CN1322607C - Method for producing positive pole material-orthorhombic system LiMnO2 of lithium secondary battery - Google Patents

Method for producing positive pole material-orthorhombic system LiMnO2 of lithium secondary battery Download PDF

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Publication number
CN1322607C
CN1322607C CNB2005100167513A CN200510016751A CN1322607C CN 1322607 C CN1322607 C CN 1322607C CN B2005100167513 A CNB2005100167513 A CN B2005100167513A CN 200510016751 A CN200510016751 A CN 200510016751A CN 1322607 C CN1322607 C CN 1322607C
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manganese
limno
lithium secondary
limno2
distilled water
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CN1674322A (en
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陈岗
赵丽竹
杜菲
王春忠
黄祖飞
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Jilin University
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Jilin University
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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
    • H01M4/36—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

Abstract

The present invention belongs to the field of battery material preparation, particularly to a hydrothermal method for preparing positive pole material-orthorhombic system LiMnO2 of lithium secondary batteries. According to the molar ratio of 1:1:7.5 to 30, manganous compounds, manganese dioxide and lithium hydroxide are dissolved in distilled water and are stirred for 4 to 6 hours in room temperature air, and then are filled in a high pressure reactor to carry out constant temperature reaction for 5 to 7 days at a temperature of 170 to 230 DEG C; after taken out of the high pressure reactor, the mixture is cleaned by thin oxalic acid until the pH value is neutral, and then is cleaned by distilled water or deionized water; finally, precipitates are dewatered and dried to obtain orthorhombic system LiMno2 powder. The method of the present invention has the advantages of low equipment requirement, simple synthetic method, low technical requirement, wide chemical proportion and easy bulk production; the material synthesized by the present invention has the characteristics of single phase, good crystallization, structure stability, large electrochemical capacity, high energy density, etc. Mn elements can completely replace poisonous Co elements, which is favorable to protect environment and greatly reduce the material cost.

