CN104638227A - Method for modifying positive electrode material of lithium ion battery - Google Patents
Method for modifying positive electrode material of lithium ion battery Download PDFInfo
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- CN104638227A CN104638227A CN201510043316.3A CN201510043316A CN104638227A CN 104638227 A CN104638227 A CN 104638227A CN 201510043316 A CN201510043316 A CN 201510043316A CN 104638227 A CN104638227 A CN 104638227A
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- lithium
- positive electrode
- melting point
- low melting
- treatment agent
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- 238000000034 method Methods 0.000 title claims abstract description 45
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 24
- 239000007774 positive electrode material Substances 0.000 title abstract 7
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 62
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 62
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 33
- 238000002844 melting Methods 0.000 claims abstract description 24
- 230000008018 melting Effects 0.000 claims abstract description 24
- 238000012986 modification Methods 0.000 claims abstract description 17
- 230000004048 modification Effects 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 10
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims abstract description 8
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims abstract description 5
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims abstract description 4
- 229940009827 aluminum acetate Drugs 0.000 claims abstract description 4
- 239000003513 alkali Substances 0.000 claims description 32
- 239000012535 impurity Substances 0.000 claims description 32
- 239000011248 coating agent Substances 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 18
- 230000014759 maintenance of location Effects 0.000 claims description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- 239000010405 anode material Substances 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- 159000000013 aluminium salts Chemical class 0.000 claims description 13
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 7
- 229910010093 LiAlO Inorganic materials 0.000 claims description 6
- 229910052596 spinel Inorganic materials 0.000 claims description 5
- 239000011029 spinel Substances 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 4
- BNUDRLITYNMTPD-UHFFFAOYSA-N acetic acid;zirconium Chemical compound [Zr].CC(O)=O BNUDRLITYNMTPD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 2
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- 239000008247 solid mixture Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 19
- 238000012545 processing Methods 0.000 abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 2
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 abstract 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical class [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 abstract 1
- 239000002002 slurry Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000243 solution Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- 239000003292 glue Substances 0.000 description 6
- 238000007711 solidification Methods 0.000 description 6
- 230000008023 solidification Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910013716 LiNi Inorganic materials 0.000 description 4
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 3
- 229910013024 LiNi0.5Mn1.5O2 Inorganic materials 0.000 description 3
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 3
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910014127 LiMn2 O4 -LiMn2 O4 Inorganic materials 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 206010016766 flatulence Diseases 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000010671 solid-state reaction Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for modifying a positive electrode material of a lithium ion battery. The method comprises the following steps: by taking aluminum or zircon salts (mainly including aluminum nitrate, aluminum acetate, zirconium nitrate, zirconium acetate, zirconium oxychloride and the like) with low melting point as alkaline processing agents, uniformly mixing the alkaline processing agents with a lithium ion battery positive electrode material with a high pH value, heating the obtained mixture till the alkaline processing agents which have the low melting point are molten and infiltrate on surface of the lithium ion battery positive electrode material, and further heating the new mixture obtained till the alkaline processing agents are fully reacted with residual alkaline lithium salts in the positive electrode material by using a two-section sintering process, and thereby obtaining a final product. According to the modified positive electrode material of the lithium ion battery, the residual alkaline lithium salt content and the pH value are obviously reduced, and a coated modification layer can be formed on the surface of the material, so that the storage property, the processing property and the circulation property of the positive electrode material can be effectively improved. The method is simple in process, convenient to operate, energy-saving, pollution-free, low in cost and suitable for industrial production.
Description
Technical field
The present invention relates to lithium ion battery electrode material field, particularly relate to a kind of method of modifying reducing the anode material for lithium-ion batteries of material pH value and surface coating modification.
Background technology
Since Japanese Sony company success commercialization of production lithium ion battery in 1991, lithium ion battery because its energy density is high, power density is high, have extended cycle life, the advantage such as pollution-free and self-discharge rate is low, obtain a wide range of applications in various fields such as consumer electronics product, electric tool, electric automobile, energy storage.Wherein, positive electrode is the part of lithium ion battery most critical, directly determines its energy density, is also the key factor affecting cell power density, cycle life and security performance.
