CN103400978A - Method for modifying lithium nickel manganese oxide material, lithium nickel manganese oxide material and lithium ion battery - Google Patents
Method for modifying lithium nickel manganese oxide material, lithium nickel manganese oxide material and lithium ion battery Download PDFInfo
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- CN103400978A CN103400978A CN2013103323594A CN201310332359A CN103400978A CN 103400978 A CN103400978 A CN 103400978A CN 2013103323594 A CN2013103323594 A CN 2013103323594A CN 201310332359 A CN201310332359 A CN 201310332359A CN 103400978 A CN103400978 A CN 103400978A
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- manganese oxide
- oxide material
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- 239000000463 material Substances 0.000 title claims abstract description 185
- 238000000034 method Methods 0.000 title claims abstract description 59
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 17
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 title abstract 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910006703 Li—Ni—Mn—O Inorganic materials 0.000 claims description 139
- 238000012986 modification Methods 0.000 claims description 37
- 230000004048 modification Effects 0.000 claims description 37
- 238000001354 calcination Methods 0.000 claims description 23
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 claims description 15
- 229910012409 LiNi0.4Mn1.6O4 Inorganic materials 0.000 claims description 7
- 229910012752 LiNi0.5Mn0.5O2 Inorganic materials 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 abstract description 16
- 238000003754 machining Methods 0.000 abstract 1
- 230000007935 neutral effect Effects 0.000 abstract 1
- 239000007774 positive electrode material Substances 0.000 abstract 1
- 229910013716 LiNi Inorganic materials 0.000 description 43
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 19
- 229910052744 lithium Inorganic materials 0.000 description 19
- 239000011572 manganese Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 13
- 238000001035 drying Methods 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 238000000498 ball milling Methods 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000007599 discharging Methods 0.000 description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 8
- 238000005245 sintering Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 229910012541 LiNi0.4Cr0.2Mn1.4O4 Inorganic materials 0.000 description 5
- 229910013022 LiNi0.5Mn1.5O3.95F0.05 Inorganic materials 0.000 description 5
- 238000000137 annealing Methods 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- -1 compound carbonate Chemical class 0.000 description 4
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910018663 Mn O Inorganic materials 0.000 description 2
- 229910003176 Mn-O Inorganic materials 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910013872 LiPF 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
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910052786 argon Inorganic materials 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
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229940008015 lithium carbonate Drugs 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 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 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a method for modifying a lithium nickel manganese oxide material, the lithium nickel manganese oxide material and a lithium ion battery. The method comprises the following step of washing the lithium nickel manganese oxide material by water or a solution containing water until a pH value of the lithium nickel manganese oxide material is 7.2-8.0. The pH value of an obtained modified lithium nickel manganese oxide material is close to neutral by washing and controlling the pH of the lithium nickel manganese oxide material during the washing process, so that the purity of the lithium nickel manganese oxide material is greatly increased; electrode machining properties of the lithium nickel manganese oxide material is increased; first coulombic efficiency of a battery by using the material as a positive electrode material is increased; and at the same time, high temperature resistance and safety performance of the battery are increased.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of method, Li-Ni-Mn-O material and lithium ion battery of Li-Ni-Mn-O material modification.
Background technology
In recent years, along with the requirement of the day by day serious and electronic product lightness of energy environment issues, people deepen continuously to the research of lithium ion battery.At present in commercial lithium-ion battery system, positive electrode adopts cobalt acid lithium more, due to rare, expensive, the poisonous contaminated environment of positive pole material of lithium cobalt acid cobalt resource used, poor stability, so it is not suitable for using in electric automobile.Positive electrode comprises the battery of LiMn2O4, owing to having the shortcomings such as high-temperature behavior is poor, thereby has limited its application in electric automobile.Positive electrode comprises that the battery of LiFePO4 exists the shortcomings such as processing characteristics, high rate performance, poor performance at low temperatures.LiNi
0.5mn
1.5o
4positive electrode as battery mainly exists the platform of 4.7V, corresponding Ni in charge and discharge process
2+/ Ni
4+oxidation-reduction process, and LiNi
0.5mn
1.5o
4theoretical capacity can reach 146.7mAh/g, there is higher specific power, use LiNi
0.5mn
1.5o
4battery as positive electrode is hopeful to be used widely as automobile power cell, therefore become the focus of current Study on Li-ion batteries using.
Current LiNi
0.5mn
1.5o
4the preparation method of material has a variety of, mainly contain solid phase method, coprecipitation, compound carbonate method, sol-gel process, Rheological Phase Method, molten salt growth method, emulsion seasoning and ullrasonic spraying high-temperature decomposition etc., use above-mentioned any method all need under high temperature (700 ℃～1000 ℃), carry out sintering in preparation process, when preparation raw material, the compound of lithium slightly excessive 2%～10%, for at high temperature a small amount of volatilization during sintering of the compound that compensates lithium, the material at this moment prepared often comprises LiNi
0.5mn
1.5o
4with the oxide of lithium, thus the oxide that makes the material finally prepared contain unnecessary lithium.The oxide that contains unnecessary lithium in material raises the pH value of material, certainly, also may contain the unnecessary oxide of other metal in material, the oxide of the oxide of unnecessary nickel or unnecessary manganese for example, these unnecessary metal oxides can both make the pH value of material raise, make like this electrode poor processability of material, use this material low as the coulombic efficiency first of the battery of positive electrode, the performances such as the battery high-temperature behavior of making, security performance are also poor, have a strong impact on its commercial applications.
