CN108083342B - Lithium-ion-power cell manganate cathode material for lithium and preparation method thereof - Google Patents
Lithium-ion-power cell manganate cathode material for lithium and preparation method thereof Download PDFInfo
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- CN108083342B CN108083342B CN201711049403.5A CN201711049403A CN108083342B CN 108083342 B CN108083342 B CN 108083342B CN 201711049403 A CN201711049403 A CN 201711049403A CN 108083342 B CN108083342 B CN 108083342B
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 77
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000010406 cathode material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 122
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 90
- 239000011572 manganese Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000000725 suspension Substances 0.000 claims abstract description 20
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000009938 salting Methods 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 7
- 238000013019 agitation Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 21
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 15
- 238000010792 warming Methods 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 11
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 11
- 229940099596 manganese sulfate Drugs 0.000 claims description 8
- 239000011702 manganese sulphate Substances 0.000 claims description 8
- 235000007079 manganese sulphate Nutrition 0.000 claims description 8
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- -1 metals Ion Chemical class 0.000 claims description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 150000002696 manganese Chemical class 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 2
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 239000002243 precursor Substances 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 31
- 239000011259 mixed solution Substances 0.000 description 24
- 230000014759 maintenance of location Effects 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000007547 defect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000005536 Jahn Teller effect Effects 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007873 sieving Methods 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
- C01G51/44—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese
- C01G51/54—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese of the type [Mn2O4]-, e.g. Li(CoxMn2-x)04, Li(MyCoxMn2-x-y)O4
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/02—Particle morphology depicted by an image obtained by optical microscopy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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 kind of preparation method of lithium-ion-power cell manganate cathode material for lithium and lithium-ion-power cell manganate cathode material for lithium obtained by this method, preparation method the following steps are included: (1) under agitation, sodium hydroxide solution and the soluble manganese salting liquid containing doped metal ion are added dropwise in electrolytic manganese dioxide suspension simultaneously, it is passed through air while dropwise addition and carries out oxidation reaction, generates spherical dopping manganese dioxide；(2) it is sintered after mixing the resulting spherical dopping manganese dioxide of step (1) and lithium source, crushes, obtain spherical lithium manganate doped presoma；(3) the resulting spherical lithium manganate doped presoma of step (2) is roasted under oxidizing atmosphere, crushes, obtains lithium-ion-power cell manganate cathode material for lithium.Obtained lithium-ion-power cell manganate cathode material for lithium has many advantages, such as high-temperature behavior and storage performance is excellent, stable structure, specific surface area are small, at low cost.
Description
Technical field
The invention belongs to electrochemical power source technical field of material more particularly to a kind of lithium-ion-power cell mangaic acids
Lithium anode material and preparation method thereof.
Background technique
Compared with other anode material for lithium-ion batteries, spinel-type LiMn2O4, synthesis abundant, at low cost with promoter manganese
Simple process, thermal stability are high, overcharge resistance performance is good, discharge voltage plateau is high, security performance is excellent and it is environmentally friendly the advantages that.
But it is especially the disadvantages of capacity attenuation is fast, high-temperature storage performance is poor under high temperature (55 DEG C) due to there is room temperature, seriously
Constrain its application of power lithium-ion battery high-end field and its be considered as low side positive electrode be mainly used in it is low
The main reason for holding in lithium ion battery, it is therefore desirable to which emphasis improves the high temperature cyclic performance of LiMn2O4, so that it meets power
The application requirement of lithium ion battery.
Currently, the preparation of LiMn2O4 mostly uses cheap electrolytic manganese dioxide for raw material, with lithium carbonate through solid phase mixing
Pyroreaction is carried out according to specific program after uniformly, LiMn2O4 product is obtained after pulverizing and sieving.Due to electrolytic manganese dioxide
Special producing process conditions determined, SO therein4 2-Content is high, and particle surface is irregular after crushed for manganese dioxide piece, and
The LiMn2O4 product granularity of broad particle distribution, large specific surface area, production is uneven, and surface is irregular, and LiMn2O4 is caused easily to exist
It is dissolved under the action of acidic electrolysis bath, influences the high temperature cyclic performance of product, even if electrolytic manganese dioxide passes through stringent crushing
Grading control program also can only slightly improve the normal-temperature circulating performance of LiMn2O4, and the circulation of product can only achieve 500-800 times,
It is unable to satisfy the production requirement of dynamic lithium manganate.