High temperature process heat is positive electrode preparation technology general at present, in the process, in order to compensate the volatilization loss of elemental lithium under high temperature, usually can be added beyond the lithium salts of the whole ratio of stoichiometry.Adding of this excessive lithium salts can also promote carrying out smoothly of solid phase reaction, increases the primary particle particle diameter of positive electrode, improves tap density and the energy density of positive electrode, promotes the security performance of battery.But generally, excessive lithium salts can't volatilize completely in high temperature solid state reaction, and part lithium salts can with Li
2it is inner and surperficial that the form of O is present in positive electrode.In addition, due to Li
+with Ni
2+ionic radius is close, in the high temperature solid-state preparation process of the nickeliferous positive electrodes such as lithium nickelate, nickel cobalt aluminium ternary, nickel-cobalt-manganese ternary, lithium nickel mixing phenomenon easily occurs, causes part lithium to be separated out from lattice structure, also can with Li
2the form of O is present in material internal or surface.
Li remaining in positive electrode
2o storage or transportation in, with the water in air or CO
2reaction is converted into Li
2cO
3or the lithium salts impurity such as LiOH, and the pH value of positive electrode is raised.This higher residual lithium salt impurity content and higher pH value have had a strong impact on the properties of material and battery.The remaining lithium salts very easily moisture absorption, causes material water content to increase, and is difficult to remove in bake process.Too high water content easily causes binding agent PVDF sex change, and the dispersiveness of slurry and stability reduce, and slurry even can be caused to lump or agglomerating etc., reduces the processing characteristics of positive electrode.In addition, in the work or storage process of battery, the LiPF in too high water content and electrolyte
6side reaction occurs and generates harmful HF, HF further erosion electrode material also causes a series of chain side reaction, destroys electrode structure and causes battery flatulence, seriously reducing battery performance.The pH value that material is higher also can corrode plus plate current-collecting body aluminium foil, and produces H
2gas, also causes battery flatulence while destroying collector.Therefore, high residual lithium salt impurity content, high ph-values are the significant problems that positive electrode especially faces in the production of nickel-base anode material and application.
The current positive electrode residual lithium salt impurity content that can reduce reduces its pH value thus the method improving positive electrode performance mainly contains following a few class:
(1) in material preparation process, reduce the extra proportion that lithium salts feeds intake, or the prolongation high temperature solid state reaction time impels excessive elemental lithium volatilization more complete, thus control residual lithium salt impurity content.Such as patent CN103151512A employing divides two sections and adds lithium salts, and reduces lithium salts ingredient proportion.But these class methods are poor for the effect reducing residual lithium salt impurity content, even cause the change of material tap density and the reduction of chemical property.
(2) by positive electrode use water, bicarbonate solution, organic acid soln or organic solvent cyclic washing or reaction, then Separation of Solid and Liquid and dry process is carried out.Such as in patent CN102683672A, cleaning solution is water, LiHCO
3or NH
4hCO
3the aqueous solution, in patent CN103700839A, cleaning solution is LiH
2pO
4water or organic solution, in patent CN103337614A, cleaning solution is organic acid alcoholic solution, and in patent CN103972486A, cleaning solution is volatile carbonic ether kind solvent.It is better that this type of technology reduces residual lithium salt impurity content effect, but technique is comparatively loaded down with trivial details, and usually need to consume a large amount of cleaning solutions, a large amount of waste liquid of even related generation.In addition, when cleaning solution solvent is water, the material after process still very easily absorbs water, and subsequent storage condition is harsh, and when cleaning solution solvent is nonaqueous solvents, cost is higher.
(3) thin layer of metal oxide, such as patent CN104051708A is formed by means such as alds at material or electrode surface.This kind of technique does not remove remaining lithium salts impurity, but realizes isolating by good covered effect and reduce the effect of pH value, and just its cost is higher, and is not suitable for suitability for industrialized production.
In addition, in battery system, in positive electrode, there is high-valence state metal ion (the such as Ni of high oxidative
4+and Co
4+), trend towards the carbonic ether kind solvent generation redox reaction in same electrolyte with reproducibility, and each metal ion species also trends towards being dissolved in electrolyte.Active substances in cathode materials that above-mentioned side reaction causes runs off, battery impedance increases and the decay of battery properties, especially the pressing issues that generally face of positive electrode.To this, more effective modified method is metal cation or anion doped modification, and the modification of the surface coating decoration such as oxide, fluoride.
