CN1244172C - Lithium manganate positive electrode material of laminated pole structure for lithium ion cell, and method for intercalation assembling and preparation thereof - Google Patents

Lithium manganate positive electrode material of laminated pole structure for lithium ion cell, and method for intercalation assembling and preparation thereof Download PDF

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CN1244172C
CN1244172C CNB031567568A CN03156756A CN1244172C CN 1244172 C CN1244172 C CN 1244172C CN B031567568 A CNB031567568 A CN B031567568A CN 03156756 A CN03156756 A CN 03156756A CN 1244172 C CN1244172 C CN 1244172C
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lithium
earth metal
presoma
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lithium manganate
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CN1595686A (en
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段雪
杨文胜
陈冬梅
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Beijing University of Chemical Technology
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    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
    • 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
    • C01P2006/40—Electric properties
    • 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
    • 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 present invention relates to a lithium manganate positive pole material with a layer post structure for a lithium ion battery and an intercalation assembling and preparing method thereof. A chemical formula of the lithium manganate positive pole material is Li <a> A <E beta> MnO2, wherein the transitional metal Mn and oxygen are combined by covalent bonds to form a MnO2 main body laid plate; lithium ions and alkaline earth metal ions are evenly distributed in an interlayer of the MnO2 main body laid plate; in a charge and discharge process of the lithium manganate positive pole material, the lithium ions Li <+> can be reversibly separated and the alkaline earth metal ions of Mg <2+>, Ca <2+> and Sr <2+> can not be separated, so in the charge and discharge process, the lithium manganate positive pole material has the advantages of stable structure, good cycle performance and high thermal stability. In the preparation method, firstly, a layered lithium manganate precursor is prepared by an oxidation-intercalation method; then, part of lithium ions Li <+> in the lithium manganate positive pole material with a layer post structure are replaced by the alkaline earth metal ions of the Mg <2+>, the Ca <2+> or the Sr <2+> to prepare layer-post lithium manganate.

Description

Lithium ion battery layer pole manganate cathode material for lithium and intercalation process for assembly preparing thereof
Technical field
The present invention relates to anode material for lithium-ion batteries and technology of preparing thereof.
Background technology
The positive electrode consumption is big in the lithium ion battery, the price height is the key factor that influences lithium ion battery overall performance and production cost, is the important step of research and development lithium ion battery, particularly research and develop novel high-performance, low-cost positive electrode, extremely people pay attention to always.
Manganese aboundresources, cheap, nontoxic pollution-free are the optimal materials that substitutes cobalt, have very bright development prospect in lithium ion battery.Manganic acid lithium electrode material mainly contains spinel-type LiMn 2O 4With layer structure LiMnO 2Spinel-type LiMn 2O 4The specific capacitance of electrode material is low, it is short to recycle the life-span, big operating current and poor than the chemical property under the elevated operating temperature, and practical application is subjected to bigger restriction.Stratiform LiMnO 2Difference according to spatial symmetry can be divided into two kinds of structures, belongs to rhombic system and monoclinic system respectively, and affiliated space group is respectively Pmnm and C2/m, and they all have the characteristic of reversible removal lithium embedded ion, wherein belong to the stratiform LiMnO of rhombic system 2Have relatively than stable structure and than excellent electrochemical properties, study more at present.
Rhombic system stratiform LiMnO 2Positive electrode in, transient metal Mn combines with strong covalent bond with oxygen, constitutes MnO 2The main body laminate, lithium ion is positioned at by MnO 2The interlayer of the main body laminate that constitutes.At stratiform LiMnO 2In the positive electrode, the Li/Mn ratio is 1/1, so this material has higher reversible removal lithium embedded ability, and theoretical capacity is 285mAhg -1, actual capacity has reached 200mAhg -1About; At stratiform LiMnO 2In, Li +With main body laminate MnO 2Between with ionic bond combination, Li +Have the stratiform diffusion admittance of two dimension, diffusion coefficient is bigger, so stratiform LiMnO 2Material has good multiplying power property.
But stratiform LiMnO 2Structural instability, at charge and discharge process, i.e. taking off in the embedding process of lithium ion, the body layer plate structure easily distorts, and changes to spinel structure, loses former stratiform LiMnO 2The architectural feature of electrode material causes the rapid decay of electrochemical specific capacity.
