CN100373668C - Laminar vanadium-manganese oxide as positive electrode material of lithium ion cell and preparation method thereof - Google Patents

Laminar vanadium-manganese oxide as positive electrode material of lithium ion cell and preparation method thereof Download PDF

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CN100373668C
CN100373668C CNB2004100428608A CN200410042860A CN100373668C CN 100373668 C CN100373668 C CN 100373668C CN B2004100428608 A CNB2004100428608 A CN B2004100428608A CN 200410042860 A CN200410042860 A CN 200410042860A CN 100373668 C CN100373668 C CN 100373668C
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vanadium
oxide
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manganese oxide
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CN1705152A (en
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段雪
卫敏
路艳罗
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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
    • H01M4/36—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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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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Abstract

The present invention refers to a laminated vanadium-manganese oxide of a lithium ion battery positive electrode material and a preparation thereof. The chemical composition formula of the laminated vanadium-manganese oxide is Mn<x>v<2-x>o<5+/-delta>. nH2O, wherein the x is not less than 0 and is not more than or equal to 0.66; the delta is not less than 0 and is not more than or equal to 0.12; the n is not less than 1.40 and is not more than or equal to 1.52; the laminated vanadium-manganese oxide has a laminated and monoclinic structure; lamination spacing is from 9 to 11*. The preparation method comprises the steps that firstly, a reducing agent is used for reducing V2O5 in a sulfuric acid solution into VOSO4 and generates an oxidation-reduction reaction with the VOSO4 by MnO2 to obtain the laminated vanadium-manganese oxide with Mn (IV) doped on a V2O5 laminated plate. In the process of the charge and discharge cycle of the positive electrode material of the laminated vanadium-manganese oxide, a lithium ion Li<+> can carry out reversible de-intercalation, the capacity is kept more than 205mAh. g<-1 > after the charge and discharge cycles of 20 times. The positive electrode material prepared by the present invention has the advantages of stable structure and large capacity, and has the advantages that the capacity does not basically fade in the process of the charge and discharge cycles, the electrochemical performance of a battery is greatly increased.