Lead to spinelle LiMn2O4The reason of high temperature cyclic performance difference mainly has following four aspect:
(1) dissolution of manganese: on the one hand it is that LiMn2O4 directly dissolves under the action of an acid, is on the other hand in charge and discharge process
The Mn of middle LiMn2O43+Disproportionated reaction occurs under acidic electrolyte bath effect, makes Mn2+It is slowly dissolved into faintly acid electrolyte；
(2) Jahn-Teller effect: regular octahedron gap changes when LiMn2O4 deep discharge, tetragonal distortion occurs,
The tetragonal phase Li of stability difference is formed in charge and discharge process in electrode surface2Mn2O4。
(3) oxygen defect: can occur capacity attenuation simultaneously in 4.0V and 4.2V platform when LiMn2O4 anoxic, and the defect of oxygen is got over
More, the capacity attenuation of battery is faster.The key between metallic atom and oxygen atom can also be weakened in the defect of oxygen in spinel structure
Can, cause the dissolution of manganese to aggravate.Cause the factor of oxygen defect mainly from two aspect: 1) under hot conditions LiMn2O4 to electrolysis
Liquid has certain catalysed oxidn, dissolution itself loses oxygen；2) synthesis condition causes in LiMn2O4 oxygen relative to standard chemical
Stoichiometric number is insufficient.
(4) electrolyte itself is unstable: in charge and discharge, electrolyte solution is easy to appear wild effect in higher-pressure region.
To solve the above-mentioned problems, a large amount of research work is dedicated to spinelle LiMn2O4Bulk phase-doped and surface is modified
And the improvement of synthesis technology is made with improving the structural stability and its stability in the electrolytic solution of material itself by doping
LiMn2O4 structure becomes stable, and by surface modification, improves the pattern of manganese dioxide, reduces specific surface area, reduces mangaic acid
Lithium and acidic electrolyte bath dissolve reaction speed.
The production of current driving force type LiMn2O4 substantially has following several method:
First is that electrolytic manganese dioxide (EMD)+excess lithium carbonate (Li2CO3) process route, it is mentioned by excessive addition lithium
High material electrochemical cycle performance and improve certain high-temperature behavior.It is wide at home at present due to simple process and at low cost
General use.But this method is limited to the high temperature cyclic performance increase rate of LiMn2O4, and the pattern of product is by EMD pattern itself
Influence it is very big.
Second is that using oxide of high activity manganese+doped chemical+excess Li2CO3The use of process route, oxide of high activity manganese can
The modification for realizing product section, the solid phase doping vario-property of higher level is realized in technical process, high-temperature behavior is made to have one
The promotion of tentering degree.However, solid phase doping cannot achieve modifying element and be uniformly mixed with Mn height.Here it is solid phase doping process
The defect of itself, i.e. doped chemical are difficult to uniformly mix with Mn, influence to adulterate effect, also influence subsequent high temperature synthesis technology, hold
Material anoxic is easily led to, to influence the chemical property of material, and leads to production cost using other oxide of high activity manganese
It increases.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art, a kind of high-temperature behavior and storage performance are provided
Excellent, stable structure, specific surface area be small, lithium-ion-power cell manganate cathode material for lithium at low cost and preparation method thereof.
In order to solve the above technical problems, the invention adopts the following technical scheme:
A kind of preparation method of lithium-ion-power cell manganate cathode material for lithium, comprising the following steps:
(1) electrolytic manganese dioxide is dispersed in water, obtains electrolytic manganese dioxide suspension；Under agitation, by hydrogen
Sodium hydroxide solution and soluble manganese salting liquid containing doped metal ion are added dropwise in the electrolytic manganese dioxide suspension simultaneously,
It is passed through air while dropwise addition and carries out oxidation reaction, generates spherical dopping manganese dioxide；
(2) it is sintered after mixing the resulting spherical dopping manganese dioxide of step (1) and lithium source, crushes, obtain spherical shape
Adulterated lithium manganate presoma；
(3) the resulting spherical lithium manganate doped presoma of step (2) is roasted under oxidizing atmosphere, crush, obtain lithium from
Sub- power battery manganate cathode material for lithium.
The present invention, using manganese salt and doped chemical as auxiliary material, is controlled using electrolytic manganese dioxide as main material by solution
Crystallisation prepares high-density spherical dopping manganese dioxide, and then with high-temperature oxygen-enriched SINTERING TECHNOLOGY, it is dynamic to prepare high circulation
Power type manganate cathode material for lithium, chemical equation are as follows:
Wherein, the chemical reaction in oxidation reaction are as follows:
2Mn2++4OH-+O2=2MnO2+2H2O
Ma++aOH-=M (OH)a；
Chemical reaction in sintering process are as follows:
w/2Li2CO3+(2-x)MnO2+xM(OH)a=LiwMn2-xMxO4+w/2CO2+ax/2H2O+(w+ax-4x)/4O2, or
wLiOH+(2-x)MnO2+xM(OH)a=LiwMn(2-x)MxO4+(w+ax)/2H2O+(w+ax-4x)/4O2。
In above-mentioned chemical reaction, the doped metallic elements such as M Al, Cr, Mg, Co, a is the coordination of doped metallic elements
Number；W, x is respectively mole value of Li and doped metallic elements M.
The preparation method of above-mentioned lithium-ion-power cell manganate cathode material for lithium, it is preferred that in the step (1),
In the soluble manganese salting liquid containing doped metal ion, Mn2+Concentration is 0.2~1.0mol/L, and Doped ions concentration is 0.1
~0.5mol/L；The concentration of sodium hydroxide is 0.5~2.0mol/L in sodium hydroxide solution；It is electric in electrolytic manganese dioxide suspension
The concentration for solving manganese dioxide is 100~300g/L, and the partial size of electrolytic manganese dioxide is 5~7 μm.