Summary of the invention
Technical problem to be solved by this invention is for above shortcomings in prior art, a kind of method, Li-Ni-Mn-O material and lithium ion battery of Li-Ni-Mn-O material modification are provided, the pH value of the Li-Ni-Mn-O material of the modification that the method obtains is close to neutrality, thereby greatly improved the purity of Li-Ni-Mn-O material, and improved and used the first coulombic efficiency of this material as the battery of positive electrode.
The technical scheme that solution the technology of the present invention problem adopts is to provide a kind of method of Li-Ni-Mn-O material modification, comprises the following steps:
Step (1): water or moisture solution are washed the Li-Ni-Mn-O material, wash to the pH value of Li-Ni-Mn-O material be 7.2～8.0.
Preferably, in described step (1), also comprise afterwards step (2): by the Li-Ni-Mn-O material calcination that to wash to the pH value be 7.2～8.0 obtained in described step (1), obtain the Li-Ni-Mn-O material of modification.
Preferably, the calcination in described step (2) is that calcination temperature is 400～700 ℃, and calcination time is 1～15 hour.
Preferably, while making water or moisture solution be washed the Li-Ni-Mn-O material described in described step (1), by ultrasonic wave, described Li-Ni-Mn-O material is disperseed in water or moisture solution.
Preferably, described hyperacoustic sound intensity is 30～120W/cm
2.
Preferably, the described time of described Li-Ni-Mn-O material being disperseed in water or moisture solution by ultrasonic wave is 10～60 minutes.
Preferably, while making water or moisture solution be washed the Li-Ni-Mn-O material described in described step (1), when the pH of described Li-Ni-Mn-O material value is greater than 11, add slightly acidic water solution to be washed, and wash to the pH value be 7.2～8.
Preferably, described Li-Ni-Mn-O material is LiNi
0.5mn
0.5o
2, LiNi
0.5mn
1.5o
4, LiNi
0.4mn
1.6o
4in any one.
Preferably, the Li-Ni-Mn-O material that described Li-Ni-Mn-O material is the metal substitute doping, described metal is any one in Co, Al, Cr, Zr, Fe, Ti, Mg, Al;
Perhaps, the Li-Ni-Mn-O material that described Li-Ni-Mn-O material is the fluorine substitute doping.
The present invention also provides a kind of Li-Ni-Mn-O material, and its method by above-mentioned modification obtains.
The present invention also provides a kind of lithium ion battery, and its positive pole comprises above-mentioned Li-Ni-Mn-O material.
The pH value of the Li-Ni-Mn-O material of the modification that the method for the pH of the method for the Li-Ni-Mn-O material modification in the present invention by washing and control the Li-Ni-Mn-O material in washing process obtains is close to neutrality, thereby greatly improved the purity of Li-Ni-Mn-O material, improved its electrode processing characteristics, and improved and used the first coulombic efficiency of this material as the battery of positive electrode, also improved resistance to elevated temperatures and the security performance of battery simultaneously.
The accompanying drawing explanation
The first charge-discharge cycle performance curve that Fig. 1 is the lithium battery made of the prepared Li-Ni-Mn-O material of Comparative Examples 1 of the present invention;
The discharge cycles performance curve that Fig. 2 is the lithium battery made of the prepared Li-Ni-Mn-O material of Comparative Examples 1 of the present invention;
The first charge-discharge cycle performance curve of the lithium battery that the Li-Ni-Mn-O material that the method that Fig. 3 is the embodiment of the present invention 1 by modification obtains is made;
The lithium battery discharge cycles performance curve that the Li-Ni-Mn-O material that the method that Fig. 4 is the embodiment of the present invention 1 by modification obtains is made.
Embodiment
For making those skilled in the art understand better technical scheme of the present invention, below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Comparative Examples 1
This Comparative Examples provides a kind of Li-Ni-Mn-O material LiNi
0.5mn
1.5o
4the preparation method, adopt the compound carbonate method, comprise the following steps:
(1) ratio according to the molal quantity of the molal quantity of nickel and manganese is the mixed aqueous solution that Ni:Mn=1:3 prepares nickel nitrate and manganese nitrate, under stirring, in mixed aqueous solution, drips Na
2cO
3solution (Na
2cO
3excessive 2%, to guarantee Ni
2+, Mn
2+ion precipitation is complete), after standing 4 hours, suction filtration, wash 3 times, 95 ℃ of dry 12h, obtain nickel manganese compound carbonate.