In order to stablize stratiform LiMnO 2Structure, improve its cycle performance, people study and have adopted several different methods, with other elements mix up replace be people study at most and effect also a kind of, this mainly comprises the anionic replacement that mixes up that mixes up replacement and lithium ion that mixes up replacements, transient metal Mn.
At document (1) Electrochemistry Communications, 2003, among the 5:124, people such as Sang-Ho Park at first adopt sol-gel processing to synthesize Na 0.7MnO 2-yS yPresoma joins then and carries out ion-exchange in the mixed liquor of ethanol and LiBr and obtain Li xMn 2-yS y, y=0.1 wherein, 0.2 or 0.3.Anion replaces sample than stratiform LiMnO 2Cycle performance had and significantly improved, but product structure is still unstable, changes the spinelle phase in the electrochemistry cyclic process into; Owing to lithium content in the product is on the low side, initial reversible capacity is lower in addition.
At document (2) Journal of the Electrochemical Society, 2000,147 (11): in 4078, the LiAl that people such as BAmmundsen adopt high temperature solid state reaction to prepare to mix up Al and mix up Cr xMn 1-xO 2And LiCr xMn 1-xO 2, chemical property is than stratiform LiMnO 2Improve a lot, but in charge and discharge process, still observed the appearance of spinelle phase.People utilize also that multiple element mixes up replacement to manganese in the periodic table of elements in addition, but except mixing Co and mix the sample of Ni, and the mixing up of other elements all can make specific discharge capacity that in various degree reduction is arranged.
In document (3) US 2002/0012843 A1, people such as Fumio Munkata adopt high temperature solid state reaction to prepare Li 1-xA xMn 1-yM yO 2Type and Li 1-xA xMnO 2The type compound, wherein A represents Na, K, monovalent metallic ions such as Ag, M represents Co, Ni, Cr, Fe, Al, Ga, In etc., the cyclical stability of sample is much improved, and after circulation 100～130 times, capacity also can keep 90% of initial capacity.But Na +, K +, Ag +Can not stable existence in electrode material Deng monovalent metallic ion, in charging process, also can deviate from, document (4) Electrochemical and Solid State Letters, 2000,3 (7): in 309, people's such as Fan Zhang work has fully confirmed this point, therefore with the carrying out of charge and discharge cycles reaction, and Na +, K +, Ag +Constantly deviate to run off Deng monovalent metallic ion, make the structural stability variation of electrode material, chemical property reduces rapidly.
Summary of the invention
The objective of the invention is in order to solve stratiform LiMnO 2The electrode material structural instability, at charge and discharge process, be the taking off in the embedding process of lithium ion, the body layer plate structure easily distorts, change to spinel structure, lose the architectural feature of former layered electrode material, cause the electrochemical specific capacity problem of decay rapidly, novel layer pole structure manganate cathode material for lithium of a kind of lithium ion battery and preparation method thereof is provided.
Layer pole structure manganate cathode material for lithium provided by the invention is with the part lithium ion Li in the layered lithium manganate electrode material +Use alkaline-earth metal ions Mg 2+, Ca 2+Or Sr 2+Replace, lithium ion and alkaline-earth metal ions are evenly distributed on by MnO 2The body layer plate holder layer that constitutes.This positive electrode in the charge and discharge cycles process, Li +Can reversiblely take off embedding, and alkaline-earth metal ions Mg 2+, Ca 2+, Sr 2+Can not deviate from, between laminate, play and stablize pillared effect, the layer structure feature that keeps electrode material, therefore layer post manganate cathode material for lithium has more stable structure, better cycle ability and higher thermal stability than the layered lithium manganate electrode material in the charge and discharge cycles process.
This layer post manganate cathode material for lithium adopts the intercalation assemble method to prepare, and promptly adopts oxidation-intercalation method to prepare layered lithium manganate LiMnO earlier 2Presoma, again by ion-exchange reactions with alkaline-earth metal ions Mg 2+, Ca 2+, Sr 2+Deng replacement lithium ion Li +Introduce MnO 2The laminate interlayer is to obtain layer post manganate cathode material for lithium.
Concrete processing step is as follows:
A adopts oxidation-intercalation method to prepare stratiform LiMnO 2Presoma;
B adopts fused salt ion-exchange or aqueous solution intermediate ion switching method with alkaline-earth metal ions Mg 2+, Ca 2+Or Sr 2+Replace Li +Be incorporated into the laminate interlayer of stratiform presoma;
C is with the consumption of ion exchange product by every gram product 20～50mL water, divide 3～4 washings with deionized water, vacuumize 2～3h in 100～150 ℃ vacuum drying chamber, heat treatment 15～30h in 150～250 ℃ of temperature ranges obtains layer post manganate cathode material for lithium.