The preparation method of above-mentioned lithium-ion-power cell manganate cathode material for lithium, it is preferred that in the step (1),
The solubility manganese salt is one of manganese chloride, manganese sulfate, manganese nitrate or a variety of, and the doped metal ion is Al3+、Cr3 +、 Mg2+、Co2+One of or it is a variety of, the corresponding soluble-salt of the doped metal ion is chloride, sulfate or nitric acid
One of salt is a variety of.
The preparation method of above-mentioned lithium-ion-power cell manganate cathode material for lithium, it is preferred that in the step (1),
The flow for being passed through air is 0.1~0.5M3/ h, the drop rate of the soluble manganese salting liquid containing doped metal ion is 0.9~
6.0mL/min, the drop rate of sodium hydroxide solution are 1.8~7.0mL/min；In oxidation reaction, system pH is 7~10,
Reaction temperature is 10~90 DEG C, and the charging reaction time is 10~20h, the reaction was continued after the completion of charging 2h.
The preparation method of above-mentioned lithium-ion-power cell manganate cathode material for lithium, it is preferred that in the step (2),
The mol ratio of Li in the lithium source and Mn in spherical dopping manganese dioxide is Li/Mn=0.53~0.6: 1.
The preparation method of above-mentioned lithium-ion-power cell manganate cathode material for lithium, it is preferred that the lithium source is hydrogen-oxygen
Change lithium or lithium carbonate, the lithium hydroxide is LITHIUM BATTERY lithium hydroxide, and the lithium carbonate is battery-level lithium carbonate.
The preparation method of above-mentioned lithium-ion-power cell manganate cathode material for lithium, it is preferred that in the step (2),
The sintering detailed process are as follows: be warming up to 400~600 DEG C with the rate of 1~5 DEG C/min, be sintered 5~10h, then with 1~5 DEG C/
The rate of min is cooled to 300 DEG C, cools to room temperature with the furnace.
The preparation method of above-mentioned lithium-ion-power cell manganate cathode material for lithium, it is preferred that in the step (3),
The detailed process of the roasting are as follows: be warming up to 800~900 DEG C with the rate of 1~5 DEG C/min, roast 10~20h, then with 1~5
DEG C/rate of min is cooled to 300 DEG C, cool to room temperature with the furnace.
The preparation method of above-mentioned lithium-ion-power cell manganate cathode material for lithium, it is preferred that in the step (3),
The oxidizing atmosphere is 0.5~2.5M to be passed through flow3The air of/h is passed through flow as 0.1~0.5M3The oxygen of/h.
The inventive concept total as one, the present invention also provides lithium ion powers obtained by a kind of above-mentioned preparation method
Battery manganate cathode material for lithium, average grain diameter are 6~8 μm, and tap density is greater than 2.2g/cm3, sulfate radical content is less than
0.04%, pattern is regular spherical.
Compared with the prior art, the advantages of the present invention are as follows:
1, the present invention, by solution crystal process, by sodium hydroxide solution and contains using cheap electrolytic manganese dioxide as raw material
The soluble manganese salting liquid of doped metal ion is added dropwise in electrolytic manganese dioxide suspension, and blowing air oxidation makes newly-generated
The hydroxide of manganese dioxide and doped metal ion is uniformly adhered in the gap of electrolytic manganese dioxide or rough
Surface has reached the dual purpose of doping and surface modification, had both overcome prior art solid phase mixing and has adulterated non-uniform defect,
The stability of product crystal structure is effectively improved, Jahn-Teller effect is inhibited, reduces manganese dissolution, high density of having got back shape
The spherical manganese dioxide of looks rule, reduces product specific surface area and sulfate radical content.By spherical dopping manganese dioxide and lithium source
Mixing, has finally obtained spherical doping dynamic lithium manganate product by high-temperature oxygen-enriched SINTERING TECHNOLOGY, because of the sulfuric acid of product
Radical content is low, and BET is smaller, is made into after battery and substantially reduces with the contact area of electrolyte, is obtained effectively by acid dissolution speed
Control, the addition of doped chemical keep product crystalline structure more stable, improve the high temperature cyclic performance of LiMn2O4.
Detailed description of the invention
Fig. 1 is the SEM figure of lithium-ion-power cell manganate cathode material for lithium made from the embodiment of the present invention 1.
Fig. 2 is the CR2025 type button electricity prepared using the lithium-ion-power cell manganate cathode material for lithium of embodiment 1
Pond is 2.8-4.5V in charging/discharging voltage, and charge-discharge magnification is room temperature (25 DEG C) cyclic curve under conditions of 0.5C.
Fig. 3 is the CR2025 type button electricity prepared using the lithium-ion-power cell manganate cathode material for lithium of embodiment 1
Pond is 2.8-4.5V in charging/discharging voltage, and charge-discharge magnification is room temperature (25 DEG C) cyclic curve under conditions of 1C.