(2) according to the molal quantity of the molal quantity of lithium and nickel and manganese and ratio be Li:(Ni+Mn)=to take respectively LiOH(Li slightly excessive 5% be in order to compensate self at high temperature volatilization on a small quantity to 1.05:2) and above-mentioned nickel manganese compound carbonate, then add planetary ball mill, add again a certain amount of ethanol, the ratio of the amount of ethanol and solid mixture is 1.1mL/g, rotating speed ball milling 8h with 300r/min, ball milling is even, takes out dry.Then by temperature programmed control sintering under air atmosphere, with the programming rate of 3 ℃/min, be heated to 500 ℃, insulation 4h; Be heated to 850 ℃ with 5 ℃/min programming rate, calcining 10h; Be down to 600 ℃ with 4 ℃/min cooling rate again, annealing 10h, finally be cooled to room temperature naturally, obtains Li-Ni-Mn-O material LiNi
0.5mn
1.5o
4.
The preparation of battery pole piece and method of testing:
By Li-Ni-Mn-O material LiNi
0.5mn
1.5o
4, conductive agent acetylene black, binding agent PVDF(Kynoar) according to mass ratio 8:1:1, mix, use the NMP(1-N-methyl-2-2-pyrrolidone N-) this mixture is modulated into to slurry, evenly be coated on aluminium foil, put into baking oven, under 80～120 ℃, dry 1h, take out and be washed into pole piece, again 85 ℃ of vacuumizes 12 hours, carry out compressing tablet, and then, 85 ℃ of vacuumizes 12 hours, make the experimental cell pole piece.Take the lithium sheet as to electrode, the LiPF that electrolyte is 1.2mol/L
6eC(ethyl carbonate ester)+the DMC(dimethyl carbonate) (volume ratio 1:1) solution, barrier film is the celgard2400 film, is assembled into CR2025 type button cell in being full of the glove box of argon gas atmosphere.
As shown in Figure 1, this button cell is carried out to the test of first charge-discharge specific capacity: the charging/discharging voltage scope is 3.5～4.9V, at charging and discharging currents, be under the condition of 0.1C, wherein, 1C=130mA/g, the initial charge specific capacity is 165.16mAh/g, first discharge specific capacity 130.32mAh/g, and coulombic efficiency is 78.91% first.
As shown in Figure 2, this button cell is carried out to the charge-discharge performance test: the charging/discharging voltage scope is 3.5～4.9V, at first charging and discharging currents is respectively 0.1C, 0.2C, each multiplying power circulates respectively 10 times, then be 1C at charging and discharging currents and carry out the cycle performance test, first discharge specific capacity 127mAh/g, the specific discharge capacity after 100 times that circulates is 121.537mAh/g, capability retention is 95.7%.
Embodiment 1
The present embodiment provides the LiNi of the Li-Ni-Mn-O material in a kind of Comparative Examples 1
0.5mn
1.5o
4the method of modification comprises the following steps:
Step (1): get the Li-Ni-Mn-O material LiNi in Comparative Examples 1
0.5mn
1.5o
4add in distilled water, magnetic agitation 40min, be uniformly dispersed it, and centrifuge washing is until 10%(m/m) the Li-Ni-Mn-O material LiNi of (mass percent)
0.5mn
1.5o
4the pH value of suspension be 7.5, then carry out drying.Certainly, also can use moisture solution to the Li-Ni-Mn-O material LiNi in Comparative Examples 1
0.5mn
1.5o
4washed, for example the mixed solution of the mixed solution of water and ethanol or water and methyl alcohol.
Step (2): the Li-Ni-Mn-O material LiNi that drying is crossed
0.5mn
1.5o
4700 ℃ of lower calcinations, calcination 1 hour, the Li-Ni-Mn-O material LiNi of the performance that improves
0.5mn
1.5o
4.
The present embodiment has obtained a kind of Li-Ni-Mn-O material LiNi by above-mentioned method
0.5mn
1.5o
4.
The present embodiment also provides a kind of lithium ion battery, and its positive pole contains above-mentioned Li-Ni-Mn-O material LiNi
0.5mn
1.5o
4.
By step (1), the oxide of the unnecessary lithium in the Li-Ni-Mn-O material as raw material can be removed, this washing process also can be removed the oxide of unnecessary nickel or the oxide of unnecessary manganese, the pH value of the Li-Ni-Mn-O material of the modification that the method for the pH by washing and control the Li-Ni-Mn-O material in washing process obtains is close to neutrality, thereby greatly improved the purity of Li-Ni-Mn-O material, improved its electrode processing characteristics, and improved and used the first coulombic efficiency of this material as the battery of positive electrode, resistance to elevated temperatures and the security performance of battery have also been improved simultaneously.
But the washing operation in step (1) can destroy the crystal formation of Li-Ni-Mn-O material to a certain extent, can reduce the oxygen defect of Li-Ni-Mn-O material by the operation of step (2), make the crystalline structure of Li-Ni-Mn-O material complete; The crystal face smoothness that it can improve material, reduce the material specific area, makes material have larger compacted density.The battery of being made by this material has higher specific energy, and the material granule Contact closely makes in battery charge and discharge process the lithium ion the evolving path shorter, is conducive to improve cycle performance and the high rate performance of Li-Ni-Mn-O material.