Description

Positive electrode material of lithium secondary cell-rhombic system LiMnO 2The preparation method
Technical field
The invention belongs to a kind of preparation method of battery material, be specifically related to positive electrode material of lithium secondary cell-rhombic system LiMnO 2Hydrothermal preparing process.
Background technology
Since lithium secondary battery comes out, be subjected to worldwide extensive concern always.In numerous areas such as portable electric appts, electric automobile, space technology and national defense industry, wide prospect and huge economic benefit have been represented with advantages such as its high voltage, high-capacitance, long service life, good cycle.
The deciding factor of lithium secondary battery performance is its positive electrode.The operating voltage of battery (lithium ion deviating from positive electrode-insert voltage), operating time (energy storage density of positive electrode and charge and discharge cycles attribute), stability critical natures such as (structural stability of positive electrode under various conditions of work) are all determined by positive electrode.At present, the positive electrode of commercialization lithium rechargeable battery is LiCoO 2LiCoO 2Has a-NaFeO 2Structure, the cubic packing of oxygen atom solid matter.After Li deviate from fully, oxygen atom rearranged the CoO that forms cubic lattice 2Although LiCoO 2Fail safe, capacitance, cycle performance all very outstanding, unfavorable to environmental protection but because the Co element is poisonous, defective such as cost an arm and a leg has limited its application on more extensive.Based on LiCoO 2Above defective, seek that chemical property is outstanding, security performance novel positive electrode material of lithium secondary cell stable more, environmentally safe becomes the task of top priority.LiMnO in numerous reserved materials 2With nontoxic, the ABUNDANT NATUREAL RESOURSES of its Mn element, advantage such as theoretical capacitance is big is considered to LiCoO 2One of best substitution material.
LiMnO 2Mainly exist: monoclinic system LiMnO with three kinds of forms 2, rhombic system LiMnO 2With cubic system LiMnO 2Monoclinic system LiMnO 2Has a-NaFeO 2Structure is with LiCoO 2Structural similarity, space group are C2/m, are write as m-LiMnO usually 2Rhombic system LiMnO 2Have the stratiform rock salt structure, space group is Pmnm, is write as o-LiMnO usually 2Cubic system LiMnO 2Be the cubic spinel phase, have unordered cube Nacl type structure, write as c-LiMnO usually 2C-LiMnO wherein 2Theoretical capacitance low, and m-LiMnO 2And o-LiMnO 2Theoretical capacitance identical, all be 286mAh/g.But because m-LiMnO 2Be difficult to synthesize, so o-LiMnO 2Become a focus of positive electrode research in the last few years.O-LiMnO 2Synthetic method mostly is high temperature solid-state method and ion-exchange, and reaction temperature is between 500 ℃-1000 ℃.Synthesis technique is strict, equipment requirements is accurate, is difficult to produce in batches.
Summary of the invention
The object of the present invention is to provide a kind of positive electrode material of lithium secondary cell-rhombic system LiMnO 2Hydrothermal preparing process.This preparation method has that reaction temperature is low, reaction process is simple, loose to the consersion unit requirement, the suitable characteristics of easily producing in batches.
The molecular formula of lithium ion secondary battery anode material of the present invention is rhombic system-LiMnO 2, molecular weight is 93.88, space group Pmnm, adjacent MnO 6Rib has high-spin manganic ion Mn altogether 3+, its theoretical capacitance can reach 286mAh/g.This material structure is stable, good crystallinity, have high electrochemical performance.Because Mn is nontoxic and at the occurring in nature aboundresources, is a kind of novel " green " electrode material.
Lithium ion secondary battery anode material rhombic system LiMnO of the present invention 2The method of synthetic employing be hydrothermal method.Hydrothermal method is that with the difference of solid phase reaction maximum " reactivity " is different.The mechanism of solid phase reaction mainly is characteristics with the interfacial diffusion; And hydro-thermal reaction mainly is characteristics with the liquid phase reactor.In hydro-thermal reaction, the system of research is in imperfect nonequilibrium condition.Under high-temperature and high-pressure conditions, water is in critical or supercriticality, and reactivity improves.Rerum natura and the chemical reaction performance of material in solvent all has very big change, so the solvent thermal chemical reaction is easy to normality greatly.
In the design process of response path, we have done suitable adjustment, make that it is simple more, be easy to produce.Method of the present invention is: the compound (as: manganese acetate Mn (CH that with mol ratio is 1: 1: 7.5～30 bivalent manganese 3COO) 2, manganese chloride MnCl 2, manganese sulfate MnSO 4With manganese nitrate Mn (NO 3) 2Deng), manganese dioxide (MnO 2) and lithium hydroxide (LiOHH 2O) be dissolved in the distilled water, in air at room temperature, stirred 4～6 hours, the autoclave of packing into then, 170～230 ℃ of isothermal reactions 5～7 days, clean to pH value neutrality with rare oxalic acid after going out still, and then with distilled water or washed with de-ionized water, the oven dry of at last sediment being anhydrated promptly obtains rhombic system LiMnO 2Powder.