Fig. 4 is the SEM figure of lithium-ion-power cell manganate cathode material for lithium made from the embodiment of the present invention 2.
Specific embodiment
Below in conjunction with Figure of description and specific preferred embodiment, the invention will be further described, but not therefore and
It limits the scope of the invention.
Embodiment 1:
A kind of preparation method of lithium-ion-power cell manganate cathode material for lithium of the invention, comprising the following steps:
(1) being dissolved in deionized water to be configured to 2L manganese sulfate concentration by manganese sulfate and aluminum sulfate is that 0.5mol/L and aluminum sulfate are dense
Degree is the mixed solution of 0.15mol/L, filters to obtain pure mixed solution.Solid sodium hydroxide is configured to 3.8L with deionized water
Concentration is the sodium hydroxide solution of 1.0mol/L, filters to obtain purified solution.
(2) electrolytic manganese dioxide that 1000g average grain diameter is 5.2 μm is tuned into 200g/L suspension with water, in stirring bar
The resulting mixed solution of step (1) and sodium hydroxide solution are added drop-wise in manganese dioxide suspension under part, mixed solution and hydrogen
Sodium hydroxide solution drop rate is respectively 2.1mL/min, 4.0mL/min, and keeping pH value of reaction system is 7~10, is passed through simultaneously
Air, air mass flow 0.25M3/ h is kept for 80 DEG C of reaction temperature, feed time 6 hours, adds the subsequent continuous insulation reaction 2 of material
Hour, it is filtered, washed after the reaction was completed, obtains spherical dopping manganese dioxide.
(3) lithium carbonate is added by Li/Mn=0.55: 1 ratio in the obtained spherical dopping manganese dioxide of step (2), sufficiently
Be warming up to 400 DEG C according to 2 DEG C/min of heating rate after evenly mixing and be sintered 7 hours, then according still further to 2 DEG C of rate of temperature fall/
After min drops to 300 DEG C, room temperature is cooled to the furnace, by crushed 200 meshes, prepare with spherical, individual particle, micron
The adulterated lithium manganate presoma of grade external appearance characteristic.
(4) by adulterated lithium manganate presoma obtained by step (3) in oxidizing atmosphere (air mass flow 0.5M3/ h) under according to heating
2 DEG C/min of rate is warming up to 850 DEG C and carries out roasting 20 hours, after then dropping to 300 DEG C according still further to 2 DEG C/min of rate of temperature fall, with
Furnace is cooled to room temperature, and by crushed 200 meshes, obtains lithium-ion-power cell manganate cathode material for lithium.
Lithium-ion-power cell manganate cathode material for lithium average grain diameter made from the present embodiment is 6.8 μm, tap density
2.21g/cm3, sulfate radical content 0.034%, microscopic appearance is as shown in Figure 1, be regular spherical as seen from the figure, granular size is equal
It is even, and surface is regular.
The electrochemical property test of lithium-ion-power cell manganate cathode material for lithium made from the present embodiment is as follows:
The manganate cathode material for lithium and acetylene black, graphite, binder (PVDF) in mass ratio 80: 5: 5: 10 prepared
Above-mentioned material stirring pulp is coated on aluminium foil, then with n-methyl-2-pyrrolidone (NMP) for solvent at 120 DEG C by mixing
Drying obtains pole piece for 24 hours in vacuum oven.Using the above-mentioned pole piece prepared as anode, lithium piece is as cathode, Celgard
2400 be diaphragm, and (volume ratio 1: 1) EC+DMC is electrolyte, is assembled into the glove box full of argon gas 1mol/L LiPF6
CR2025 type button cell carries out electrochemical property test to material.Using LAND battery test system, battery is in 2.8-
It is activated under 4.5V, 0.1C, is then recycled at 2.8-4.5V, 0.5C, 1C.
The CR2025 type button cell prepared with the lithium-ion-power cell of the present embodiment with manganate cathode material for lithium, is filling
Discharge voltage is 2.8-4.5V, under conditions of charge-discharge magnification is 0.5C, as shown in Fig. 2, the first discharge specific capacity of the battery
For 102mAh/g, capacity retention ratio that circulation is 3000 times is up to 80.3% or more.Under conditions of charge-discharge magnification is 1C, such as Fig. 3
Shown, the first discharge specific capacity of the battery is 97mAh/g, and the capacity retention ratio that circulation is 2500 times is up to 80.5% or more.
Embodiment 2:
A kind of preparation method of lithium-ion-power cell manganate cathode material for lithium of the invention, comprising the following steps:
(1) manganese nitrate and cobaltous sulfate are dissolved in pure water and are configured to 5L manganese nitrate concentration as 0.2mol/L and cobalt sulfate concentration
The mixed solution of 0.1mol/L filters to obtain pure mixed solution.Solid sodium hydroxide, which is configured to 6L concentration with pure water, is
The sodium hydroxide solution of 0.5mol/L filters to obtain purified solution.