Can also remove the crystallization water in the material produced due to washing by step (2).If this crystallization water is not removed, so this Li-Ni-Mn-O material can caused to battery generation inflatable after positive electrode is made into battery, and the electrolyte lithium hexafluoro phosphate meets water and can decompose and produce HF, HF corrosivity is strong, and then destroys battery.
According to preparing the method for button cell in Comparative Examples 1, the Li-Ni-Mn-O material LiNi that uses the method for the present embodiment by modification to obtain
0.5mn
1.5o
4material is made button cell, as shown in Figure 3, and this button cell is carried out to the test of first charge-discharge specific capacity: the charging/discharging voltage scope is 3.5～4.9V, at charging and discharging currents, be under the condition of 0.1C, wherein, 1C=130mA/g, the initial charge specific capacity is 146.016mAh/g, first discharge specific capacity 128.259mAh/g, coulombic efficiency is 87.84% first.
As shown in Figure 4, this button cell is carried out to the charge-discharge performance test: the charging/discharging voltage scope is 3.5～4.9V, the first charge-discharge electric current is respectively 0.1C, 0.2C, each multiplying power circulates respectively 10 times, then be 1C at charging and discharging currents and carry out the cycle performance test, first discharge specific capacity 123.38mAh/g, the specific discharge capacity after 100 times that circulates is 119.774mAh/g, capability retention is 97.1%.
Compare the Li-Ni-Mn-O material LiNi that uses the method for the present embodiment by modification to obtain with Comparative Examples 1
0.5mn
1.5o
4efficiency first and the cycle performance of the battery that material is made have larger lifting, adopt the chemical property of the battery of the material in the scheme in the present embodiment obviously to improve.
Comparative Examples 2
This Comparative Examples provides a kind of Li-Ni-Mn-O material LiNi
0.5mn
1.5o
4the preparation method, adopt solid phase method, it comprises the following steps:
Ratio according to the molal quantity of the molal quantity of the molal quantity of lithium, nickel, manganese is that Li:Ni:Mn=1.06:0.5:1.5 takes respectively Li
2cO
3(Li slightly excessive 6% is in order to compensate self at high temperature volatilization on a small quantity), Ni
2o
3, MnO
2, then add planetary ball mill, with the rotating speed ball milling 6h of 400r/min, ball milling is even, takes out dry.Then temperature programmed control sintering under air atmosphere, be heated to 900 ℃ with 5 ℃/min programming rate, calcining 10h; Be down to 700 ℃ with 4 ℃/min cooling rate again, annealing 10h, finally be cooled to room temperature naturally, obtains Li-Ni-Mn-O material LiNi
0.5mn
1.5o
4.
According to preparing the method for button cell in Comparative Examples 1, the Li-Ni-Mn-O material LiNi that uses this Comparative Examples to prepare
0.5mn
1.5o
4material is made button cell, for the test data of battery in Table 1.
Embodiment 2
The present embodiment provides the LiNi of the Li-Ni-Mn-O material in a kind of Comparative Examples 2
0.5mn
1.5o
4the method of modification comprises the following steps:
Step (1): get the Li-Ni-Mn-O material LiNi in Comparative Examples 2
0.5mn
1.5o
4be added to the water, magnetic agitation 30min, be uniformly dispersed it, and centrifuge washing is until 10%(m/m) Li-Ni-Mn-O material LiNi
0.5mn
1.5o
4the pH value of suspension be 7.2, then carry out drying, the Li-Ni-Mn-O material LiNi of the performance that improves
0.5mn
1.5o
4.Certainly, also can use moisture solution to the Li-Ni-Mn-O material LiNi in Comparative Examples 1
0.5mn
1.5o
4washed, for example the mixed solution of the mixed solution of water and ethanol or water and methyl alcohol.
The present embodiment has obtained a kind of Li-Ni-Mn-O material LiNi by above-mentioned method
0.5mn
1.5o
4.
The present embodiment also provides a kind of lithium ion battery, and its positive pole contains above-mentioned Li-Ni-Mn-O material LiNi
0.5mn
1.5o
4.
According to preparing the method for button cell in Comparative Examples 1, the Li-Ni-Mn-O material LiNi that uses the method for the present embodiment by modification to obtain
0.5mn
1.5o
4material is made button cell, for the test data of battery in Table 1.
Compare the Li-Ni-Mn-O material LiNi that uses the method for the present embodiment by modification to obtain with Comparative Examples 2
0.5mn
1.5o
4efficiency first and the cycle performance of the battery that material is made have larger lifting, adopt the chemical property of the battery of the material in the scheme in the present embodiment obviously to improve.