Summary of the invention
The invention provides a kind of method of modifying of anode material for lithium-ion batteries, the method effectively can not only reduce the residual lithium salt impurity content of positive electrode, reduce the pH value of positive electrode, and can at positive electrode Surface Creation surface coating modification layer, while the processing characteristics improving positive electrode, also improve the memory property of battery, cycle performance and security performance.
To achieve these goals, the invention provides following technical scheme:
A method of modifying for anode material for lithium-ion batteries, is completed by following steps:
(1) detect and analyze lithium salts impurity content remaining in positive electrode, take the low melting point aluminium salt of certain mol proportion example or zirconates as alkali treatment agent, to join in positive electrode and to mix;
(2) solid mixture obtained in step (1) is heated to alkali treatment agent infiltrated with molten metal, and is incubated;
(3) gained mixture in step (2) is heated to further alkali treatment agent decompose and react with the lithium salts impurity of remnants in positive electrode, and is incubated.
Preferably, positive electrode described in step (1) comprises one or more in the acid of stratiform cobalt lithium, lithium nickelate, nickle cobalt lithium manganate ternary, nickel cobalt lithium aluminate ternary, lithium-rich manganese base material or lithium manganate having spinel structure, nickel ion doped material; Described low melting point alkali treatment agent is one or more in aluminum nitrate, aluminum acetate, zirconium nitrate, acetic acid zirconium, basic zirconium chloride.
Preferably, in step (1), when adopting low melting point aluminium salt as alkali treatment agent, the lithium salts Li of low melting point aluminium salt and remnants in positive electrode
2cO
3molar ratio be 2:1 ~ 10:1; When adopting low melting point zirconates as alkali treatment agent, the lithium salts Li of low melting point zirconates and remnants in positive electrode
2cO
3molar ratio be 1:1 ~ 5:1.
Preferably, the heating-up temperature described in step (2) is 75 ~ 500 DEG C, and temperature retention time is 0.5 ~ 8 hour.
Preferably, the heating-up temperature described in step (3) is 600 ~ 900 DEG C, and temperature retention time is 1 ~ 10 hour.
Preferably, in modified positive electrode, residual lithium salt impurity content significantly reduces, and there is coating modification layer on positive electrode surface.
Preferably, described coating modification layer comprises LiAlO
2and Li
2zrO
3in at least one, when adopt alkali treatment agent excessive time, described coating modification layer also comprises Al
2o
3and ZrO
2in at least one.
Preferably, alkali treatment agent is excessive to be referred to: when adopting low melting point aluminium salt as alkali treatment agent, low melting point aluminium salt and remaining lithium salts Li
2cO
3molar ratio more than 2:1, or when adopting low melting point zirconates as alkali treatment agent, low melting point zirconates and remaining lithium salts Li
2cO
3molar ratio more than 1:1.
The method of modifying of anode material for lithium-ion batteries provided by the invention has following beneficial effect:
(1) adopt the aluminium salt of low melting point or zirconates as alkali treatment agent, adopt double sintering technique, realize alkali treatment agent at a lower temperature fully to contact with residual lithium salt impurity in positive electrode with the state of melting, be conducive to follow-up fully carrying out except alkali reaction, significantly can reduce the pH value of positive electrode.
(2) adopt aluminium salt or zirconates as alkali treatment agent, react with residual lithium salt impurity in positive electrode, can at positive electrode Surface Creation LiAlO
2or Li
2zrO
3coating modification layer.
(3) adopt aluminium salt or zirconates as alkali treatment agent, when alkali treatment agent is excessive, can Al be decomposed into
2o
3or ZrO
2coating modification layer.
(4) according to the modified positive electrode that method of modifying provided by the invention obtains, residual lithium salt impurity content is low, material pH value is low, and there is coating modification layer on surface, there is good processing characteristics, memory property, cycle performance and security performance, have a good application prospect in high performance lithium ion battery field.