The oxidation of the described layered lithium manganate presoma of steps A-intercalation preparation method, its concrete steps are as follows: a. is with Mn (NO 3) 2, MnSO 4, MnCl 2, Mn (CH 3COO) 2Etc. in the soluble manganese salt any one, under nitrogen protection, be dissolved in the deionized water that boiled, being mixed with concentration is 0.5～2.0molL -1Manganese salt solution; Highly basic KOH or NaOH are dissolved under nitrogen protection and are mixed with concentration in the deionized water that boiled is 0.5～2.0molL -1Strong base solution; The two is pressed generation Mn (OH) 2Stoichiometric proportion or ratio hybrid reaction and ageing 2～10h under 60～80 ℃ of temperature of highly basic excessive 5%～20%, obtain layer structure Mn (OH) 2Suspension-turbid liquid;
B. be 5～15 ratio in the Li/Mn mol ratio, the LiOH pressed powder is joined Mn (OH) 2In the suspension-turbid liquid; Again by general+divalent manganese be oxidized to+to drip concentration be 0.1～1.0molL in 3 valency manganese metering or excessive 10%～50% -1Potassium peroxydisulfate K 2S 2O 8, ammonium persulfate (NH 4) 2S 2O 8, clorox NaClO or hydrogen peroxide H 2O 2In a kind of oxidant to assist the carrying out of intercalation, oxidation intercalation time 5～20h;
C. the product suction filtration of step b and divide 3～4 washings with deionized water by the consumption of every gram product 20～50mL water, vacuumize 6～24h under 100～150 ℃ of temperature makes stratiform LiMnO then 2Presoma.
The alkaline earth metal compound that the described fused salt ion-exchange reactions of step B method is adopted can be Mg (NO 3) 26H 2O (89 ℃ of fusing points), MgCl 26H 2O (116 ℃ of fusing points), CaCl 26H 2O (29.9 ℃ of fusing points), Ca (NO 3) 24H 2O (42.7 ℃ of fusing points) etc. has low-melting compound, it is melted being higher than under 20～50 ℃ of temperature of its fusing point, it according to the mol ratio of layered lithium manganate presoma/alkaline earth metal compound 1/5～1/15 ratio, the layered lithium manganate presoma joined carry out ion-exchange reactions in the alkaline-earth metal melting compound, reaction time is 10min～180min, obtains a layer post LiMn2O4.
The alkaline earth metal compound that the described aqueous solution intermediate ion of step B exchange reaction method is adopted can be MgCl 2, Mg (NO 3) 2, MgSO 4, CaCl 2, Ca (NO 3) 2, Sr (NO 3) 2Deng the compound with higher solubility, it is made into concentration is 1.0～10molL -1Solution, be that 1/5～1/15 ratio adds above-mentioned solution with the layered lithium manganate presoma according to the mol ratio of layered lithium manganate presoma alkaline earth metal compound, be to react 1～4 day under 60～90 ℃ of conditions in the synthesis under normal pressure temperature; Or 120～180 ℃ of reaction temperatures, hydro-thermal reaction 2～24h under reaction pressure 1.0～10MPa condition obtains a layer post LiMn2O4.
By the layer post manganic acid lithium electrode material that above-mentioned intercalation assemble method is prepared, its chemical composition is Li αA E βMnO 2, AE=Mg wherein, Ca, Sr; 0.80≤α＜1.0,0＜β≤0.10,0.90≤α+2 β≤1.05;
Adopt day island proper Tianjin XRD-6000 type x-ray powder diffraction instrument (Cu K αRadiation, λ=1.5406 ) characterizes product structure, day island proper Tianjin ICPS-7500 type inductive coupling plasma emission spectrograph is measured the content of alkali metal, alkaline-earth metal and manganese element in the product, the Mastersizer of Britain Ma Erwen company 2000 type laser particle size analyzers are measured the particle diameter and the distribution of product, test result proves: this layer post manganic acid lithium electrode material has above-mentioned chemical composition, and its structure is a rhombic system.Particle diameter is at 0.4～0.7 μ m, and purity＞98% has good crystal formation.