Comparative Examples 3
This Comparative Examples provides a kind of Li-Ni-Mn-O material LiNi
0.4cr
0.2mn
1.4o
4the preparation method, adopt Rheological Phase Method, it comprises the following steps:
Ratio according to the molal quantity of the molal quantity of the molal quantity of the molal quantity of lithium, nickel, chromium, manganese is that Li:Ni:Cr:Mn=1.04:0.4:0.2:1.4 takes respectively lithium acetate (Li slightly excessive 4% is in order to compensate self at high temperature volatilization on a small quantity), nickel acetate, chromic nitrate and manganese acetate, mix, add a certain amount of ethanol, the amount ratio of ethanol and solid is 0.8mL/g, be adjusted to pasty state, add 20mL ammoniacal liquor (mass fraction is 20%), ball milling is even, takes out dry.Then temperature programmed control, at the air atmosphere sintering, is heated to 400 ℃ with 4 ℃/min programming rate, insulation 4h; Be heated to 800 ℃ with 3 ℃/min programming rate, calcining 12h; Be down to 600 ℃ with 4 ℃/min cooling rate again, annealing 12h, finally be cooled to room temperature naturally, obtains Li-Ni-Mn-O material LiNi
0.4cr
0.2mn
1.4o
4.
According to preparing the method for button cell in Comparative Examples 1, the Li-Ni-Mn-O material LiNi that uses this Comparative Examples to prepare
0.5mn
1.5o
4liNi
0.4cr
0.2mn
1.4o
4material is made button cell, for the test data of battery in Table 1.
Embodiment 3
The present embodiment provides the LiNi of the Li-Ni-Mn-O material in a kind of Comparative Examples 3
0.4cr
0.2mn
1.4o
4the method of modification comprises the following steps:
Step (1): get the Li-Ni-Mn-O material LiNi in Comparative Examples 3
0.4cr
0.2mn
1.4o
4add in distilled water, by ultrasonic wave, it is uniformly dispersed, hyperacoustic sound intensity is 70W/cm
2, ultrasonic time is 10 minutes.Li-Ni-Mn-O material LiNi now
0.4cr
0.2mn
1.4o
4the pH value be 11.0, the aqueous solution by acetic acid carries out centrifuge washing until 10%(m/m to it) Li-Ni-Mn-O material LiNi
0.4cr
0.2mn
1.4o
4the pH value of suspension be 8.0, then carry out drying.
Step (2): the Li-Ni-Mn-O material LiNi that drying is crossed
0.4cr
0.2mn
1.4o
4400 ℃ of lower calcinations, calcination 15 hours, the Li-Ni-Mn-O material LiNi of the performance that improves
0.4cr
0.2mn
1.4o
4.
The present embodiment has obtained a kind of Li-Ni-Mn-O material LiNi by above-mentioned method
0.4cr
0.2mn
1.4o
4.Li-Ni-Mn-O material LiNi in the present embodiment
0.4cr
0.2mn
1.4o
4li-Ni-Mn-O material for the chromium substitute doping.
Certainly, the method of in the present embodiment, the Li-Ni-Mn-O material being carried out to modification is applicable to the Li-Ni-Mn-O material that metal replaces, the concrete Li-Ni-Mn-O material replaced for Cr in the present embodiment, described metal can be also any one in Co, Al, Zr, Fe, Ti, Mg, Al, all is applicable to use this method.
The present embodiment also provides a kind of lithium ion battery, and its positive pole contains above-mentioned Li-Ni-Mn-O material LiNi
0.4cr
0.2mn
1.4o
4.
According to preparing the method for button cell in Comparative Examples 1, the Li-Ni-Mn-O material LiNi that uses the method for the present embodiment by modification to obtain
0.4cr
0.2mn
1.4o
4material is made button cell, for the test data of battery in Table 1.
Compare the Li-Ni-Mn-O material LiNi that uses the method for the present embodiment by modification to obtain with Comparative Examples 3
0.4cr
0.2mn
1.4o
4efficiency first and the cycle performance of the battery that material is made have larger lifting, adopt the chemical property of the battery of the material in the scheme in the present embodiment obviously to improve.
The discharge cycles test data of the battery that table 1. Comparative Examples 1～3, the prepared Li-Ni-Mn-O material of embodiment 1～3 make
Embodiment 4
The present embodiment provides a kind of Li-Ni-Mn-O material LiNi
0.5mn
0.5o
2the preparation method, adopt sol-gal process, it comprises the following steps:
Molal quantity according to lithium, the molal quantity of nickel, the ratio of the molal quantity of manganese is Li:Ni:Mn=1.05:0.5:0.5 preparation lithium nitrate (Li slightly excessive 5% is in order to compensate self at high temperature volatilization on a small quantity), nickel nitrate, the mixed aqueous solution of manganese nitrate, add again chelating agent, the amount of substance of chelating agent and the lithium in mixed aqueous solution, nickel, the amount of substance of manganese ion and ratio be 1:(1～1.1), regulating the pH value with ammoniacal liquor is between 9～10, then by this clear solution in 110～150 ℃ of lower evaporates to dryness, obtained the xerogel predecessor, temperature programmed control is sintering under air atmosphere, be heated to 400～600 ℃ with 0.5～10 ℃/min programming rate, insulation 2～12h, be heated to 750～950 ℃ with 0.5～10 ℃/min programming rate, calcine 2～24h, finally naturally be cooled to room temperature, obtain Li-Ni-Mn-O material LiNi
0.5mn
0.5o
2.