(5) modified technique provided by the invention is simple, easy to operate, and saving power and preventing pollution contaminates, with low cost, is applicable to suitability for industrialized production.
Embodiment
In order to understand content of the present invention better, be described further below in conjunction with instantiation, the positive electrode in each comparative example and embodiment is tested as follows:
method of testing to material property in comparative example and embodiment:
Positive electrode residual lithium salt impurity content is tested: adopt hydrochloric acid standard solution titration positive electrode, by consuming the volume of watery hydrochloric acid, to calculate in positive electrode lithium salts impurity (with Li
2cO
3meter) content.
Positive electrode pH value is tested: get 5g positive electrode and join in 45ml deionized water, and ultrasonic disperse also, after leaving standstill, measures supernatant liquor pH value with pH meter.
Positive electrode slurry bond time is tested: with the mass ratio of 84:8:8, take active substances in cathode materials, conductive agent carbon black and binding agent PVDF respectively, add after appropriate dispersant NMP mixes and obtain positive electrode slurry.Be positioned in closed container by deployed anode sizing agent, temperature is 25 DEG C, and ambient humidity is 80%.Observe slurry gum deposit situation per half an hour, investigate the bond time of recording materials.
Positive electrode is applied to the electrochemical property test of lithium ion battery: be coated on aluminium foil by deployed positive electrode slurry, and as positive pole after oven dry roll-in, be to electrode with lithium sheet, electrolyte adopts LiPF
6for solute, EC+DEC+DMC(volume ratio is 1:1:1) be solvent, concentration is 1mol/L, and barrier film is polypropylene microporous film, at Ar
2cR2016 button cell is assembled in the glove box of atmosphere.Battery testing temperature is 20 DEG C, and test voltage is interval relevant with positive electrode kind, and in cycle performance test, size of current is 1C.
comparative example 1:after testing, cobalt acid lithium LiCoO
2middle residual lithium salt impurity content is that 0.13%(is with Li
2cO
3meter), pH value is 11.17, and slurry bond time is that under 18h, 3.0-4.3V, after 1C current cycle 100 times, capability retention is 90.1%.
embodiment 1:take the cobalt acid lithium LiCoO in 100.0g comparative example 1
2, wherein residual lithium salt Li
2cO
3for 0.13g.Add 1.1169g aluminum nitrate Al (NO
3)
39H
2o(and residual lithium salt Li
2cO
3molar ratio be 2:1) as alkali treatment agent, with cobalt acid lithium material mix, in atmosphere 75 DEG C process 0.5h, continue in atmosphere 600 DEG C process 5h, can obtain basicity reduce and Surface coating LiAlO
2modified cobalt acid lithium material.After testing, modified cobalt acid lithium LiCoO
2middle residual lithium salt impurity content is that 0.02%(is with Li
2cO
3meter), pH value reduces to 10.06, and in 48 hours, slurry has no glue solidification, under 3.0-4.3V after 1C current cycle 100 times capability retention up to 97.5%.
comparative example 2: after testing, LiMn2O4 LiMn
2o
4middle residual lithium salt impurity content is that 0.11%(is with Li
2cO
3meter), pH value is 11.04, and slurry bond time is that under 22h, 3.0-4.3V, after 1C current cycle 100 times, capability retention is 92.5%.
embodiment 2: take the LiMn2O4 LiMn in 100.0g comparative example 2
2o
4, wherein residual lithium salt Li
2cO
3for 0.11g.Add 1.2154g aluminum acetate Al (CH
3cOO)
3(with residual lithium salt Li
2cO
3molar ratio be 4:1) as alkali treatment agent, mix with lithium manganate material, in atmosphere 190 DEG C process 2h, continue in atmosphere 850 DEG C process 1h, can obtain basicity reduce and Surface coating LiAlO
2and Al
2o
3modified lithium manganate material.After testing, modified LiMn2O4 LiMn
2o
4middle residual lithium salt impurity content is that 0.02%(is with Li
2cO
3meter), pH value reduces to 10.03, and in 48 hours, slurry has no glue solidification, under 3.0-4.3V after 1C current cycle 100 times capability retention up to 98.2%.