Respectively different electrode materials and commercially available acetylene black conductive agent and the polytetrafluoroethylene binding agent mass fraction by (85: 10: 5) is mixed, and the thickness of compressing tablet to 100 μ m, in 120 ℃ of vacuum (＜1Pa) dry 24h.As to electrode, adopt Celgard 2400 barrier films, 1molL with metal lithium sheet -1LiPF 6+ EC+DMC (EC/DMC volume ratio 1: 1) is an electrolyte, at the German M. Braun Unlab of company type dry argon gas glove box (H 2O＜1ppm, O 2＜be assembled into Experimental cell sample 1～3 and comparative sample 1～2 in 1ppm), adopt the blue electric BTI1-10 type cell tester in Wuhan to carry out electrochemical property test, operating voltage range is 2.5～4.5V (vs Li), operating current is 0.1mAcm -2, its cycle performance test result sees Table 1.
Wherein sample 1～3 is respectively the layer post manganic acid lithium electrode material that obtains by the embodiment of the invention 1～3; Comparative sample 1 is the stratiform LiMnO without ion-exchange 2The Li that comparative sample 2 prepares for the high-temperature solid phase reaction method that adopts document (3) 0.95K 0.05MnO 2
The cycle performance of table 1 electrode material
Sample The electrode material chemical composition The reversible capacity mAhg of some all after dates circulates -1
First 10 20 30
Sample 1 Li 0.9Ca 0.05MnO 2 204 198 194 191
Sample 2 Li 0.93Mg 0.04MnO 2 202 197 194 192
Sample 3 Li 0.89Sr 0.04MnO 2 199 194 190 187
Comparative sample 1 LiMnO 2 202 181
Comparative sample 2 Li 0.95K 0.05MnO 2 201 191 182 175
As can be seen from Table 1, adopt the layer post LiMn2O4 Li of the inventive method preparation αA E βMnO 2With layered lithium manganate LiMnO 2Reversible capacity first suitable, but cycle performance obviously is better than layered lithium manganate, also obviously is better than mixing up with monovalent metallic ion the Li of replacement 0.95K 0.05MnO 2Electrode material.
With sample 1～3 and comparative sample 2, after 10 weeks of charge and discharge cycles, 30 weeks, in the dry argon gas glove box, take apart, electrode slice is fully washed the back drying with isopropanol solvent, measure the wherein content of metallic element then, test result sees Table 2.
The results of elemental analyses of table 2 sample
Sample Chemical composition Initially (K, A E)/Mn (K, A after 10 weeks of circulation E)/Mn (K, A after 30 weeks of circulation E)/Mn
Sample
1 Li 0.9Ca 0.05MnO 2 0.05 0.05 0.05
Sample 2 Li 0.93Mg 0.04MnO 2 0.04 0.04 0.04
Sample 3 Li 0.89Sr 0.04MnO 2 0.04 0.04 0.04
Comparative sample 2 Li 0.95K 0.05MnO 2 0.05 0.04 0.02
As shown in Table 2, mix up K +The sample Li of ion 0.95K 0.05MnO 2Tangible potassium ion K just appearred after 10 weeks in charge and discharge cycles +Leakage, and layer post LiMn2O4 Li αA E βMnO 2Electrode material alkaline-earth metal ions after the circulation of 30 weeks does not have loss, and promptly alkaline-earth metal ions can stably be present in the laminate interlayer of electrode material, plays and stablizes pillared effect, and the cycle performance of manganic acid lithium electrode material is improved significantly.
With sample 1～3 and comparative sample 1～2, charging to difference by in the dry argon gas glove box, taking apart behind the voltage, electrode slice is fully washed the back drying with isopropanol solvent, use the TG-DTA curve of PCT-1A type differential thermal analyzer working sample in air atmosphere then, heating rate is 10 ℃ of min -1, the heat decomposition temperature of each sample is shown in Table 3, and visible layer post LiMn2O4 has the best thermal stability.