(2) electrolytic manganese dioxide that 1000g average grain diameter is 7.0 μm is tuned into 100g/L suspension with water, in stirring bar
The resulting mixed solution of step (1) and sodium hydroxide solution are added drop-wise in electrolytic manganese dioxide suspension under part, mixed solution
It is respectively 5.6mL/min, 6.7mL/min with sodium hydroxide solution drop rate, keeping pH value of reaction system is 7~10, simultaneously
It is passed through air, air mass flow 0.5M3/ h is kept for 10 DEG C of reaction temperature, feed time 15 hours, it is anti-to add the subsequent continuation of insurance temperature of material
It answers 2 hours, is filtered, washed after the reaction was completed, obtain spherical dopping manganese dioxide.
(3) lithium carbonate is added by Li/Mn=0.6: 1 ratio in the obtained spherical dopping manganese dioxide of step (2), sufficiently
It is warming up to 500 DEG C according to 1 DEG C/min of heating rate after even mixing to be sintered 5 hours, then according still further to 1 DEG C/min of rate of temperature fall
After dropping to 300 DEG C, room temperature is cooled to the furnace, by crushed 200 meshes, prepare outside with spherical, individual particle, micron order
See the adulterated lithium manganate presoma of feature.
(4) by adulterated lithium manganate presoma obtained by step (3) in oxidizing atmosphere (air mass flow 1.5M3/ h) under according to heating
1 DEG C/min of rate is warming up to 800 DEG C and carries out roasting 15 hours, after then dropping to 300 DEG C according still further to 1 DEG C/min of rate of temperature fall, with
Furnace is cooled to room temperature, and by crushed 200 meshes, obtains lithium-ion-power cell manganate cathode material for lithium.
Lithium-ion-power cell manganate cathode material for lithium average grain diameter made from the present embodiment is 7.2 μm, tap density
2.24g/cm3, sulfate radical content 0.037%, microscopic appearance is as shown in figure 4, be regular spherical as seen from the figure, granular size is equal
It is even, and surface is regular.
By the lithium-ion-power cell of the present embodiment with manganate cathode material for lithium prepare CR2025 type button cell, method with
Embodiment 1 is identical, is 2.8-4.5V in charging/discharging voltage, under conditions of charge-discharge magnification is 0.5C, the electric discharge for the first time of the battery
Specific capacity is 100mAh/g, and the capacity retention ratio that circulation is 3000 times is up to 80.2% or more.Under conditions of charge-discharge magnification is 1C,
The first discharge specific capacity of the battery is 95mAh/g, and the capacity retention ratio that circulation is 2500 times is up to 80.1% or more.
Embodiment 3:
A kind of preparation method of lithium-ion-power cell manganate cathode material for lithium of the invention, comprising the following steps:
(1) manganese chloride, magnesium sulfate and cobaltous sulfate are dissolved in deionized water and are configured to 2.5L manganese chloride concentration as 0.4mol/
L, the mixed solution that magnesium sulfate concentration is 0.1mol/L, cobalt sulfate concentration is 0.1mol/L filters to obtain pure mixed solution.By hydrogen
Sodium oxide molybdena is configured to the sodium hydroxide solution that 5L concentration is 0.6mol/L with deionized water, filters to obtain purified solution.
(2) electrolytic manganese dioxide that 1000g average grain diameter is 5.8 μm is tuned into 300g/L suspension with water, in stirring bar
The resulting mixed solution of step (1) and sodium hydroxide solution are added drop-wise in manganese dioxide suspension under part, mixed solution and hydrogen
Sodium hydroxide solution drop rate is respectively 3.5mL/min, 6.9mL/min, and keeping pH value of reaction system is 7~10, is passed through simultaneously
Air, air mass flow 0.35M3/ h is kept for 70 DEG C of reaction temperature, feed time 12 hours, adds the subsequent continuous insulation reaction 2 of material
Hour, it is filtered, washed after the reaction was completed, obtains spherical dopping manganese dioxide.
(3) lithium hydroxide is added by Li/Mn=0.58: 1 ratio in the obtained spherical dopping manganese dioxide of step (2), filled
Point being warming up to 450 DEG C according to 3 DEG C/min of heating rate after evenly mixing is sintered 10 hours, then according still further to rate of temperature fall 3
DEG C/after min drops to 300 DEG C, cool to room temperature with the furnace, by crushed 200 meshes, prepare with spherical, individual particle,
The adulterated lithium manganate presoma of micron order external appearance characteristic.
(4) by adulterated lithium manganate presoma obtained by step (3) in oxidizing atmosphere (oxygen flow 0.5M3/ h) under according to heating
3 DEG C/min of rate is warming up to 840 DEG C and carries out roasting 10 hours, after then dropping to 300 DEG C according still further to 3 DEG C/min of rate of temperature fall, with
Furnace is cooled to room temperature, and by crushed 200 meshes, obtains lithium-ion-power cell manganate cathode material for lithium.