The present embodiment provides a kind of above-mentioned Li-Ni-Mn-O material LiNi prepared
0.5mn
0.5o
2the method of modification comprises the following steps:
Step (1): get above-mentioned Li-Ni-Mn-O material LiNi
0.5mn
0.5o
2be added to the water, by ultrasonic wave, it be uniformly dispersed, hyperacoustic sound intensity is 30W/cm
2, ultrasonic time is 60 minutes.Li-Ni-Mn-O material LiNi now
0.5mn
0.5o
2the pH value be 12.0, by aqueous acetic acid, it is carried out to centrifuge washing until 10%(m/m) Li-Ni-Mn-O material LiNi
0.5mn
0.5o
2the pH value of suspension be 7.8, then carry out drying.
Step (2): the Li-Ni-Mn-O material LiNi that drying is crossed
0.5mn
0.5o
2600 ℃ of lower calcinations, calcination 10 hours, the Li-Ni-Mn-O material LiNi of the performance that improves
0.5mn
0.5o
2.
The present embodiment has obtained a kind of Li-Ni-Mn-O material LiNi by above-mentioned method
0.5mn
0.5o
2.
The present embodiment also provides a kind of lithium ion battery, and its positive pole contains above-mentioned Li-Ni-Mn-O material LiNi
0.5mn
0.5o
2.
Embodiment 5
The present embodiment provides a kind of Li-Ni-Mn-O material LiNi
0.4mn
1.6o
4the preparation method, adopt the compound carbonate method, comprise the following steps:
(1) ratio according to the molal quantity of the molal quantity of nickel and manganese is the mixed aqueous solution that Ni:Mn=1:4 prepares nickel nitrate and manganese nitrate, under stirring, in mixed aqueous solution, drips Na
2cO
3solution (Na
2cO
3excessive 2%, to guarantee Ni
2+, Mn
2+ion precipitation is complete), after standing 4 hours, suction filtration, wash 3 times, 95 ℃ of dry 12h, obtain nickel manganese compound carbonate.
(2) according to the molal quantity of the molal quantity of lithium and nickel and manganese and ratio be Li:(Ni+Mn)=to take respectively LiOH(Li slightly excessive 5% be in order to compensate self at high temperature volatilization on a small quantity to 1.05:2) and above-mentioned nickel manganese compound carbonate, then add planetary ball mill, add again a certain amount of ethanol, the ratio of the amount of ethanol and solid mixture is 1.1mL/g, rotating speed ball milling 8h with 300r/min, ball milling is even, takes out dry.Then by temperature programmed control sintering under air atmosphere, with the programming rate of 3 ℃/min, be heated to 500 ℃, insulation 4h; Be heated to 850 ℃ with 5 ℃/min programming rate, calcining 10h; Be down to 600 ℃ with 4 ℃/min cooling rate again, annealing 10h, finally be cooled to room temperature naturally, obtains Li-Ni-Mn-O material LiNi
0.4mn
1.6o
4.
The present embodiment provides a kind of above-mentioned Li-Ni-Mn-O material LiNi prepared
0.4mn
1.6o
4the method of modification comprises the following steps:
Step (1): get above-mentioned Li-Ni-Mn-O material LiNi
0.4mn
1.6o
4add in distilled water, by ultrasonic wave, it is uniformly dispersed, hyperacoustic sound intensity is 120W/cm
2, ultrasonic time is 40 minutes.Li-Ni-Mn-O material LiNi now
0.4mn
1.6o
4the pH value be 13.0, the aqueous solution by acetic acid carries out centrifuge washing until 10%(m/m to it) Li-Ni-Mn-O material LiNi
0.4mn
1.6o
4the pH value of suspension be 7.3, then carry out drying.
Step (2): the Li-Ni-Mn-O material LiNi that drying is crossed
0.4mn
1.6o
4500 ℃ of lower calcinations, calcination 8 hours, the Li-Ni-Mn-O material LiNi of the performance that improves
0.4mn
1.6o
4.
The present embodiment has obtained a kind of Li-Ni-Mn-O material LiNi by above-mentioned method
0.4mn
1.6o
4.
The present embodiment also provides a kind of lithium ion battery, and its positive pole contains above-mentioned Li-Ni-Mn-O LiNi
0.4mn
1.6o
4.
Embodiment 6
The present embodiment provides a kind of Li-Ni-Mn-O material LiNi
0.5mn
1.5o
3.95f
0.05the preparation method, adopt Rheological Phase Method, comprise the following steps:
(1) take respectively lithium carbonate, nickel acetate, manganese acetate, lithium fluoride according to amount of substance ratio Li:Ni:Mn:F=0.9975:0.5:1.5:0.05, add planetary ball mill, with the rotating speed ball milling 6h of 350r/min, ball milling mixes.Add a certain amount of ethanol, the ratio of the amount of ethanol and solid is 1(mL/g), be modulated into rheology state starchiness, drying, obtain persursor material.