The consumption of distilled water assurance reactive material can fully dissolve and get final product in the said method, and concrete can be with the lithium hydroxide (LiOHH that respectively is compound, manganese dioxide and the 0.075mol～0.30mol of the bivalent manganese of 0.01mol 2O) carry out next step reaction again after being dissolved in 40～80ml distilled water.
The reaction raw materials source is as follows: manganese acetate Mn (CH 3COO) 2, manganese chloride MnCl 2Originate from the Beijing Chemical Plant; Manganese dioxide (MnO 2) originate from Tianjin chemical reagent three factories; Lithium hydroxide (LiOHH 2O) originate from Shenyang City Xin Xi chemical reagent work.
This preparation method is low for equipment requirements, synthetic method is simple, technological requirement is low, stoicheiometry is loose, be easy to batch process.Characteristics such as that synthetic material has is single-phase, good crystallinity, Stability Analysis of Structures, electrochemistry capacitance are big, high-energy-density.Material replaces poisonous Co element fully with the Mn element, has both helped environmental protection, has reduced the cost of material again significantly.
Description of drawings
The rhombic system LiMnO of Fig. 1: embodiment 1 preparation 2The X-RAY diffracting spectrum of dusty material;
LiOHH among Fig. 2 (a) and (b): the embodiment 2 2When the O consumption is 0.075mol, make the sample photo of the scanning electron microscopy shooting of sample;
The X-RAY diffracting spectrum of three samples among Fig. 3: the embodiment 2.
As shown in Figure 1, through comparing, with card 01-086-355 with rhombic system dusty material standard spectrum [2](rhombic system LiMnO 2) meet fully, illustrate that this material belongs to rhombic system LiMnO 2The peak position at three strongest ones peak is as follows: 15.419 °; 24.951 °; 45.127 °.Cell parameter is as follows: a=4.5670; B=5.7447; C=2.8059; V=73.6157.We can see that the diffraction linearity is sharp keen from figure, there is no other diffracted rays and occur.People such as Kim [1]Prove that by experiment the shape of (110) diffraction maximum directly influences the cycle performance of battery.(110) peak of the sample that our hydro-thermal is synthetic, narrow bandwidth, intensity are strong, are indicating to have good electrochemistry cycle performance.
Fig. 2 is LiOHH in the example 2 2When the O consumption is 0.075mol, make the sample photo of the scanning electron microscopy shooting of material sample.Two photos (a) and (b) come from same sample, the selected location difference.As can be seen from the figure the crystal grain of sample is more even, on average below 500nm, can expect to have electrochemical properties preferably.
Embodiment
Embodiment 1:
With molal quantity is the Mn (CH of 0.01mol, 0.01mol, 0.17mol 3OO) 24H 2O, MnO 2, LiOHH 2O joins in the 40mL distilled water, stirs 4 hours in air at room temperature, in the 40ml autoclave of packing into then, 170 ℃ of constant temperature 5 days, clean to pH value neutrality with rare oxalic acid after going out still, and then use washed with de-ionized water, the oven dry of at last sediment being anhydrated obtains rhombic system LiMnO 2Powder.
At the synthetic LiMnO of hydro-thermal 2In the process, reactant liquor poured into the PH of test solution equals 14 before the reactor, present strong basicity, after 170 ℃ of isothermal reactions, survey the solution pH value when going out still again and still equal 14, we know LiMnO thus 2Require the strong basicity environment in the hydro-thermal building-up process.So when the raw material proportioning, will add excessive lithium hydroxide (LiOHH 2O), carry out to guarantee to be reflected under the strong basicity environment.
Embodiment 2:
Choose commercially available molecular weight and be 245.09 Mn (CH 3OO) 24H 2O, molecular weight are 86.94 MnO 2, molecular weight is 41.96 LiOHH 2O is as reaction raw materials.Mn (CH 3OO) 24H 2O, MnO 2Consumption, hydro-thermal synthesis temperature, reaction time and course of reaction identical with embodiment 1.Add raw material Li OHH 2The consumption of O is respectively: 0.075mol; 0.095mol; 0.14mol, resulting rhombic system LiMnO 2Performance, effect and embodiment 1 in basic identical.
We can learn orthorhombic-LiMnO from the XRD spectrum of sample 2Half-peak breadth along with the increase of LiOH concentration also slightly increases, but maximum also only has 0.261 ° (as shown in table 1).The orthorhombic-LiMnO that this explanation is synthesized with hydrothermal method 2Crystallinity is very intact.
Table 1:XRD spectrum top four peak bandwidth value
Embodiment 3:
Hydro-thermal synthesis temperature, reaction time and course of reaction are identical with embodiment 1.Be the influence of research differential responses raw material for product, we choose molecular weight is 197.91 manganese chloride (MnCl 24H 2O), molecular weight is 86.94 MnO 2, molecular weight is 41.96 LiOHH 2O is as reaction raw materials.The mol ratio of reaction raw materials is 0.005: 0.005: 0.14.React resulting product orthorhombic-LiMnO 2Performance, effect and embodiment 1 in basic identical.
List of references
[1]Jung-Min?Kim，Hoon-Taek?Chung，J.Power?Sources，2003，115：125
[2]Croguennec.L，Deniard.P，Bruce，R.，Lecerf.，J.Mater.Chem.Volume?5?page?1919(1995)