Lithium-ion-power cell manganate cathode material for lithium average grain diameter made from the present embodiment is 7.5 μm, tap density
2.28g/cm3, sulfate radical content 0.032%, pattern is regular spherical.
By the lithium-ion-power cell of the present embodiment with manganate cathode material for lithium prepare CR2025 type button cell, method with
Embodiment 1 is identical, is 2.8-4.5V in charging/discharging voltage, under conditions of charge-discharge magnification is 0.5C, the electric discharge for the first time of the material
Specific capacity is 101mAh/g, and the capacity retention ratio that circulation is 3000 times is up to 80.2%.Under conditions of charge-discharge magnification is 1C, the material
The first discharge specific capacity of material is 97mAh/g, and the capacity retention ratio that circulation is 2500 times is up to 80.0%.
Embodiment 4:
A kind of preparation method of lithium-ion-power cell manganate cathode material for lithium of the invention, comprising the following steps:
(1) by manganese sulfate be dissolved in pure water or deionized water be configured to manganese sulfate that 1.2L concentration is 0.8mol/L and
The chromium chloride mixed solution of 0.4mol/L filters to obtain pure mixed solution.Sodium hydroxide is configured to pure water or deionized water
1.68L concentration is the sodium hydroxide solution of 2.0mol/L, filters to obtain purified solution.
(2) electrolytic manganese dioxide that 1000g average grain diameter is 5.0 μm is tuned into 250g/L suspension with water, in stirring bar
The resulting mixed solution of step (1) and sodium hydroxide solution are added drop-wise in manganese dioxide suspension under part, mixed solution and hydrogen
Sodium hydroxide solution drop rate is respectively 2.0mL/min, 2.8mL/min, and keeping pH value of reaction system is 7~10, is passed through simultaneously
Air, air mass flow 0.4M3/ h is kept for 60 DEG C of reaction temperature, feed time 10 hours, adds the subsequent continuous insulation reaction 2 of material
Hour, it is filtered, washed after the reaction was completed, obtains spherical dopping manganese dioxide.
(3) lithium hydroxide is added by Li/Mn=0.56: 1 ratio in the obtained spherical dopping manganese dioxide of step (2), filled
Point being warming up to 550 DEG C according to 4 DEG C/min of heating rate after evenly mixing is sintered 8 hours, then according still further to 5 DEG C of rate of temperature fall
After/min drops to 300 DEG C, room temperature is cooled to the furnace, by crushed 200 meshes, prepare with spherical, individual particle, micron
The adulterated lithium manganate presoma of grade external appearance characteristic.
(4) the resulting adulterated lithium manganate presoma of step (3) is heated up under oxidizing atmosphere according to 5 DEG C/min of heating rate
Roasting 12 hours, oxygen flow 0.1M are carried out to 880 DEG C3Then/h drops to 300 DEG C according still further to 5 DEG C/min of rate of temperature fall after, with
Furnace is cooled to room temperature, and by crushed 200 meshes, obtains lithium-ion-power cell manganate cathode material for lithium.
Lithium-ion-power cell manganate cathode material for lithium average grain diameter made from the present embodiment is 8.0 μm, tap density
2.24g/cm3, sulfate radical content 0.04%, pattern is regular spherical.
By the lithium-ion-power cell of the present embodiment with manganate cathode material for lithium prepare CR2025 type button cell, method with
Embodiment 1 is identical, is 2.8-4.5V in charging/discharging voltage, under conditions of charge-discharge magnification is 0.5C, the electric discharge for the first time of the material
Specific capacity is 102mAh/g, and the capacity retention ratio that circulation is 3000 times is up to 80.5%.Under conditions of charge-discharge magnification is 1C, the material
The first discharge specific capacity of material is 96mAh/g, and the capacity retention ratio that circulation is 2500 times is up to 80.1%.
Embodiment 5:
A kind of preparation method of lithium-ion-power cell manganate cathode material for lithium of the invention, comprising the following steps:
(1) being dissolved in deionized water to be configured to 1.6L manganese sulfate concentration by manganese sulfate and aluminium chloride is 0.6mol/L and aluminium chloride
For the mixed solution of 0.3mol/L, pure mixed solution is filtered to obtain.Sodium hydroxide is configured to 2.24L concentration with deionized water
For the sodium hydroxide solution of 1.5mol/L, purified solution is filtered to obtain.
(2) electrolytic manganese dioxide that 1000g average grain diameter is 5.5 μm is tuned into 150g/L suspension with water, in stirring bar
The resulting mixed solution of step (1) and sodium hydroxide solution are added drop-wise in electrolytic manganese dioxide suspension under part, mixed solution
It is respectively 1.3mL/min, 1.9mL/min with sodium hydroxide solution drop rate, keeping pH value of reaction system is 7~10, simultaneously
It is passed through air, air mass flow 0.3M3/ h is kept for 90 DEG C of reaction temperature, feed time 20 hours, it is anti-to add the subsequent continuation of insurance temperature of material
It answers 2 hours, is filtered, washed after the reaction was completed, obtain spherical dopping manganese dioxide.