(2) above-mentioned persursor material is heated to 500 ℃ with the programming rate of 3 ℃/min, insulation 6h, carry out preliminary treatment.Take out material and carry out fragmentation, ball milling mixes, and obtains powder body material.Then temperature programmed control air atmosphere sintering, be heated to 800 ℃ with 5 ℃/min programming rate, calcining 12h; 4 ℃/min cooling rate is down to 600 ℃ again, annealing 15h; Finally naturally be cooled to room temperature, obtain LiNi
0.5mn
1.5o
3.95f
0.05material.
The present embodiment provides a kind of above-mentioned Li-Ni-Mn-O material LiNi prepared
0.5mn
1.5o
3.95f
0.05the method of modification comprises the following steps:
Step (1): get above-mentioned Li-Ni-Mn-O material LiNi
0.5mn
1.5o
3.95f
0.05add in distilled water, by ultrasonic wave, it is uniformly dispersed, hyperacoustic sound intensity is 90W/cm
2, ultrasonic time is 20 minutes.Li-Ni-Mn-O material LiNi now
0.5mn
1.5o
3.95f
0.05the pH value be 9.0, by distilled water, it is carried out to centrifuge washing until 10%(m/m) Li-Ni-Mn-O material LiNi
0.5mn
1.5o
3.95f
0.05the pH value of suspension be 7.5, then carry out drying.
Step (2): the Li-Ni-Mn-O material LiNi that drying is crossed
0.5mn
1.5o
3.95f
0.05400 ℃ of lower calcinations, calcination 4 hours, the Li-Ni-Mn-O material LiNi of the performance that improves
0.5mn
1.5o
3.95f
0.05.
The present embodiment has obtained a kind of Li-Ni-Mn-O material LiNi by above-mentioned method
0.5mn
1.5o
3.95f
0.05.Li-Ni-Mn-O material LiNi in the present embodiment
0.5mn
1.5o
3.95f
0.05li-Ni-Mn-O material for the fluorine substitute doping.
The present embodiment also provides a kind of lithium ion battery, and its positive pole contains above-mentioned Li-Ni-Mn-O LiNi
0.5mn
1.5o
3.95f
0.05.
Be understandable that, above execution mode is only the illustrative embodiments adopted for principle of the present invention is described, yet the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement also are considered as protection scope of the present invention.
Claims (10)
1. the method for a Li-Ni-Mn-O material modification, is characterized in that, comprises the following steps:
Step (1): water or moisture solution are washed the Li-Ni-Mn-O material, wash to the pH value of Li-Ni-Mn-O material be 7.2～8.0.
2. the method for Li-Ni-Mn-O material modification according to claim 1, it is characterized in that, also comprise afterwards step (2) in described step (1): by the Li-Ni-Mn-O material calcination that to wash to the pH value be 7.2～8.0 obtained in described step (1), obtain the Li-Ni-Mn-O material of modification.
3. the method for Li-Ni-Mn-O material modification according to claim 2, is characterized in that, the calcination in described step (2) is that calcination temperature is 400～700 ℃, and calcination time is 1～15 hour.
4. the method for Li-Ni-Mn-O material modification according to claim 1, it is characterized in that, while making water or moisture solution be washed the Li-Ni-Mn-O material described in described step (1), by ultrasonic wave, described Li-Ni-Mn-O material is disperseed in water or moisture solution.
5. the method for Li-Ni-Mn-O material modification according to claim 4, is characterized in that, described hyperacoustic sound intensity is 30～120W/cm
2,
And/or the described time of described Li-Ni-Mn-O material being disperseed in water or moisture solution by ultrasonic wave is 10～60 minutes.
6. the method for Li-Ni-Mn-O material modification according to claim 1, it is characterized in that, while making water or moisture solution be washed the Li-Ni-Mn-O material described in described step (1), when the pH of described Li-Ni-Mn-O material value is greater than 11, add slightly acidic water solution to be washed, and wash to the pH value be 7.2～8.
7. the method for Li-Ni-Mn-O material modification according to claim 1, is characterized in that, described Li-Ni-Mn-O material is LiNi
0.5mn
0.5o
2, LiNi
0.5mn
1.5o
4, LiNi
0.4mn
1.6o
4in any one.
8. the method for Li-Ni-Mn-O material modification according to claim 1, is characterized in that, the Li-Ni-Mn-O material that described Li-Ni-Mn-O material is the metal substitute doping, and described metal is any one in Co, Al, Cr, Zr, Fe, Ti, Mg, Al;
Perhaps, the Li-Ni-Mn-O material that described Li-Ni-Mn-O material is the fluorine substitute doping.
9. a Li-Ni-Mn-O material, is characterized in that, its method by the described modification of claim 1～8 any one obtains.
