CN103943849A - Preparation method of nickel-doping lithium manganate anode material for lithium ion battery - Google Patents
Preparation method of nickel-doping lithium manganate anode material for lithium ion battery Download PDFInfo
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- CN103943849A CN103943849A CN201410183047.6A CN201410183047A CN103943849A CN 103943849 A CN103943849 A CN 103943849A CN 201410183047 A CN201410183047 A CN 201410183047A CN 103943849 A CN103943849 A CN 103943849A
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- nickel
- manganese
- lithium manganate
- polyvinylpyrrolidone
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 11
- 239000010405 anode material Substances 0.000 title abstract description 7
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 20
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 18
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 18
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 239000002105 nanoparticle Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 5
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 42
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- CCJVDILPJUXPMF-UHFFFAOYSA-N [Mn].N#CO.[Ni] Chemical compound [Mn].N#CO.[Ni] CCJVDILPJUXPMF-UHFFFAOYSA-N 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- 229910015645 LiMn Inorganic materials 0.000 claims description 4
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 4
- 229910016897 MnNi Inorganic materials 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- ZVCDLGYNFYZZOK-UHFFFAOYSA-M sodium cyanate Chemical compound [Na]OC#N ZVCDLGYNFYZZOK-UHFFFAOYSA-M 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- RZYIBXBPVOVBJQ-UHFFFAOYSA-K [O-]C#N.[Na+].[Ni+2].[O-]C#N.[O-]C#N Chemical compound [O-]C#N.[Na+].[Ni+2].[O-]C#N.[O-]C#N RZYIBXBPVOVBJQ-UHFFFAOYSA-K 0.000 abstract 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910014689 LiMnO Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 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
- 229940011182 cobalt acetate Drugs 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 2
- 229940071257 lithium acetate Drugs 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) 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
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
-
- 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)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparation method of a nickel-doping lithium manganate anode material. The chemical formula of the nickel-doping lithium manganate anode material is LiMn1-xNixO2, wherein x is between 0.12 and 0.15. The preparation method comprises the following steps: (1) preparing mixed solution of manganese acetate and polyvinylpyrrolidone, dropwise adding a nickel sodium cyanate (Na2Ni(CN)4) aqueous solution into the mixed solution of manganese acetate and polyvinylpyrrolidone, controlling the dropping quantity and keeping the mole ratio of nickel ions and manganese ions to be 1:1, standing after magnetically stirring, carrying out centrifugal separation to obtain nickel sodium cyanate nano particles, and calcining the nano particles to obtain a precursor MnNiO3; (2) mixing lithium hydroxide, precursor MnNiO3 and manganese hydroxide, adding deionized water, stirring the mixture into thick pulp, and reacting at the constant temperature between 150 DEG C and 250 DEG C to obtain the nickel-doping lithium manganate. The anode material takes the MnNiO3 which is prepared by a wet method and has high purity and a microcellular structure as the main raw material, and the nickel-doping lithium manganate composite material with high energy density and good consistency is obtained by a low-temperature solid phase method.
Description
Affiliated technical field
The present invention relates to the preparation method of nickel adulterated lithium manganate positive electrode for a kind of lithium ion battery.
Background technology
Lithium rechargeable battery has high-energy-density, lightweight, free from environmental pollution, memory-less effect, stable work in work, the feature such as safe and reliable, since coming out, be widely used, having become main compact power at present, is also the developing focus of high-power moving battery.
Stratiform anode material for lithium-ion batteries is the focus of research in field.The material in theory with layer structure and spinel structure, can be as the positive electrode of lithium ion battery, but due to the difficulty in material self property difference and preparation technology, at present conventional anode material for lithium-ion batteries is still with the oxide LiCoO of cobalt, nickel, manganese
2, LiNiO
2, LiMnO
2be main.The LiMn2O4 LiMnO wherein with layer structure
2as anode material for lithium-ion batteries tool, have the following advantages: 1, theoretical capacity 285mAh/g, actual capacity can reach 250mAh/g left and right---surpass LiCoO
21.5 times; 2, fail safe is good; 3, aboundresources, cheap, toxicity is little; Its major defect is but cycle performance is poor that in discharge process, structure is stable not.
