrolyte separator coated (comparative example 1), and the ratio of its 1.0C specific discharge capacity and 0.2C specific discharge capacity also will apparently higher than the sample only having electrolyte separator coated (comparative example 1).This shows, the surface modification effect of this special coated mode to cobalt acid lithium is obvious, significantly improves specific discharge capacity and the high rate performance of sample.
Specific discharge capacity (3.0 ~ 4.5V) under table 2 each embodiment different multiplying condition
Claims (7)
1. a cobalt acid lithium material for surface modification treatment, is characterized in that, comprise 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, and described doped chemical M comprises one or more in Mg, Ti, Al; 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 coated, 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%, 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%.
2. the cobalt acid lithium material of surface modification treatment as claimed in claim 1, 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 containing 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 containing 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 containing Ni element; Described lithium nickel cobalt dioxide predecessor is one or more in the oxide of lithium nickel cobalt dioxide, 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.
3. the cobalt acid lithium material of surface modification treatment as claimed in claim 1, 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 containing 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 containing 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 containing 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 containing 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 containing 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 containing 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 containing Ca element.
4. prepare a preparation method for the cobalt acid lithium material of surface modification treatment as claimed in claim 1, comprise the steps:
(1) by Li element compound, Co element compound and be Li:(Co+M containing the compound of doped metallic elements M according to mol ratio)=1 ~ 1.2:1 mixes;
(2) mixed raw material is placed in baking furnace, roasting in air atmosphere, sintering temperature is 600 ~ 1100 DEG C, and roasting time is 4 ~ 20 hours, obtains monocrystalline cobalt acid lithium;
(3) pulverized by described monocrystalline cobalt acid lithium, obtain 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 obtained in step (3) acid lithium is joined in above-mentioned mixed liquor, and dry 2 ~ 6 hours at 100 ~ 300 DEG C, finally, 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) coated for electrolyte separator material 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 obtained in step (4) acid lithium material is joined in above-mentioned mixed liquor, and dry 2 ~ 6 hours at 100 ~ 300 DEG C, 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 of coating 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 sintered under normal pressure and air atmosphere, first 300 ~ 500 DEG C of preliminary treatment 3 ~ 15 hours, then 500 ~ 1000 DEG C of heat treatments 3 ~ 15 hours.
5. the preparation method of the cobalt acid lithium material of surface modification treatment as claimed in claim 4, it 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.
6. the preparation method of the cobalt acid lithium material of surface modification treatment as claimed in claim 4, 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 containing 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 containing 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 containing Ni element; Described lithium nickel cobalt dioxide predecessor is one or more in the oxide of lithium nickel cobalt dioxide, hydroxide; Described nickle cobalt lithium manganate predecessor is one or more in nickle cobalt lithium manganate oxide, hydroxide.
7. the preparation method of the cobalt acid lithium material of surface modification treatment as claimed in claim 4, it is characterized in that, described in step (5), the coated material of electrolyte separator 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 containing 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 containing 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 containing 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 containing 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 containing 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 containing 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 containing Ca element.
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|---|---|---|---|
| CN201310594556.3A CN103606674B (en) | 2013-11-21 | 2013-11-21 | Cobalt acid lithium material of a kind of surface modification treatment and preparation method thereof |
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