The thermal stability test result of table 3 sample
Sample The sample chemical formula Charge to decomposition temperature behind the different potentials/℃
4.0V vs Li 4.2V vs Li 4.4V vs Li
Sample 1 Li 0.9Ca 0.05MnO 2 241 232 221
Sample 2 Li 0.93Mg 0.04MnO 2 244 233 223
Sample 3 Li 0.89Sr 0.04MnO 2 238 231 219
Comparative sample 1 LiMnO 2 214 201 185
Comparative sample 2 Li 0.95K 0.05MnO 2 225 215 202
Remarkable result of the present invention is: adopt intercalation assemble method provided by the invention can obtain to have the layer post manganic acid lithium electrode material of new structure, layer post LiMn2O4 utilizes the pillared alkaline-earth metal ions of laminate interlayer to stablize veneer structure preferably, therefore layer post LiMn2O4 has more stable structure and excellent cycle performance than layered lithium manganate, and, novel layer post LiMn2O4 compares with the sample that replaces with monovalent metallic ions such as alkali metal, alkaline-earth metal is more stable at the laminate interlayer, stablizes the better effects if of laminate and electrode material structure.
Description of drawings
Fig. 1. the structural representation of layer post manganic acid lithium electrode material, wherein 1 is oxonium ion O 2-, 2 is transition metal ions Mn 3+, 3 is lithium ion Li +And alkaline-earth metal ions Mg 2+, Ca 2+, Sr 2+
Embodiment
Embodiment 1:
Take by weighing MnSO 4H 2O 16.90g (0.10mol), NaOH 8.80g (0.22mol) is at N 2Protection is dissolved in respectively down in the deionized water that 90mL boiled; Under stirring fast, NaOH solution is splashed into MnSO 4In the solution, the Mn that obtains (OH) 2Be deposited in 80 ℃ of water-baths ageing 10 hours; Take by weighing LiOHH 2O pressed powder 41.96g (1.0mol) joins above-mentioned Mn (OH) 2In the suspension-turbid liquid and stirring and dissolving; Take by weighing (NH 4) 2S 2O 8Oxidant 17.10g (0.075mol) is dissolved in the deionized water that 70mL boiled, and is added drop-wise in the reaction system with even velocity in 2h, continues reaction 15h in 80 ℃ of water-baths; Product is washed suction filtration 3 times with 180mL deionization moisture again with the glass sand hourglass suction filtration, at 120 ℃ of vacuumize 8h, make stratiform LiMnO then 2Presoma; With LiMnO 2Presoma joins 236g (1mol) at the four water-calcium nitrate Ca of 80 ℃ of fusions (NO 3) 24H 2React 40min in the O fused salt; Ion exchange product is washed for 4 times with 300mL deionization moisture, and vacuumize 2h in 120 ℃ vacuum drying chamber at 200 ℃ of heat treatment 20h, obtains product of the present invention, and ICP and XRD analysis show that product consists of Li 0.92Ca 0.05MnO 2, belonging to rhombic system, Electrochemical results sees Table 1
Embodiment 2:
Adopt with embodiment 1 same procedure and prepare stratiform LiMnO 2Presoma; With LiMnO 2It is 5molL that presoma adds 100mL concentration -1MgCl 2In the solution, 140 ℃ of reaction temperatures, hydro-thermal reaction 6h under the reaction pressure 2.0MPa condition; Ion exchange product is washed for 4 times with 300mL deionization moisture, and vacuumize 2h in 120 ℃ vacuum drying chamber at 200 ℃ of heat treatment 20h, obtains product of the present invention, and ICP and XRD analysis show that product consists of Li 0.93Mg 0.04MnO 2, belonging to rhombic system, Electrochemical results sees Table 1.
Embodiment 3:
Adopt with embodiment 1 same procedure and prepare stratiform LiMnO 2Presoma; With LiMnO 2It is 5molL that presoma adds 100mL concentration -1Strontium nitrate Sr (NO 3) 2In the solution,, react 24h under 80 ℃ of conditions of reaction temperature at normal pressure; Ion exchange product is washed for 4 times with 300mL deionization moisture, and vacuumize 2h in 120 ℃ vacuum drying chamber at 200 ℃ of heat treatment 20h, obtains product of the present invention, and ICP and XRD analysis show that product consists of Li 0.89Sr 0.04MnO 2, belonging to rhombic system, Electrochemical results sees Table 1.

Claims (4)

1, a kind of lithium ion battery layer pole type manganate cathode material for lithium, its chemical composition general formula is Li αA E βMnO 2, A in the formula EA kind of among alkali earth metal Mg, Ca, the Sr, and 0.80≤α＜1.0,0＜β≤0.10,0.90≤α+2 β≤1.05; Transient metal Mn and oxygen constitute MnO with covalent bonds 2The main body laminate, lithium ion and alkaline-earth metal ions are evenly distributed on by MnO 2The interlayer of the main body laminate that constitutes, this layer post manganate cathode material for lithium belongs to rhombic system, has the Pmm spatial symmetry.