Claims (2)

1, positive electrode material of lithium secondary cell-rhombic system LiMnO 2The preparation method, the steps include: with mol ratio to be that compound, manganese dioxide and the lithium hydroxide of 1: 1: 7.5～30 bivalent manganese is dissolved in the distilled water, in air at room temperature, stirred 4～6 hours, the autoclave of packing into then, 170～230 ℃ of isothermal reactions 5～7 days, clean to pH value neutrality with rare oxalic acid after going out still, and then with distilled water or washed with de-ionized water, the oven dry of at last sediment being anhydrated promptly obtains rhombic system LiMnO 2Powder.
2, positive electrode material of lithium secondary cell as claimed in claim 1-rhombic system LiMnO 2The preparation method, it is characterized in that: the compound of bivalent manganese is manganese acetate, manganese chloride, manganese sulfate or manganese nitrate.
CNB2005100167513A 2005-04-27 2005-04-27 Method for producing positive pole material-orthorhombic system LiMnO2 of lithium secondary battery Expired - Fee Related CN1322607C (en)

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Publication number Priority date Publication date Assignee Title
CN100345769C (en) * 2006-03-14 2007-10-31 浙江大学 One step directly preparing process for lithium manganate as lithium ion cell positive pole material
CN103928670B (en) * 2013-06-26 2016-12-28 华中农业大学 A kind of positive electrode material of lithium secondary cell LiMnO2preparation method

Citations (4)

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Publication number Priority date Publication date Assignee Title
US5981106A (en) * 1996-06-13 1999-11-09 Japan Storage Battery Co., Ltd. Positive electrode active material for lithium battery, method for producing the same, and lithium battery containing the same
CN1553529A (en) * 2003-05-27 2004-12-08 北京化工大学 Preparation of oxidized inserting layer of laminated lithium manganate as lithium ion battery anode
CN1595686A (en) * 2003-09-10 2005-03-16 北京化工大学 Lithium manganate positive electrode material of laminated pole structure for lithium ion cell, and method for intercalation assembling and preparation thereof
CN1601785A (en) * 2004-10-20 2005-03-30 天津化工研究设计院 Method of prepn, of positive electrode laminated cell lithium manganate of lithium ion

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US5981106A (en) * 1996-06-13 1999-11-09 Japan Storage Battery Co., Ltd. Positive electrode active material for lithium battery, method for producing the same, and lithium battery containing the same
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CN1553529A (en) * 2003-05-27 2004-12-08 北京化工大学 Preparation of oxidized inserting layer of laminated lithium manganate as lithium ion battery anode
CN1595686A (en) * 2003-09-10 2005-03-16 北京化工大学 Lithium manganate positive electrode material of laminated pole structure for lithium ion cell, and method for intercalation assembling and preparation thereof
CN1601785A (en) * 2004-10-20 2005-03-30 天津化工研究设计院 Method of prepn, of positive electrode laminated cell lithium manganate of lithium ion

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Title
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Hydrothermal synthesis and electrochemical behavior of orthorhombic LiMnO2 Seung.Taek Myung,Shinichi Komaba,Naoaki Kumagai,Electrochimica Acta,Vol.20 No.47 2002;Low temperature hydrothermally synthesized nanocrystalline orthorhombic LiMnO2 cathode material for lithium-ion cells Mengqiang Wu,Ai Chen,Rongqing Xu,Yue Li,Microelectronic Engineering,Vol.38721 No.66 2003 *
Low temperature hydrothermally synthesized nanocrystalline orthorhombic LiMnO2 cathode material for lithium-ion cells Mengqiang Wu,Ai Chen,Rongqing Xu,Yue Li,Microelectronic Engineering,Vol.38721 No.66 2003 *

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