(3) lithium carbonate is added by Li/Mn=0.59: 1 ratio in the obtained spherical dopping manganese dioxide of step (2), sufficiently
Be warming up to 600 DEG C according to 2 DEG C/min of heating rate after evenly mixing and be sintered 6 hours, then according still further to 2 DEG C of rate of temperature fall/
After min drops to 300 DEG C, room temperature is cooled to the furnace, by crushed 200 meshes, prepare with spherical, individual particle, micron
The adulterated lithium manganate presoma of grade external appearance characteristic.
(4) by adulterated lithium manganate presoma obtained by step (3) in oxidizing atmosphere (oxygen flow 0.3M3/ h) under according to heating
2 DEG C/min of rate is warming up to 900 DEG C and carries out roasting 17 hours, after then dropping to 300 DEG C according still further to 2 DEG C/min of rate of temperature fall, with
Furnace is cooled to room temperature, and by crushed 200 meshes, obtains lithium-ion-power cell manganate cathode material for lithium.
Lithium-ion-power cell manganate cathode material for lithium average grain diameter made from the present embodiment is 6.5 μm, tap density
2.20g/cm3, sulfate radical content 0.035%, pattern is regular spherical.
By the lithium-ion-power cell of the present embodiment with manganate cathode material for lithium prepare CR2025 type button cell, method with
Embodiment 1 is identical, is 2.8-4.5V in charging/discharging voltage, under conditions of charge-discharge magnification is 0.5C, the electric discharge for the first time of the battery
Specific capacity is 102mAh/g, and the capacity retention ratio that circulation is 3000 times is up to 80.0%.Under conditions of charge-discharge magnification is 1C, the electricity
The first discharge specific capacity in pond is 95mAh/g, and the capacity retention ratio that circulation is 2500 times is up to 80.2%.
Embodiment 6:
A kind of preparation method of lithium-ion-power cell manganate cathode material for lithium of the invention, comprising the following steps:
(1) manganese nitrate and magnesium sulfate are dissolved in pure water be configured to 1.0L manganese nitrate concentration be 1.0mol/L and magnesium sulfate it is dense
Degree is the mixed solution of 0.5mol/L, filters to obtain pure mixed solution.Sodium hydroxide, which is configured to 2.5L concentration with pure water, is
The sodium hydroxide solution of 1.2mol/L filters to obtain purified solution.
(2) electrolytic manganese dioxide that 1000g average grain diameter is 5.1 μm is tuned into 180g/L suspension with water, in stirring bar
Mixed solution and sodium hydroxide solution are added dropwise in manganese dioxide suspension under part, mixed solution and sodium hydroxide solution drop
Rate of acceleration is respectively 0.93mL/min, 2.3mL/min, and keeping pH value of reaction system is 7~10, while being passed through air, air stream
Amount is 0.2M3/ h is kept for 40 DEG C of reaction temperature, feed time 18 hours, adds material subsequent continuous insulation reaction 2 hours, reacted
It is filtered, washed after, obtains spherical dopping manganese dioxide.
(3) lithium carbonate is added by Li/Mn=0.53: 1 ratio in the obtained spherical dopping manganese dioxide of step (2), sufficiently
Be warming up to 450 DEG C according to 5 DEG C/min of heating rate after evenly mixing and be sintered 9 hours, then according still further to 5 DEG C of rate of temperature fall/
After min drops to 300 DEG C, room temperature is cooled to the furnace, by crushed 200 meshes, prepare with spherical, individual particle, micron
The adulterated lithium manganate presoma of grade external appearance characteristic.
(4) by the resulting adulterated lithium manganate presoma of step (3) in oxidizing atmosphere (air mass flow 2.5M3/ h) under according to liter
Warm 5 DEG C/min of rate is warming up to 870 DEG C and carries out roasting 14 hours, after then dropping to 300 DEG C according still further to 5 DEG C/min of rate of temperature fall,
It cooling to room temperature with the furnace, by crushed 200 meshes, obtaining lithium-ion-power cell manganate cathode material for lithium.
Lithium-ion-power cell manganate cathode material for lithium average grain diameter made from the present embodiment is 6.0 μm, tap density
2.31g/cm3, sulfate radical content 0.038%, pattern is regular spherical.
By the lithium-ion-power cell of the present embodiment with manganate cathode material for lithium prepare CR2025 type button cell, method with
Embodiment 1 is identical, is 2.8-4.5V in charging/discharging voltage, under conditions of charge-discharge magnification is 0.5C, the electric discharge for the first time of the battery
Specific capacity is 101mAh/g, and the capacity retention ratio that circulation is 3000 times is up to 80.4%.Under conditions of charge-discharge magnification is 1C, the electricity
The first discharge specific capacity in pond is 97mAh/g, and the capacity retention ratio that circulation is 2500 times is up to 80.3%.
