CN103943849B - The preparation method of nickel adulterated lithium manganate positive electrode for a kind of lithium ion battery - Google Patents
The preparation method of nickel adulterated lithium manganate positive electrode for a kind of lithium ion battery Download PDFInfo
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- CN103943849B CN103943849B CN201410183047.6A CN201410183047A CN103943849B CN 103943849 B CN103943849 B CN 103943849B CN 201410183047 A CN201410183047 A CN 201410183047A CN 103943849 B CN103943849 B CN 103943849B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 22
- 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 17
- 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
- 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
- 239000002002 slurry Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- CCJVDILPJUXPMF-UHFFFAOYSA-N [Mn].N#CO.[Ni] Chemical compound [Mn].N#CO.[Ni] CCJVDILPJUXPMF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 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
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 239000002105 nanoparticle Substances 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 229910016897 MnNi Inorganic materials 0.000 claims abstract description 5
- 238000013019 agitation Methods 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 238000005119 centrifugation Methods 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
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 5
- ZVCDLGYNFYZZOK-UHFFFAOYSA-M sodium cyanate Chemical compound [Na]OC#N ZVCDLGYNFYZZOK-UHFFFAOYSA-M 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 229910016141 LiMn1-x Inorganic materials 0.000 claims abstract description 3
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract 2
- 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
- 239000011572 manganese Substances 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
- 239000007789 gas Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 6
- 239000002243 precursor Substances 0.000 abstract description 4
- 239000002131 composite material Substances 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
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 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
- 229910052748 manganese Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 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
- 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
- 238000002156 mixing Methods 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
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 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
- 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
- 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
- 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
- 238000005516 engineering process 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
- 238000005304 joining Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000002696 manganese Chemical class 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
- 229920000131 polyvinylidene Polymers 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 present invention relates to a kind of preparation method of nickel adulterated lithium manganate positive electrode, the chemical formula of this material is LiMn1-xNixO2, wherein: x=0.12-0.15, the method comprises the steps: (1) preparation manganese acetate and polyvinylpyrrolidone mixed solution; By nickel Zassol (Na2Ni(CN)4) aqueous solution, being added drop-wise in above-mentioned manganese acetate and polyvinylpyrrolidone mixed solution, it is 1:1 that dripping quantity control makes the mol ratio of nickel ion and manganese ion, after dropwising, after magnetic agitation, leave standstill, centrifugation obtains nickel cyanic acid manganese (MnNi (CN)4) nano particle, nano particle calcining is obtained to presoma MnNiO3; (2) by lithium hydroxide, precursor MnNiO3, manganous hydroxide mix, add deionized water, stir into thickness slurry, under the constant temperature of 150-250 DEG C, react, obtain nickel adulterated lithium manganate. Positive electrode prepared by the present invention, the high-purity that uses wet method to prepare has the MnNiO of multi-cellular structure3As primary raw material, in conjunction with low-temperature solid-phase method to obtain the nickel adulterated lithium manganate composite of higher energy density, high conformity.
Description
Affiliated technical field
The present invention relates to the preparation method of a kind of lithium ion battery nickel adulterated lithium manganate positive electrode.
Background technology
Lithium rechargeable battery have high-energy-density, lightweight, free from environmental pollution, memory-less effect, stable work in work,The feature such as safe and reliable has been widely used since coming out, and has become main compact power at present, is also high-power movingThe developing focus of battery.
Stratiform anode material for lithium-ion batteries is the focus of research in field. There is in theory layer structure and spinel structureMaterial, can serve as the positive electrode of lithium ion battery, but due in material self property difference and preparation technologyDifficulty, at present conventional anode material for lithium-ion batteries is still with the oxide LiCoO of cobalt, nickel, manganese2、LiNiO2、LiMnO2Be main. Wherein there is the LiMn2O4 LiMnO of layer structure2Have the following advantages as anode material for lithium-ion batteries tool: 1,Theoretical capacity 285mAh/g, actual capacity can reach 250mAh/g left and right---exceed LiCoO21.5 times; 2, safetyProperty is good; 3, aboundresources, cheap, toxicity is little; Its major defect is but cycle performance is poor, structure in discharge processStable 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 is wantedMore than 700 DEG C, calcination time is long, energy consumption is high, product crystal grain large (micron order), uniformity is poor, and material is initialSpecific discharge capacity is lower, and capacity activation cycle number of times is more; Wet method reaction temperature is low, and grain growth is easily controlled, materialInitial capacity higher.
Summary of the invention
The preparation method who the invention provides a kind of lithium ion battery nickel adulterated lithium manganate positive electrode, uses the method to preparePositive electrode, high conformity, when thering is higher initial capacity, the also good cyclical stability of tool.
