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CN1254872C - Preparation of oxidized inserting layer of laminated lithium manganate as lithium ion battery anode - Google Patents

Preparation of oxidized inserting layer of laminated lithium manganate as lithium ion battery anode Download PDF

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CN1254872C
CN1254872C CNB031386261A CN03138626A CN1254872C CN 1254872 C CN1254872 C CN 1254872C CN B031386261 A CNB031386261 A CN B031386261A CN 03138626 A CN03138626 A CN 03138626A CN 1254872 C CN1254872 C CN 1254872C
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intercalation
lithium
lithium manganate
manganese
layered
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CN1553529A (en
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段雪
杨文胜
李晓丹
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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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • 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

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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

The present invention relates to oxidation of layer lithium manganate of positive electrode material of a lithium ion battery, namely a preparation method of intercalation, which belongs to the technical field of material preparation of a lithium ion battery. The present invention is characterized in that manganese salt and strong alkali are respectively dissolved in boiled deionized water under nitrogen protection, and precursor material of manganese hydroxide Mn(OH)2 with a layered structure is prepared; an intercalation object of a lithium compound is added to a layered precursor suspension according to certain proportion, intercalation reaction is carried out under synergistic effect of oxidant, layered lithium manganate is prepared, and the chemical composition formula is Li<x>MnO2(x is larger than or equal to 0.8 and is smaller than or equal to 1.0). The layered lithium manganate belongs to an orthorhombic system, and has the advantages of spatial symmetry of Pmnm, high product purity, no impurity phase and uniform and controllable particle diameter. Specific capacity is high and cycle performance is good by using the layered lithium manganate as positive electrode material of a lithium ion battery. The present invention has the advantages of no need for expensive apparatus and treating process with high temperature, simple technology, easy obtainment of raw material, low cost and easy realization of mass industrial production.