The preparation method of layered lithium manganate mainly contains two classes at present: solid phase method and wet method (hydro thermal method, sol-gel process etc.), solid phase method can be prepared burden by required stoichiometric proportion, suitability for industrialized large-scale production, but in preparation process preparation temperature will more than 700 ℃, calcination time is long, energy consumption is high, product crystal grain large (micron order), consistency is poor, and the initial discharge specific capacity of material is lower, and capacity activation cycle number of times is more; Wet method reaction temperature is low, and grain growth is easily controlled, and the initial capacity of material is higher.
Summary of the invention
The invention provides the preparation method of nickel adulterated lithium manganate positive electrode for a kind of lithium ion battery, the positive electrode that uses the method to prepare, high conformity, when thering is higher initial capacity, the good cyclical stability of tool also.
To achieve these goals, the preparation method of nickel adulterated lithium manganate positive electrode for a kind of lithium ion battery provided by the invention, the chemical formula of this positive electrode is LiMn
1-xni
xo
2, wherein: x=0.12-0.15, the method comprises the steps:
(1) presoma MnNiO
3preparation
By in manganese acetate and the water-soluble and ethanolic solution of polyvinylpyrrolidone, obtain manganese acetate and polyvinylpyrrolidone mixed solution, wherein the molar concentration of manganese acetate is 1-1.5mol/L, and the molar concentration of polyvinylpyrrolidone is 0.5-1mol/L, and the volume ratio of water and ethanol is 3:1-2;
At the temperature of 60-80 ℃, the nickel Zassol (Na that is 1-2mol/L by molar concentration
2ni (CN)
4) aqueous solution, being added drop-wise in above-mentioned manganese acetate and polyvinylpyrrolidone mixed solution, dripping quantity is controlled and made the mol ratio of nickel ion and manganese ion is 1:1, after dropwising, after magnetic agitation, standing 20-25h, centrifugation obtains nickel cyanic acid manganese (MnNi (CN)
4) nano particle;
Above-mentioned nickel cyanic acid manganese nano particle is placed in crucible, and under air atmosphere, the temperature lower calcination 1-2h with 450-500 ℃, can obtain presoma MnNiO
3;
(2) prepare stratiform nickel adulterated lithium manganate
By lithium hydroxide, above-mentioned precursor MnNiO
3, manganous hydroxide in molar ratio the proportioning of Li:Mn:Ni:Co=1:1-x:x mix, in ball mill, with the speed mechanical of 400-500r/min, mix 10-15h and obtain mixed-powder, ratio according to solid, liquid volume ratio 1:2-4 adds deionized water in described mixed-powder, stirs into thickness slurry;
Described slurry is inserted in a container with opening, make slurry volume account for the 1/10-1/5 of reactor volume, and to pass into volume be container volume 10-15 argon gas doubly, then container is airtight, closed container is put into insulating box, under the constant temperature of 150-250 ℃, react 10-15h, obtain nickel adulterated lithium manganate.
Positive electrode prepared by the present invention, the high-purity of using wet method to prepare has the MnNiO of multi-cellular structure
3as one of primary raw material, in conjunction with solid-phase low-temperature method, to obtain the nickel adulterated lithium manganate composite material of higher energy density, high conformity, make this material possess higher energy density and electrochemical stability.Therefore this composite material, when for lithium ion battery, has higher specific capacity and longer useful life.
Embodiment
Embodiment mono-
The chemical formula of positive electrode prepared by the present embodiment is LiMn
0.88ni
0.12o
2.