To achieve these goals, the preparation side of nickel adulterated lithium manganate positive electrode for a kind of lithium ion battery provided by the inventionMethod, the chemical formula of this positive electrode is LiMn1-xNixO2, wherein: x=0.12-0.15, the method comprises the steps:
(1) presoma MnNiO3Preparation
By in manganese acetate and the water-soluble and ethanolic solution of polyvinylpyrrolidone, obtain manganese acetate and polyvinylpyrrolidone and mixSolution, wherein the molar concentration of manganese acetate is 1-1.5mol/L, the molar concentration of polyvinylpyrrolidone is 0.5-1mol/L,The volume ratio of water and ethanol is 3:1-2;
At the temperature of 60-80 DEG C, the nickel Zassol (Na that is 1-2mol/L by molar concentration2Ni(CN)4) aqueous solution,Be added drop-wise in above-mentioned manganese acetate and polyvinylpyrrolidone mixed solution, dripping quantity control makes rubbing of nickel ion and manganese ionYou,, than being 1:1, after dropwising, after magnetic agitation, leave standstill 20-25h, and centrifugation obtains nickel cyanic acid manganese (MnNi (CN)4)Nano particle;
Above-mentioned nickel cyanic acid manganese nano particle is placed in crucible, under air atmosphere, with the temperature lower calcination of 450-500 DEG C1-2h, can obtain presoma MnNiO3；
(2) prepare stratiform nickel adulterated lithium manganate
By lithium hydroxide, above-mentioned precursor MnNiO3, manganous hydroxide joining of Li:Mn:Ni=1:1-x:x in molar ratioThan mixing, in ball mill, mix 10-15h with the speed mechanical of 400-500r/min and obtain mixed-powder, according to solid, liquidThe ratio of 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, andPass into volume and be container volume 10-15 argon gas doubly, then that container is airtight, closed container is put into insulating box,Under the constant temperature of 150-250 DEG C, react 10-15h, obtain nickel adulterated lithium manganate.
Positive electrode prepared by the present invention, the high-purity that uses wet method to prepare has the MnNiO of multi-cellular structure3As mainlyOne of raw material, in conjunction with solid-phase low-temperature method to obtain the nickel adulterated lithium manganate composite of higher energy density, high conformity,Make this material possess higher energy density and electrochemical stability. Therefore this composite is when for lithium ion battery,There is higher specific capacity and longer service life.
Detailed description of the invention
Embodiment mono-
The chemical formula of positive electrode prepared by the present embodiment is LiMn0.88Ni0.12O2。
By in manganese acetate and the water-soluble and ethanolic solution of polyvinylpyrrolidone, obtain manganese acetate and polyvinylpyrrolidone and mixSolution, wherein the molar concentration of manganese acetate is 1mol/L, the molar concentration of polyvinylpyrrolidone is 0.5mol/L, water andThe volume ratio of ethanol is 3:1;
At the temperature of 60 DEG C, the nickel Zassol (Na that is 1mol/L by molar concentration2Ni(CN)4) aqueous solution, dripIn above-mentioned manganese acetate and polyvinylpyrrolidone mixed solution, dripping quantity control makes the mol ratio of nickel ion and manganese ionFor 1:1, after dropwising, after magnetic agitation, leave standstill 20h, centrifugation obtains nickel cyanic acid manganese (MnNi (CN)4) nanoparticleSon; Above-mentioned nickel cyanic acid manganese nano particle is placed in crucible, under air atmosphere, with the temperature lower calcination 2h of 450 DEG C,Can obtain presoma MnNiO3；
By lithium hydroxide, above-mentioned precursor MnNiO3, manganous hydroxide Li:Mn:Ni=1:0.88:0.12 in molar ratioProportioning mix, in ball mill, mix 15h with the speed mechanical of 400r/min and obtain mixed-powder, according to solid, liquid bodyAmass and in described mixed-powder, add deionized water than the ratio of 1:2, stir into thickness slurry.
Described slurry is inserted in a container with opening, make slurry volume account for 1/10 of reactor volume, and pass intoVolume is the argon gas of 10 times of container volumes, then that container is airtight, closed container is put into insulating box, at 150 DEG CConstant temperature under react 15h, obtain nickel adulterated lithium manganate.