The above is only a preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-mentioned implementation
Example.All technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It is noted that for the art
Those of ordinary skill for, improvements and modifications without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of preparation method of lithium-ion-power cell manganate cathode material for lithium, comprising the following steps:
(1) electrolytic manganese dioxide is dispersed in water, obtains electrolytic manganese dioxide suspension；Under agitation, by hydroxide
Sodium solution and soluble manganese salting liquid containing doped metal ion are added dropwise in the electrolytic manganese dioxide suspension simultaneously, are added dropwise
While be passed through air and carry out oxidation reaction, generate spherical dopping manganese dioxide；The soluble manganese containing doped metal ion
In salting liquid, Mn2+Concentration is 0.2~1.0mol/L, and Doped ions concentration is 0.1~0.5mol/L；Hydrogen in sodium hydroxide solution
The concentration of sodium oxide molybdena is 0.5~2.0mol/L；In electrolytic manganese dioxide suspension the concentration of electrolytic manganese dioxide be 100~
300g/L, the partial size of electrolytic manganese dioxide are 5~7 μm, and the flow for being passed through air is 0.1~0.5M3/h；
(2) it is sintered after mixing the resulting spherical dopping manganese dioxide of step (1) and lithium source, crushes, obtain spherical doping
Manganate precursor for lithium；
(3) the resulting spherical lithium manganate doped presoma of step (2) is roasted under oxidizing atmosphere, is crushed, it is dynamic to obtain lithium ion
Power battery manganate cathode material for lithium.
2. the preparation method of lithium-ion-power cell manganate cathode material for lithium according to claim 1, which is characterized in that
In the step (1), the solubility manganese salt is one of manganese chloride, manganese sulfate, manganese nitrate or a variety of, the doping metals
Ion is Al3+、Cr3+、Mg2+、Co2+One of or it is a variety of, the corresponding soluble-salt of the doped metal ion be chloride,
One of sulfate or nitrate are a variety of.
3. the preparation method of lithium-ion-power cell manganate cathode material for lithium according to claim 1 or 2, feature exist
In in the step (1), the drop rate of the soluble manganese salting liquid containing doped metal ion is 0.9~6.0mL/min, hydrogen
The drop rate of sodium hydroxide solution is 1.8~7.0mL/min；In oxidation reaction, system pH is 7~10, reaction temperature 10
~90 DEG C, the charging reaction time is 10~20h, the reaction was continued after the completion of charging 2h.
4. the preparation method of lithium-ion-power cell manganate cathode material for lithium according to claim 3, which is characterized in that
In the step (2), the mol ratio of Li in the lithium source and the Mn in spherical dopping manganese dioxide be Li/Mn=0.53~
0.6∶1。
5. the preparation method of lithium-ion-power cell manganate cathode material for lithium according to claim 4, which is characterized in that
The lithium source is lithium hydroxide or lithium carbonate, and the lithium hydroxide is LITHIUM BATTERY lithium hydroxide, and the lithium carbonate is LITHIUM BATTERY carbon
Sour lithium.
6. the preparation method of lithium-ion-power cell manganate cathode material for lithium according to claim 4 or 5, feature exist
In, in the step (2), the sintering detailed process are as follows: be warming up to 400~600 DEG C with the rate of 1~5 DEG C/min, sintering 5
~10h, then 300 DEG C are cooled to the rate of 1~5 DEG C/min, cool to room temperature with the furnace.
7. the preparation method of lithium-ion-power cell manganate cathode material for lithium according to claim 6, which is characterized in that
In the step (3), the detailed process of the roasting are as follows: be warming up to 800~900 DEG C with the rate of 1~5 DEG C/min, roasting 10
~20h, then 300 DEG C are cooled to the rate of 1~5 DEG C/min, cool to room temperature with the furnace.
8. the preparation method of lithium-ion-power cell manganate cathode material for lithium according to claim 7, which is characterized in that
In the step (3), the oxidizing atmosphere is 0.5~2.5M to be passed through flow3The air of/h or be passed through flow be 0.1~
0.5M3The oxygen of/h.
9. lithium-ion-power cell obtained by a kind of preparation method as described in any one of claims 1 to 8 with LiMn2O4 just
Pole material, average grain diameter are 6~8 μm, and tap density is greater than 2.2g/cm3, for sulfate radical content less than 0.04%, pattern is regular ball
Shape.
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| CN110257851B (en) * | 2019-06-11 | 2020-08-21 | 湖南顺隆能源有限公司 | Special electrolytic manganese dioxide for lithium manganate battery and preparation method thereof |
| CN111170375A (en) * | 2020-01-07 | 2020-05-19 | 万华化学集团股份有限公司 | Ternary positive electrode material precursor and preparation method thereof |
| CN114044539B (en) * | 2021-10-30 | 2023-06-30 | 湖南海利锂电科技有限公司 | Preparation method of high-cycle power lithium manganate |
| CN114349072B (en) * | 2021-12-27 | 2023-08-22 | 湖南海利锂电科技有限公司 | High-voltage nickel-manganese binary positive electrode material and preparation method and application thereof |
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