comparative example 3: after testing, nickel-cobalt-manganese ternary LiNi
0.5co
0.2mn
0.3o
2middle residual lithium salt impurity content is that 0.31%(is with Li
2cO
3meter), pH value is 11.95, and slurry bond time is that under 8.5h, 3.0-4.3V, after 1C current cycle 100 times, capability retention is 91.4%.
embodiment 3: take the nickel-cobalt-manganese ternary LiNi in 100.0g comparative example 3
0.5co
0.2mn
0.3o
2, wherein residual lithium salt Li
2cO
3for 0.31g.Add 15.7383g aluminum nitrate Al (NO
3)
39H
2o(and residual lithium salt Li
2cO
3molar ratio be 10:1) as alkali treatment agent, mix with nickel-cobalt-manganese ternary material, in atmosphere 90 DEG C process 8h, continue in atmosphere 700 DEG C process 5h, can obtain basicity reduce and Surface coating LiAlO
2and Al
2o
3modification ternary LiNi
0.5co
0.2mn
0.3o
2material.After testing, modified LiNi
0.5co
0.2mn
0.3o
2in material, residual lithium salt impurity content is that 0.05%(is with Li
2cO
3meter), pH value reduces to 10.49, and in 48 hours, slurry has no glue solidification, under 3.0-4.3V after 1C current cycle 100 times capability retention up to 98.0%.
comparative example 4: after testing, nickel-cobalt-manganese ternary LiNi
0.6co
0.2mn
0.2o
2middle residual lithium salt impurity content is that 0.38%(is with Li
2cO
3meter), pH value is 12.27, and slurry bond time is that under 4h, 3.0-4.3V, after 1C current cycle 100 times, capability retention is 89.3%.
embodiment 4: take the nickel-cobalt-manganese ternary LiNi in 100.0g comparative example 4
0.6co
0.2mn
0.2o
2, wherein residual lithium salt Li
2cO
3for 0.38g.Add 5.5197g zirconium nitrate Zr (NO
3)
35H
2o(and residual lithium salt Li
2cO
3molar ratio be 2.5:1) as alkali treatment agent, mix with nickel-cobalt-manganese ternary material, in atmosphere 135 DEG C process 3h, continue in atmosphere 900 DEG C process 4h, can obtain basicity reduce and Surface coating Li
2zrO
3and ZrO
2modification ternary LiNi
0.6co
0.2mn
0.2o
2material.After testing, modified LiNi
0.6co
0.2mn
0.2o
2in material, residual lithium salt impurity content is that 0.05%(is with Li
2cO
3meter), pH value reduces to 10.57, and in 36 hours, slurry has no glue solidification, under 3.0-4.3V after 1C current cycle 100 times capability retention up to 96.2%.
comparative example 5: after testing, nickel cobalt aluminium ternary LiNi
0.8co
0.15al
0.05o
2middle residual lithium salt impurity content is that 0.48%(is with Li
2cO
3meter), pH value is 12.73, and slurry bond time is that under 2h, 3.0-4.3V, after 1C current cycle 100 times, capability retention is 86.6%.
embodiment 5: take the nickel cobalt aluminium ternary LiNi in 100.0g comparative example 5
0.8co
0.15al
0.05o
2, wherein residual lithium salt Li
2cO
3for 0.48g.Add 10.4669g basic zirconium chloride ZrOCl
28H
2o(and residual lithium salt Li
2cO
3molar ratio be 5:1) as alkali treatment agent, mix with nickel cobalt aluminium ternary material, in atmosphere 500 DEG C process 4h, continue in atmosphere 800 DEG C process 10h, can obtain basicity reduce and Surface coating Li
2zrO
3and ZrO
2modification ternary LiNi
0.8co
0.15al
0.05o
2material.After testing, modified LiNi
0.8co
0.15al
0.05o
2in material, residual lithium salt impurity content is that 0.06%(is with Li
2cO
3meter), pH value reduces to 10.71, and in 36 hours, slurry has no glue solidification, under 3.0-4.3V after 1C current cycle 100 times capability retention up to 94.7%.
comparative example 6: after testing, spinel nickel manganese LiNi
0.5mn
1.5o
2middle residual lithium salt impurity content is that 0.15%(is with Li
2cO
3meter), pH value is 11.34, and slurry bond time is that under 16.5h, 3.0-5.0V, after 1C current cycle 100 times, capability retention is 95.2%.