Description

The oxidized inserting layer preparation method of positive electrode laminated cell lithium manganate of lithium ion
Technical field
A kind of oxidized inserting layer preparation method of positive electrode laminated cell lithium manganate of lithium ion belongs to the lithium ion battery material preparing technical field.
Background technology
In the lithium ion battery, electrode material is its important component part, and particularly the positive electrode consumption is big, and the price height is the key factor that influences lithium ion battery performance and production cost.
The commercialization lithium ion battery adopts layer structure cobalt acid lithium LiCoO more at present 2As positive electrode.Cobalt acid lithium has excellent electrochemical properties.But cobalt costs an arm and a leg, and environment is had certain pollution, and the popularizing of lithium ion battery that this makes with the sour lithium of cobalt is positive electrode is very limited, and particularly at aspects such as development large capacity electric vehicle electrokinetic cells, this contradiction is just more outstanding.
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 2, layer structure LiMnO 2Be divided into two kinds of quadrature and monocline symmetries (space group is respectively Pmnm and C2/m), all have the characteristic of reversible taking off/embedding lithium.Spinel-type LiMn 2O 4The specific capacitance of electrode material is low, recycle short, big operating current of life-span and poor than the chemical property under the elevated operating temperature, and practical application area is narrow.With spinel-type LiMn 2O 4Compare layered lithium manganate LiMnO 2Theoretical specific capacitance height, operating current are big, are a kind of even more ideal positive electrodes.But because Mn 3+Have stronger Jahn-Teller effect, cause the material structure instability, the preparation difficulty big.In order to obtain Stability Analysis of Structures, the layered lithium manganate electrode material that chemical property is good, people have researched and developed multiple preparation method, as high-temperature solid phase reaction method, hydrothermal synthesis reaction method, ion-exchange reactions method and melt impregnation method etc., but all there is weak point in these synthetic methods.
High-temperature solid phase reaction method: at document (1) Journal of Power Sources, 1995, among the 54:232, people such as Davidson I.J. are with β-MnO 2And Li 2CO 3By mass ratio is 2: 1 mixed pressuring plates, and ℃ preliminary treatment several hrs in 6O0～650 at first is to remove CO 2, under argon gas atmosphere, 800～1000 ℃ of reaction 1～3d repeat above-mentioned heat treatment process 1～2 time, can obtain to belong to the stratiform LiMnO of rhombic system then 2At voltage range 1.5～4.0V (vs.Li), current density 1.26mAg -1Test condition under, reversible capacity is about 130mAhg -1High-temperature solid phase reaction method needs high-temperature service, and the reaction time is long, and generally needs inert gas shielding, complex process, cost height; The layered lithium manganate that adopts high-temperature solid phase reaction method to prepare in addition often contains the impurity phase, pattern is irregular, granularity is big, particle size distribution is inhomogeneous, and the chemical property of product is poor.
The hydrothermal synthesis reaction method: at document (2) Journal of Power Sources, 1999, among the 81-82:49, people such as Yoshiaki Nitta are with γ-MnOOH and LiOHH 2The O mixed pressuring plate is put into autoclave at 130 ℃, pressure about 3 * 10 5Hydro-thermal reaction 0.5～4h under the Pa condition, vacuumize then promptly gets the stratiform LiMnO that belongs to rhombic system 2, at voltage range 2.0～4.3V (vs.Li), current density 0.5mAcm -2Test condition under, reversible capacity is 160～190mAhg -1At document (3) Electrochimica Acta, 2002, among the 47:3287, people such as Seung-Taek Myung are with Mn 3O 4And LiOHH 2O is a reaction raw materials, at 170 ℃ of autoclave internal reaction 4d, has also obtained to belong to the stratiform LiMnO of rhombic system 2, at voltage range 2.0～4.3V (vs.Li), current density 22.5mAg -1(C/12.9) under the test condition, reversible capacity reaches 200mAhg -1The product of hydrothermal synthesis reaction method preparation has excellent electrochemical properties, but this method needs expensive Special Equipment-autoclave, is subjected to the reaction vessel capacity limitation in addition, is not easy to realize large-scale industrial production.
The ion-exchange reactions method: at document (4) Nature, 1996, among the 381:499, people such as Robert Armstrong A are with Na 2CO 3And Mn 2O 3Mix by stoichiometric proportion, under argon atmospher,, obtain α-NaMnO in 700～730 ℃ of solid phase reaction 18～72h 2, then with a certain amount of α-NaMnO 2Join in the n-hexyl alcohol that contains excessive LiCl or LiBr, at 145～150 ℃ of heating 6～8h that reflux, filter behind the cool to room temperature, use n-hexyl alcohol and alcohol flushing respectively, drying obtains monocline phase LiMnO then 2, at voltage range 3.4～4.3V (vs.Li), current density 10 μ Acm -2Test condition under, the initial charge capacity is 270mAhg -1, when current density is 0.5mAcm -2The time, the initial charge capacity is near 200mAhg -1But the reversible capacity of this material (being discharge capacity) is low, lamellar precursor in the ion-exchange reactions method generally need adopt the high-temperature solid phase reaction method preparation in addition, ion exchange process needs the expensive raw material of some prices, complex manufacturing, severe reaction conditions are unfavorable for large-scale production.
The melt impregnation method: at document (5) Journal of Power Sources, 1995, among the 54:483, people such as YoshiioM are at first with lithium salts (LiNO 3Or LiI) is heated to fusing point, makes the lithium salts of fusion be immersed in MnO 2The hole in, and then be heated to predetermined reaction temperature, can obtain to belong to the stratiform Li of rhombic system xMnO 2, but this method obtains the lithiumation degree not high (x＜0.5) of product, is unfavorable for obtaining the height ratio capacity electrode material.
Summary of the invention
The oxidized inserting layer preparation method who the purpose of this invention is to provide a kind of positive electrode laminated cell lithium manganate of lithium ion.Promptly with stratiform manganous hydroxide Mn (OH) 2As precursor material, lithium compound is as the intercalation object, lithium ion is inserted into stratiform Mn (OH) under the synergy of oxidant 2Between the laminate of precursor material, can obtain to belong to the high-purity stratiform LiMn2O4 of rhombic system thus.Controlled with the product cut size homogeneous that this method obtains, specific capacity is high and have an excellent cycle performance.
Concrete steps of the present invention comprise:
A is dissolved in soluble manganese salt, highly basic in the deionized water that boiled under nitrogen protection respectively, and being mixed with concentration is 0.5～2.0molL -1Manganese salt solution and strong base solution, with the two by generating Mn (OH) 2Stoichiometric proportion or ratio hybrid reaction and ageing 5～20h under 60～80 ℃ of temperature of highly basic excessive 5%～20%, obtain layer structure Mn (OH) 2The suspension-turbid liquid precursor material;
B is 5～15 ratio in the Li/Mn mol ratio, and lithium compound intercalation object 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% -1Oxidant to assist the carrying out of intercalation, oxidation intercalation time 5～20h.Excessive LiOH, the solubility lithium salts in reaction back can reclaim use.
C also uses deionized water wash 3～4 times with the product suction filtration of step B, and vacuumize 6～24h under 100～150 ℃ of temperature makes layered lithium manganate Li then xMnO 2
The used soluble manganese salt of steps A is manganese nitrate Mn (NO 3) 2, manganese sulfate MnSO 4, manganese chloride MnCl 2, manganese acetate Mn (CH 3COO) 2In any one; The described highly basic of steps A is potassium hydroxide KOH or NaOH NaOH.
The used lithium compound intercalation of step B object is the LiOH pressed powder, or solubility lithium salts LiCl, LiNO 3, Li 2SO 4Any one or multiple mixture, but when adding the solubility lithium salts, simultaneously will be to Mn (OH) 2Add NaOH NaOH or potassium hydroxide KOH in the suspension-turbid liquid, to guarantee OH in this reaction system -Molar concentration 〉=1molL -1Used oxidant can be potassium peroxydisulfate K 2S 2O 8, ammonium persulfate (NH 4) 2S 2O 8, clorox NaClO or hydrogen peroxide H 2O 2In any one.
Adopt day island proper Tianjin XRD-6000 type x-ray powder diffraction instrument (CuK αRadiation, λ=1.5406 ) characterizes product structure, day island proper Tianjin ICPS-7500 type inductive coupling plasma emission spectrograph is measured the content of lithium and manganese element in the product, and 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 shows the oxidized inserting layer method provided by the present invention that adopts, and by the control synthetic technological condition, can obtain chemical composition is Li xMnO 20.8≤x≤1.0 wherein belong to the layered lithium manganate of rhombic system, and the product purity height, and crystal formation is good, uniform particle diameter controlled (0.4～0.7 μ m).
The mass fraction that adopts the synthetic layered lithium manganate electrode material of the inventive method and commercially available acetylene black conductive agent and polytetrafluoroethylene binding agent to press (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 in 1ppm).Adopt the blue electric BTI1-10 type cell tester in Wuhan to carry out electrochemical property test, test result sees Table 1, and table 1 has also been listed the test result that has higher chemical property sample in the bibliographical information.
The table 1 chemical property table of comparisons
Sample Synthetic method Test voltage and electric current Reversible specific discharge capacity
Embodiment
1 The oxidized inserting layer method 2.5～4.5V，0.1mA·cm -2 180mAh·g -1
Embodiment 2 The oxidized inserting layer method 2.5～4.5V，0.1mA·cm -2 193mAh·g -1
Embodiment 3 The oxidized inserting layer method 2.5～4.5V，0.1mA·cm -2 202mAh·g -1
Document (2) Hydrothermal synthesis method 2.0～4.3V，0.5mA·cm -2 160～190mAh·g -1
Document (3) Hydrothermal synthesis method 2.0～4.3V，C/12.9 200mAh·g -1
As can be seen from Table 1, adopt the layered lithium manganate of the inventive method preparation at narrower charging/discharging voltage scope (2.5～4.5V vs Li), bigger operating current (0.1mAcm -2) under, reversible capacity reaches 180～200mAhg -1More than, reach the highest level of bibliographical information.
The technology that the present invention compares existing preparation layered lithium manganate has following advantage:
1, process using softening method of the present invention is synthetic, with stratiform Mn (OH) 2As the reaction precursor body,, therefore can keep the layer structure feature of presoma preferably, and can obtain the non-stoichiometric product without pyroprocess.
2, it is synthetic that technology of the present invention belongs to wet method, do not need high-temperature process, so the product uniform particle diameter is controlled, reaction thoroughly, free from admixture phase, purity height.
3, the inventive method technology is simple, no complexity and expensive device, and raw material cheaply is easy to get, and production cost is low, realizes large-scale industrial production easily.
With the layered lithium manganate of the inventive method preparation at narrower charging/discharging voltage scope (2.5～4.5V vsLi), bigger operating current (0.1mAcm -2) under, reversible capacity reaches 180～200mAhg -1More than, reach the highest level of bibliographical information.
Description of drawings
Fig. 1. the XRD spectra of layered lithium manganate product
Fig. 2. the charging and discharging curve of layered lithium manganate product and cycle performance
Execution mode
Embodiment 1:
Take by weighing MnSO 4H 2O 16.90g (0.10mol), NaOH 8.00g (0.20mol) 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 60 ℃ of water-baths ageing 10 hours; Take by weighing LiOHH 2O pressed powder 20.98g (0.5mol) joins above-mentioned Mn (OH) 2In the suspension-turbid liquid and stirring and dissolving; Take by weighing oxidant (NH 4) 2S 2O 817.10g (0.075mol), be dissolved in the deionized water that 70mL boiled, in 2h, be added drop-wise in the reaction system, in 80 ℃ of water-baths, continue reaction 10h with even velocity; With product glass sand hourglass suction filtration, with 3 washings of 180mL deionization moisture suction filtration, at 120 ℃ of vacuumize 8h, make product of the present invention then again, ICP and XRD analysis show that product consists of Li 0.83MnO 2, belonging to rhombic system layered lithium manganate structure (Fig. 1), electro-chemical test shows reversible capacity 180mAhg first -1, 10 times circulation back reversible capacity has still kept 162mAhg -1(Fig. 2).
Embodiment 2:
Take by weighing MnSO 4H 2O 16.90g (0.10mol), KOH 12.34g (0.22mol) is at N 2Protection is dissolved in respectively down in the deionized water that 90mL boiled; Under stirring fast, KOH 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 K 2S 2O 8Oxidant 16.20g (0.06mol) 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 10h 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 12h, make product of the present invention then.ICP and XRD analysis show that product consists of Li 0.91MnO 2, belonging to rhombic system layered lithium manganate structure, electro-chemical test shows reversible capacity 193mAhg first -1Capacity still keeps 90% of initial capacity after the circulation of 10 weeks.
Embodiment 3:
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 product of the present invention then.ICP and XRD analysis show that product consists of Li 0.99MnO 2, belonging to rhombic system layered lithium manganate structure, electro-chemical test shows reversible capacity 202mAhg first -1, 10 times circulation back reversible capacity has still kept 90% of initial capacity.