Embodiment bis-
The chemical formula of positive electrode prepared by the present embodiment is LiMn0.85Ni0.15O2。
By in manganese acetate and the water-soluble and ethanolic solution of polyvinylpyrrolidone, obtain manganese acetate and polyvinylpyrrolidone and mixSolution, wherein the molar concentration of manganese acetate is 1.5mol/L, the molar concentration of polyvinylpyrrolidone is 1mol/L, water andThe volume ratio of ethanol is 3:2;
At the temperature of 80 DEG C, the nickel Zassol (Na that is 2mol/L by molar concentration2Ni(CN)4) aqueous solution, dripIn above-mentioned manganese acetate and polyvinylpyrrolidone mixed solution, dripping quantity control makes the mol ratio of nickel ion and manganese ionFor 1:1, after dropwising, after magnetic agitation, leave standstill 25h, centrifugation obtains nickel cyanic acid manganese (MnNi (CN)4) nanoparticleSon; Above-mentioned nickel cyanic acid manganese nano particle is placed in crucible, under air atmosphere, with the temperature lower calcination 1h of 500 DEG C,Can obtain presoma MnNiO3；
By lithium hydroxide, above-mentioned precursor MnNiO3, manganous hydroxide Li:Mn:Ni=1:0.85:0.15 in molar ratioProportioning mix, in ball mill, mix 10h with the speed mechanical of 500r/min and obtain mixed-powder, according to solid, liquid bodyAmass and in described mixed-powder, add deionized water than the ratio of 1:4, stir into thickness slurry.
Described slurry is inserted in a container with opening, make slurry volume account for 1/5 of reactor volume, and pass intoVolume is the argon gas of 15 times of container volumes, then that container is airtight, closed container is put into insulating box, at 250 DEG CConstant temperature under react 10h, obtain nickel adulterated lithium manganate.
Comparative example
Be 1/3: 1/3: 1/3 in molar ratio by nickel acetate, cobalt acetate, manganese acetate, lithium acetate: be dissolved in deionized water at 1: 0In, the total concentration of nickel acetate, cobalt acetate, manganese acetate and lithium acetate is 0.4mol/L, adds concentration to be after mixingThe 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; InstituteStating nickel salt, cobalt salt and the total amount of manganese salt and the mol ratio of chelating agent is 1: 1; By the mixed solution obtaining in the water of 50 DEG CIn bath, heating is with transpiring moisture, and the heat time is 18 hours, and constantly stirs, and mixing speed is 200 revs/min, obtainsGelinite; Gelinite is dried in air dry oven, and bake out temperature is 80 DEG C, and drying time is 30 hours, obtainsDry gelinite; Dry gelinite is carried out to pre-burning, and calcined temperature is 200 DEG C, and the pre-burning time is 20 hours,To presoma; Presoma naturally cools to after room temperature in grinding in ball grinder 0.5 hour, by the presoma after grinding at 650 DEG CUnder calcine, calcination time is 30 hours, after calcining, naturally cool to again on ball mill, grind after room temperature 0.5 littleTime, obtain described polynary positive pole material of lithium ion cell LiNi1/3Co1/3Mn1/3O2。
By above-described embodiment one, two and comparative example products therefrom respectively with conductive carbon black, binding agent PVDF (polyvinylidene fluorideAlkene) mix at 90: 5: 5 in mass ratio, be coated on Copper Foil, taking metal lithium sheet as to the utmost point, the LiPF that electrolyte is 1mol/L6Solution, solvent is the mixed solvent of EC, DEC and EMC, volume ratio is 1: 1: 1. At the glove box of argon shieldInterior positive pole, negative pole, electrolyte, barrier film and battery case are assembled into button cell. Be to carry out at 25 DEG C at probe temperatureElectric performance test, compared with the product of this embodiment mono-and two material and comparative example, specific capacity has improved first after tested21-25%, bring up to more than 33% service 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 LiMn1-xNixO2, wherein: x=0.12-0.15, the method comprises the steps:
(1) presoma MnNiO3Preparation
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 DEG C, the nickel Zassol (Na that is 1-2mol/L by molar concentration2Ni(CN)4) aqueous solution, being added drop-wise in above-mentioned manganese acetate and polyvinylpyrrolidone mixed solution, it is 1:1 that dripping quantity control makes the mol ratio of nickel ion and manganese ion, after dropwising, after magnetic agitation, leave standstill 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, under air atmosphere, with the temperature lower calcination 1-2h of 450-500 DEG C, can obtains presoma MnNiO3；
(2) prepare stratiform nickel adulterated lithium manganate
By lithium hydroxide, above-mentioned presoma MnNiO3, manganous hydroxide in molar ratio Li:Mn:Ni=1:1-x:x proportioning mix, in ball mill, mix 10-15h with the speed mechanical of 400-500r/min 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 DEG C, react 10-15h, obtain nickel adulterated lithium manganate.
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| CN102354741A (en) * | 2011-09-09 | 2012-02-15 | 中国科学院宁波材料技术与工程研究所 | Preparation method of high-capacity layered lithium-rich manganese-based oxide |
| CN102437324A (en) * | 2011-12-12 | 2012-05-02 | 中国科学技术大学 | Preparation method of cobalt-manganese composite oxide nanoparticles and cobalt-manganese composite oxide nanoparticles prepared by adopting same |
| CN102544473A (en) * | 2012-02-29 | 2012-07-04 | 河南理工大学 | Lithium ion battery anode material layered lithium manganese oxide and manufacturing method thereof |
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