embodiment 6: take the spinel nickel manganese LiNi in 100.0g comparative example 6
0.5mn
1.5o
2, wherein residual lithium salt Li
2cO
3for 0.15g.Add 0.6646g acetic acid zirconium Zr (CH
3cOO)
3(with residual lithium salt Li
2cO
3molar ratio be 1:1) as alkali treatment agent, mix with spinel nickel manganese material, in atmosphere 300 DEG C process 2h, continue in atmosphere 750 DEG C process 6h, can obtain basicity reduce and Surface coating Li
2zrO
3modified spinelle nickel manganese LiNi
0.5mn
1.5o
2material.After testing, modified LiNi
0.5mn
1.5o
2in material, residual lithium salt impurity content is that 0.03%(is with Li
2cO
3meter), pH value reduces to 10.17, and in 48 hours, slurry has no glue solidification, under 3.0-5.0V after 1C current cycle 100 times capability retention up to 99.1%.
Above-described embodiment of the present invention, does not form limiting the scope of the present invention.Any amendment done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within claims of the present invention.
Claims (8)
1. a method of modifying for anode material for lithium-ion batteries, is characterized in that, is completed by following steps:
(1) detect and analyze lithium salts impurity content remaining in positive electrode, take the low melting point aluminium salt of certain mol proportion example or zirconates as alkali treatment agent, to join in positive electrode and to mix;
(2) solid mixture obtained in step (1) is heated to alkali treatment agent infiltrated with molten metal, and is incubated;
(3) gained mixture in step (2) is heated to further alkali treatment agent decompose and react with the lithium salts impurity of remnants in positive electrode, and is incubated.
2. the method for modifying of anode material for lithium-ion batteries according to claim 1, it is characterized in that, positive electrode described in step (1) comprises the acid of stratiform cobalt lithium, lithium nickelate, nickle cobalt lithium manganate ternary, nickel cobalt lithium aluminate ternary, lithium-rich manganese base material or lithium manganate having spinel structure, one or more in nickel ion doped material; Described low melting point alkali treatment agent is one or more in aluminum nitrate, aluminum acetate, zirconium nitrate, acetic acid zirconium, basic zirconium chloride.
3. the method for modifying of anode material for lithium-ion batteries according to claim 1, is characterized in that, in step (1), when adopting low melting point aluminium salt as alkali treatment agent, and the lithium salts Li of low melting point aluminium salt and remnants in positive electrode
2cO
3molar ratio be 2:1 ~ 10:1; When adopting low melting point zirconates as alkali treatment agent, the lithium salts Li of low melting point zirconates and remnants in positive electrode
2cO
3molar ratio be 1:1 ~ 5:1.
4. the method for modifying of anode material for lithium-ion batteries according to claim 1, is characterized in that, the heating-up temperature described in step (2) is 75 ~ 500 DEG C, and temperature retention time is 0.5 ~ 8 hour.
5. the method for modifying of anode material for lithium-ion batteries according to claim 1, is characterized in that, the heating-up temperature described in step (3) is 600 ~ 900 DEG C, and temperature retention time is 1 ~ 10 hour.
6. the method for modifying of anode material for lithium-ion batteries according to claim 1, is characterized in that, in modified positive electrode, residual lithium salt impurity content significantly reduces, and there is coating modification layer on positive electrode surface.
7. the method for modifying of anode material for lithium-ion batteries according to claim 6, is characterized in that, described coating modification layer comprises LiAlO
2and Li
2zrO
3in at least one, when adopt alkali treatment agent excessive, described coating modification layer also comprises Al
2o
3and ZrO
2in at least one.
8. the method for modifying of anode material for lithium-ion batteries according to claim 7, is characterized in that, alkali treatment agent is excessive to be referred to: when adopting low melting point aluminium salt as alkali treatment agent, low melting point aluminium salt and remaining lithium salts Li
2cO
3molar ratio more than 2:1, or when adopting low melting point zirconates as alkali treatment agent, low melting point zirconates and remaining lithium salts Li
2cO
3molar ratio more than 1:1.
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