10. a lithium ion battery, is characterized in that, its positive pole comprises Li-Ni-Mn-O material claimed in claim 9.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140339464A1 (en) * | 2013-05-20 | 2014-11-20 | Shenzhen Btr New Energy Materials Inc. | Method for modification of lithium ion battery positive electrode material |
| CN105609715A (en) * | 2015-12-18 | 2016-05-25 | 浙江天能能源科技有限公司 | Aluminum-titanium-co-doped nickel lithium manganate lithium ion battery positive electrode material and preparation method therefor |
| CN108063245A (en) * | 2017-10-30 | 2018-05-22 | 广东邦普循环科技有限公司 | A kind of method for reducing rich nickel ternary material surface lithium impurity |
| CN108321386A (en) * | 2018-01-10 | 2018-07-24 | 湖南邦普循环科技有限公司 | A method of control stratiform high-nickel material surface residual lithium content |
| CN109546088A (en) * | 2018-11-19 | 2019-03-29 | 常州大学 | A kind of nickelic tertiary cathode material method for washing |
| US10361423B2 (en) | 2016-01-18 | 2019-07-23 | Grst International Limited | Method of preparing battery electrodes |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003017054A (en) * | 2001-06-29 | 2003-01-17 | Sony Corp | Positive electrode active material, and manufacturing method of non-aqueous electrolyte battery |
| JP2009230863A (en) * | 2008-03-19 | 2009-10-08 | Panasonic Corp | Non-aqueous electrolyte secondary battery, and manufacturing method of positive electrode active material thereof |
| JP2009266712A (en) * | 2008-04-28 | 2009-11-12 | Sakai Chem Ind Co Ltd | Positive active material for lithium secondary battery and its manufacturing method |
| CN101771144A (en) * | 2009-01-04 | 2010-07-07 | 北京有色金属研究总院 | Method for improving capacity and cycle performance of spinel LiMn2O4 as anode material of lithium-ion battery |
| JP2011100633A (en) * | 2009-11-06 | 2011-05-19 | Sumitomo Electric Ind Ltd | Positive electrode active material for nonaqueous electrolyte battery, method of manufacturing the same, and nonaqueous electrolyte battery |
| CN102683672A (en) * | 2012-01-06 | 2012-09-19 | 吉安市优特利科技有限公司 | Method for decreasing pH value of ternary material |
| CN102738460A (en) * | 2012-07-17 | 2012-10-17 | 中国电子科技集团公司第十八研究所 | Surface passivating treatment method of spinel type manganese-based positive pole material |
-
2013
- 2013-08-01 CN CN2013103323594A patent/CN103400978A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003017054A (en) * | 2001-06-29 | 2003-01-17 | Sony Corp | Positive electrode active material, and manufacturing method of non-aqueous electrolyte battery |
| JP2009230863A (en) * | 2008-03-19 | 2009-10-08 | Panasonic Corp | Non-aqueous electrolyte secondary battery, and manufacturing method of positive electrode active material thereof |
| JP2009266712A (en) * | 2008-04-28 | 2009-11-12 | Sakai Chem Ind Co Ltd | Positive active material for lithium secondary battery and its manufacturing method |
| CN101771144A (en) * | 2009-01-04 | 2010-07-07 | 北京有色金属研究总院 | Method for improving capacity and cycle performance of spinel LiMn2O4 as anode material of lithium-ion battery |
| JP2011100633A (en) * | 2009-11-06 | 2011-05-19 | Sumitomo Electric Ind Ltd | Positive electrode active material for nonaqueous electrolyte battery, method of manufacturing the same, and nonaqueous electrolyte battery |
| CN102683672A (en) * | 2012-01-06 | 2012-09-19 | 吉安市优特利科技有限公司 | Method for decreasing pH value of ternary material |
| CN102738460A (en) * | 2012-07-17 | 2012-10-17 | 中国电子科技集团公司第十八研究所 | Surface passivating treatment method of spinel type manganese-based positive pole material |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140339464A1 (en) * | 2013-05-20 | 2014-11-20 | Shenzhen Btr New Energy Materials Inc. | Method for modification of lithium ion battery positive electrode material |
| US9440861B2 (en) * | 2013-05-20 | 2016-09-13 | Shenzhen Btr New Energy Materials Inc. | Method for modification of lithium ion battery positive electrode material |
| CN105609715A (en) * | 2015-12-18 | 2016-05-25 | 浙江天能能源科技有限公司 | Aluminum-titanium-co-doped nickel lithium manganate lithium ion battery positive electrode material and preparation method therefor |
| CN105609715B (en) * | 2015-12-18 | 2018-07-06 | 浙江天能能源科技股份有限公司 | Ti doped nickel ion doped anode material for lithium-ion batteries of a kind of aluminium and preparation method thereof |
| US10361423B2 (en) | 2016-01-18 | 2019-07-23 | Grst International Limited | Method of preparing battery electrodes |
| CN108063245A (en) * | 2017-10-30 | 2018-05-22 | 广东邦普循环科技有限公司 | A kind of method for reducing rich nickel ternary material surface lithium impurity |
| CN108063245B (en) * | 2017-10-30 | 2020-06-30 | 广东邦普循环科技有限公司 | Method for reducing lithium impurities on surface of nickel-rich ternary material |
| CN108321386A (en) * | 2018-01-10 | 2018-07-24 | 湖南邦普循环科技有限公司 | A method of control stratiform high-nickel material surface residual lithium content |
| CN109546088A (en) * | 2018-11-19 | 2019-03-29 | 常州大学 | A kind of nickelic tertiary cathode material method for washing |
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