By in manganese acetate and the water-soluble and ethanolic solution of polyvinylpyrrolidone, obtain manganese acetate and polyvinylpyrrolidone mixed solution, wherein the molar concentration of manganese acetate is 1mol/L, and the molar concentration of polyvinylpyrrolidone is 0.5mol/L, and the volume ratio of water and ethanol is 3:1;
At the temperature of 60 ℃, the nickel Zassol (Na that is 1mol/L by molar concentration
2ni (CN)
4) aqueous solution, being added drop-wise in above-mentioned manganese acetate and polyvinylpyrrolidone mixed solution, dripping quantity is controlled and made the mol ratio of nickel ion and manganese ion is 1:1, after dropwising, after magnetic agitation, standing 20h, centrifugation obtains nickel cyanic acid manganese (MnNi (CN)
4) nano particle; Above-mentioned nickel cyanic acid manganese nano particle is placed in crucible, and under air atmosphere, the temperature lower calcination 2h with 450 ℃, can obtain presoma MnNiO
3;
By lithium hydroxide, above-mentioned precursor MnNiO
3, manganous hydroxide in molar ratio the proportioning of Li:Mn:Ni:Co=1:0.88:0.12 mix, in ball mill, with the speed mechanical of 400r/min, mix 15h and obtain mixed-powder, ratio according to solid, liquid volume ratio 1:2 adds deionized water in described mixed-powder, stirs into thickness slurry.
Described slurry is inserted in a container with opening, make slurry volume account for 1/10 of reactor volume, and pass into the argon gas that volume is 10 times of container volumes, then container is airtight, closed container is put into insulating box, under the constant temperature of 150 ℃, react 15h, obtain nickel adulterated lithium manganate.
Embodiment bis-
The chemical formula of positive electrode prepared by the present embodiment is LiMn
0.85ni
0.15o
2.
By in manganese acetate and the water-soluble and ethanolic solution of polyvinylpyrrolidone, obtain manganese acetate and polyvinylpyrrolidone mixed solution, wherein the molar concentration of manganese acetate is 1.5mol/L, and the molar concentration of polyvinylpyrrolidone is 1mol/L, and the volume ratio of water and ethanol is 3:2;
At the temperature of 80 ℃, the nickel Zassol (Na that is 2mol/L by molar concentration
2ni (CN)
4) aqueous solution, being added drop-wise in above-mentioned manganese acetate and polyvinylpyrrolidone mixed solution, dripping quantity is controlled and made the mol ratio of nickel ion and manganese ion is 1:1, after dropwising, after magnetic agitation, standing 25h, centrifugation obtains nickel cyanic acid manganese (MnNi (CN)
4) nano particle; Above-mentioned nickel cyanic acid manganese nano particle is placed in crucible, and under air atmosphere, the temperature lower calcination 1h with 500 ℃, can obtain presoma MnNiO
3;
By lithium hydroxide, above-mentioned precursor MnNiO
3, manganous hydroxide in molar ratio the proportioning of Li:Mn:Ni:Co=1:0.85:0.15 mix, in ball mill, with the speed mechanical of 500r/min, mix 10h and obtain mixed-powder, ratio according to solid, liquid volume ratio 1:4 adds deionized water in described mixed-powder, stirs into thickness slurry.
Described slurry is inserted in a container with opening, make slurry volume account for 1/5 of reactor volume, and pass into the argon gas that volume is 15 times of container volumes, then container is airtight, closed container is put into insulating box, under the constant temperature of 250 ℃, react 10h, obtain nickel adulterated lithium manganate.
Comparative example
By nickel acetate, cobalt acetate, manganese acetate, lithium acetate, be 1/3: 1/3: 1/3 in molar ratio: be dissolved in deionized water at 1: 0, the total concentration of nickel acetate, cobalt acetate, manganese acetate and lithium acetate is 0.4mol/L, after mixing, adding concentration is the aqueous citric acid solution of 0.5mol/L, then to add mass percentage concentration be that to regulate pH value be 10 for 15% ammonia spirit; Described nickel salt, cobalt salt and the total amount of manganese salt and the mol ratio of chelating agent are 1: 1; The mixed solution obtaining is heated with transpiring moisture in the water-bath of 50 ℃, and be 18 hours heating time, and constantly stir, and mixing speed is 200 revs/min, obtains gelinite; Gelinite is dried in air dry oven, and bake out temperature is 80 ℃, and drying time is 30 hours, obtains dry gelinite; Dry gelinite is carried out to pre-burning, and calcined temperature is 200 ℃, and the pre-burning time is 20 hours, obtains presoma; Presoma naturally cools to after room temperature in grinding in ball grinder 0.5 hour, presoma after grinding is calcined at 650 ℃, calcination time is 30 hours, after naturally cooling to room temperature after calcining, again on ball mill, grind 0.5 hour, obtain described polynary positive pole material of lithium ion cell LiNi
1/3co
1/3mn
1/3o
2.