2, a kind of intercalation process for assembly preparing of lithium ion battery layer pole manganate cathode material for lithium as claimed in claim 1, processing step is as follows:
A adopts the oxidized inserting layer method to prepare stratiform LiMnO 2Presoma
A. with Mn (NO 3) 2, MnSO 4, MnCl 2, Mn (CH 3COO) 2Etc. in the soluble manganese salt any one, under nitrogen protection, be dissolved in the deionized water that boiled, being mixed with concentration is 0.5～2.0molL -1Manganese salt solution; Highly basic KOH or NaOH are dissolved under nitrogen protection and are mixed with concentration in the deionized water that boiled is 0.5～2.0molL -1Strong base solution; The two is pressed generation Mn (OH) 2Stoichiometric proportion or ratio hybrid reaction and ageing 2～10h under 60～80 ℃ of temperature of highly basic excessive 5%～20%, obtain layer structure Mn (OH) 2Suspension-turbid liquid;
B. be 5～15 ratio in the Li/Mn mol ratio, the LiOH pressed powder is joined Mn (OH) 2In the suspension-turbid liquid; Again by general+divalent manganese be oxidized to+to drip concentration be 0.1～1.0molL in 3 valency manganese metering or excessive 10%～50% -1Potassium peroxydisulfate K 2S 2O 8, ammonium persulfate (NH 4) 2S 2O 8, clorox NaClO or hydrogen peroxide H 2O 2In a kind of oxidant to assist the carrying out of intercalation, oxidation intercalation time 5～20h;
C. the product suction filtration of step b and divide 3～4 washings with deionized water by the consumption of every gram product 20～50mL water, vacuumize 6～24h under 100～150 ℃ of temperature makes stratiform LiMnO then 2Presoma;
B adopts fused salt ion-exchange or aqueous solution intermediate ion switching method, with alkaline-earth metal ions Mg 2+, Ca 2+Or Sr 2+Be incorporated into stratiform LiMnO 2The laminate interlayer of presoma, part replaces lithium ion Li +
C is with the consumption of ion exchange product by every gram product 20～50mL water, divide 3～4 washings with deionized water, vacuumize 2～3h in 100～150 ℃ vacuum drying chamber, heat treatment 15～30h in 150～250 ℃ of temperature ranges obtains a layer post manganate cathode material for lithium.
3, the intercalation process for assembly preparing of lithium ion battery layer pole manganate cathode material for lithium according to claim 2 is characterized in that the described fused salt ion-exchange reactions of step B method, is with Mg (NO 3) 26H 2O, MgCl 26H 2O, CaCl 26H 2O or Ca (NO 3) 24H 2Any one melts O being higher than under 20～50 ℃ of temperature of its fusing point, it according to the mol ratio of layered lithium manganate presoma/alkaline earth metal compound 1/5～1/15 ratio, the layered lithium manganate presoma joined carry out ion-exchange reactions in the molten caustic soda earth metal compound, reaction time is 10min～180min, obtains a layer post LiMn2O4.
4, the intercalation process for assembly preparing of lithium ion battery layer pole manganate cathode material for lithium according to claim 2 is characterized in that the described aqueous solution intermediate ion of step B exchange reaction method, is with MgCl 2, Mg (NO 3) 2, MgSO 4, CaCl 2, Ca (NO 3) 2Or Sr (NO 3) 2Any one is made into concentration is 1.0～10mo1L -1Solution, be that 1/5～1/15 ratio adds above-mentioned solution with the layered lithium manganate presoma according to the mol ratio of layered lithium manganate presoma/alkaline earth metal compound, be to react 1～4 day under 60～90 ℃ of conditions in the synthesis under normal pressure temperature; Or 120～180 ℃ of reaction temperatures, hydro-thermal reaction 2～24h under reaction pressure 1.0～10MPa condition obtains a layer post manganate cathode material for lithium.
CNB031567568A 2003-09-10 2003-09-10 Lithium manganate positive electrode material of laminated pole structure for lithium ion cell, and method for intercalation assembling and preparation thereof Expired - Fee Related CN1244172C (en)

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CN112563564B (en) * 2020-11-13 2021-11-09 上海空间电源研究所 Soft chemical synthesis method for preparing sodium ion solid electrolyte
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