Claims (4)

1, a kind of positive electrode laminated cell lithium manganate of lithium ion Li xMnO 20.8 the oxidation of≤x≤1.0-intercalation preparation method, processing step comprises:
A is dissolved in soluble manganese salt, highly basic in the deionized water that boiled under nitrogen protection respectively, and being mixed with concentration is 0.5～2.0molL -1Manganese salt solution and strong base solution, with the two by generating Mn (OH) 2Stoichiometric proportion or ratio hybrid reaction and ageing 5～20h under 60～80 ℃ of temperature of highly basic excessive 5%～20%, obtain layer structure Mn (OH) 2The suspension-turbid liquid precursor material;
B is 5～15 ratio in the Li/Mn mol ratio, and lithium compound intercalation object 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% -1Oxidant to assist the carrying out of intercalation, oxidation intercalation time 5～20h;
C also uses deionized water wash 3～4 times with the product suction filtration of step B, and vacuumize 6～24h under 100～150 ℃ of temperature makes layered lithium manganate Li then xMnO 2
2, layered lithium manganate Li according to claim 1 xMnO 20.8 the oxidation of≤x≤1.0-intercalation preparation method is characterized in that the described soluble manganese salt of steps A is manganese nitrate Mn (NO 3) 2, manganese sulfate MnSO 4, manganese chloride MnCl 2, manganese acetate Mn (CH 3COO) 2In any one; The described highly basic of steps A is potassium hydroxide KOH or NaOH NaOH.
3, layered lithium manganate Li according to claim 1 xMnO 20.8 the oxidation of≤x≤1.0-intercalation preparation method is characterized in that the described lithium compound intercalation of step B object is the LiOH pressed powder, or solubility lithium salts LiCl, LiNO 3, Li 2SO 4Any one or multiple mixture, but when adding the solubility lithium salts, simultaneously will be to Mn (OH) 2Add NaOH NaOH or potassium hydroxide KOH in the suspension-turbid liquid, to guarantee OH in this reaction system -Molar concentration 〉=1molL -1, excessive LiOH, the solubility lithium salts in reaction back reclaims and uses.
4, layered lithium manganate Li according to claim 1 xMnO 20.8 the oxidation of≤x≤1.0-intercalation preparation method is characterized in that the described oxidant of step B is potassium peroxydisulfate K 2S 2O 8, ammonium persulfate (NH 4) 2S 2O 8, clorox NaClO or hydrogen peroxide H 2O 2In any one.
CNB031386261A 2003-05-27 2003-05-27 Preparation of oxidized inserting layer of laminated lithium manganate as lithium ion battery anode Expired - Fee Related CN1254872C (en)

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CN1322607C (en) * 2005-04-27 2007-06-20 吉林大学 Method for producing positive pole material-orthorhombic system LiMnO2 of lithium secondary battery
CN100459239C (en) * 2005-12-28 2009-02-04 比亚迪股份有限公司 Method for preparation of the anode of lithium ion battery
CN102983325B (en) * 2012-12-28 2015-09-30 长沙矿冶研究院有限责任公司 The preparation method of positive electrode laminated cell lithium manganate of lithium ion
CN104966832A (en) * 2015-06-02 2015-10-07 中国科学院青海盐湖研究所 Method for electrochemical-chemical reaction preparation of metal oxide or multi-metal oxide electrode material
JP6956039B2 (en) * 2018-03-06 2021-10-27 Ｊｘ金属株式会社 Positive Active Material for Lithium Ion Battery, Method for Manufacturing Positive Active Material for Lithium Ion Battery, Positive Positive for Lithium Ion Battery and Lithium Ion Battery
CN112701262B (en) * 2020-12-29 2022-07-22 浙江工业大学 Inert Li2MnO3Phase-doped layered lithium manganate material and preparation and application thereof
CN113078310B (en) * 2021-04-19 2023-03-21 贵州源驰新能源科技有限公司 Intercalation MnO 2 And method for preparing the same
CN114497526B (en) * 2022-01-28 2023-11-14 中南大学 Method for synthesizing ternary positive electrode material

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