Above-described embodiment one, two and comparative example products therefrom are mixed in mass ratio with conductive carbon black, binding agent PVDF (Kynoar) respectively at 90: 5: 5, be coated on Copper Foil, take metal lithium sheet as to the utmost point, the LiPF that electrolyte is 1mol/L
6solution, solvent is the mixed solvent of EC, DEC and EMC, volume ratio is 1: 1: 1.In the glove box of argon shield, positive pole, negative pole, electrolyte, barrier film and battery case are assembled into button cell.At probe temperature, be at 25 ℃, to carry out electric performance test, this embodiment mono-compares with the product of comparative example with two material after tested, and specific capacity has improved 21-25% first, and bring up to more than 33% useful life.
Claims (1)
1. a preparation method for nickel adulterated lithium manganate positive electrode for lithium ion battery, the chemical formula of this positive electrode is LiMn
1-xni
xo
2, wherein: x=0.12-0.15, the method comprises the steps:
(1) presoma MnNiO
3preparation
By in manganese acetate and the water-soluble and ethanolic solution of polyvinylpyrrolidone, obtain manganese acetate and polyvinylpyrrolidone mixed solution, wherein the molar concentration of manganese acetate is 1-1.5mol/L, and the molar concentration of polyvinylpyrrolidone is 0.5-1mol/L, and the volume ratio of water and ethanol is 3:1-2;
At the temperature of 60-80 ℃, the nickel Zassol (Na that is 1-2mol/L by molar concentration
2ni (CN)
4) aqueous solution, being added drop-wise in above-mentioned manganese acetate and polyvinylpyrrolidone mixed solution, dripping quantity is controlled and made the mol ratio of nickel ion and manganese ion is 1:1, after dropwising, after magnetic agitation, standing 20-25h, centrifugation obtains nickel cyanic acid manganese (MnNi (CN)
4) nano particle;
Above-mentioned nickel cyanic acid manganese nano particle is placed in crucible, and under air atmosphere, the temperature lower calcination 1-2h with 450-500 ℃, can obtain presoma MnNiO
3;
(2) prepare stratiform nickel adulterated lithium manganate
By lithium hydroxide, above-mentioned precursor MnNiO
3, manganous hydroxide in molar ratio the proportioning of Li:Mn:Ni:Co=1:1-x:x mix, in ball mill, with the speed mechanical of 400-500r/min, mix 10-15h and obtain mixed-powder, ratio according to solid, liquid volume ratio 1:2-4 adds deionized water in described mixed-powder, stirs into thickness slurry;
Described slurry is inserted in a container with opening, make slurry volume account for the 1/10-1/5 of reactor volume, and to pass into volume be container volume 10-15 argon gas doubly, then container is airtight, closed container is put into insulating box, under the constant temperature of 150-250 ℃, react 10-15h, obtain nickel adulterated lithium manganate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104393287A (en) * | 2014-12-20 | 2015-03-04 | 刘娜 | Method for preparing porous carbon coated nickel-doped lithium cobalt oxide composite anode material |
| CN105742623A (en) * | 2016-04-07 | 2016-07-06 | 华南师范大学 | Nanometer prismatic lithium-rich material and preparation method and application thereof |
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|---|---|---|---|---|
| US20110143020A1 (en) * | 2007-09-19 | 2011-06-16 | Park Ky-Sung | Cathode and lithium battery including the same |
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| CN104393287A (en) * | 2014-12-20 | 2015-03-04 | 刘娜 | Method for preparing porous carbon coated nickel-doped lithium cobalt oxide composite anode material |
| CN105742623A (en) * | 2016-04-07 | 2016-07-06 | 华南师范大学 | Nanometer prismatic lithium-rich material and preparation method and application thereof |
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| CN103943849B (en) | 2016-05-04 |
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