Description

Anode material for lithium-ion batteries stratiform vanadium Mn oxide and preparation method thereof
Technical field:
The present invention relates to a kind of anode material for lithium-ion batteries stratiform vanadium Mn oxide and preparation method thereof.
Background technology:
The positive electrode reversible specific capacity is lower in the lithium ion battery, cycle performance is relatively poor, it is the governing factor that influences the lithium ion battery overall performance, it is the important step of research and development lithium ion battery, the positive electrode that particularly research and develop novel height ratio capacity, has extended cycle life, extremely people pay attention to always.
At present, people mainly concentrate on LiCoO to the research of anode material for lithium-ion batteries 2, LiNiO 2With spinelle LiMn 2O 4On the different materials, and less to the research of lithium-barium oxide.Lithium-barium oxide is as electrode material and LiCoO 2Compare and have the low advantage of cost, with LiNiO 2Compare advantage, with spinelle LiMn with easy preparation 2O 4Compare and have the high advantage of specific capacity, in addition, barium oxide also have stable in the air and voltage platform low, be not easy to cause advantages such as electrolyte decomposition.Therefore, it is a kind of very promising positive electrode active materials.Because the multivalence of vanadium can form VO 2, V 2O 5, V 6O 13, V 4O 9And V 3O 7Etc. multiple barium oxide, these barium oxides can form stratiform lithium intercalation compound Li xVO 2And Li 1+xV 3O 8, can form spinel-type Li again xV 2O 4And inverse spinel structure LiNiVO 4Deng lithium intercalation compound.
The barium oxide structure is of a great variety, and is bigger as the electrode material lithium-inserting amount, still, and spinel-type Li xV 2O 4And inverse spinel structure LiNiVO 4Chemical property Deng lithium intercalation compound is relatively poor, and capacity attenuation is very fast in charge and discharge process.The layer structure lithium-barium oxide has good embedding lithium ability, as positive electrode have the specific capacity height, advantage such as have extended cycle life, but its structural instability, thereby cause the electrochemistry cycle performance relatively poor, the electrochemical specific capacity decay is very fast.In order to stablize the structure of stratiform barium oxide, improve its cycle performance, people study and have adopted several different methods, carry out with other elements that the pillared people of being study at most and effect is also a kind of, mainly comprise pillared and organic molecule tetramethyl amine pillared etc. of pillared, transient metal Mn, Zn and the Fe of alkali metal ion.
At document (1) Journal of Power Sources, 2001, among the 92:204, people such as Ping Liu use KMnO under hydrothermal condition 4Oxidation VOSO 4Obtain K 0.16Mn 0.04V 2O 4.940.14H 2O, XRD result is indicated as layer structure, and interlamellar spacing is 10.88 , and K and Mn ion are positioned at V 2O 5Interlayer, stablized layer structure, reversible charge/discharge capacity reaches 190mAhg -1, capacity attenuation is slow in the charge and discharge cycles process.
At document (2) Electrochemistry Communications, 2000, among the 2:69, people such as Fan Zhang prepare δ-[N (CH under hydrothermal condition 3) 4] zMn yV 2O 5NH 2O, interlayer adopts N (CH 3) 4 +And Mn 2+Pillared, interlamellar spacing reaches 13 , and discharge capacity reaches 220mAhg first -1, cycle performance is tested.
At document (3) Materials Research Bulletin, 1997, among the 32:701, Fan Zhang etc. has prepared ferrovanadium oxide and almagrerite oxide, and interlayer adopts N (CH 3) 4 +Pillared rock-steady structure, interlamellar spacing are respectively 13.1  and 10.43 , [N (CH 3) 4] zFe yV 2O 5NH 2After the O roasting, has only orthohormbic structure V among the XRD 2O 5The diffraction maximum of phase.[N (CH 3) 4] zFe yV 2O 5NH 2The reaction of embedding lithium, the Li of about 0.88mol are carried out in O assembled battery +Between embeding layer, charge/discharge capacity is lower, but cycle performance is better.[N (CH 3) 4] zZn yV 2O 5NH 2O has lower lithium-inserting amount.The first charge-discharge capacity of pillared vanadium oxide reaches 150～200mAhg -1, but capacity is constantly decayed in charge and discharge process.
Summary of the invention:
The objective of the invention is in order to solve V 2O 5Change easily as the electrode material structure, the problem that electrochemical specific capacity is decayed rapidly in charge and discharge process provides unattenuated substantially anode material for lithium-ion batteries stratiform vanadium Mn oxide of a kind of Stability Analysis of Structures, electrochemical specific capacity and preparation method thereof.
Stratiform vanadium manganese oxide anode material provided by the invention is that the position of the part of V (V) on the stratiform vanadium oxide laminate is replaced with Mn (IV), and Mn (IV) is evenly distributed on by V 2O 5On the main body laminate that constitutes, its chemical formula can be expressed as:
Mn xV 2-xO 5±δ·nH 2O
0＜x≤0.66,0＜δ≤0.12,0＜n≤1.52 wherein;
Its structure is a monoclinic system, and interlamellar spacing 9～11 , c direction of principal axis grain size are at 10～200nm, and Mn and V exist with+5 valencys with+4 respectively in the sample;
This stratiform vanadium manganese oxide anode material adopts oxide-reduction method to prepare, and promptly adopts reducing process to prepare solubility VOSO earlier 4, prepare the stratiform vanadium oxide by redox reaction again, simultaneously manganese is introduced on the laminate, to obtain stratiform vanadium manganese oxide anode material.
Concrete processing step is as follows:
A. press V 2O 5With the sulfuric acid mol ratio be 1～10: 1 ratio, with commercially available orthohormbic structure V 2O 5Join in the sulfuric acid solution, be heated to 40～100 ℃, add the reducing agent of scheduled volume again, at 40～100 ℃ of heating 1～10h, it is reacted completely, the solution that obtains is cooled to room temperature, remove by filter wherein a small amount of insoluble matter, filtrate is VOSO 4Solution;
Wherein reducing agent is H 2Any in S, sulfurous acid, oxalic acid, tartaric acid, formic acid, the acetate, the reducing agent consumption is by with V in the above-mentioned solution 2O 5Middle V (V) is reduced to V (IV) aequum and adds.
B. the pure potassium permanganate of commercially available analysis is put into crucible, in electric furnace, be warming up to 400～800 ℃ with the speed of 10～100 ℃/h, keep 5～10h, reduce to room temperature, fully wash with deionized water again, filter, filter cake obtains stratiform δ-MnO at 20～100 ℃ of drying 10～60h 2
C. the VOSO that steps A is obtained 4Solution is transferred in the reaction vessel that band stirs, and is 0.1～2: 1 ratio in the Mn/V mol ratio, stratiform δ-MnO that step B is obtained 2Be added to VOSO 4In the solution, under 20～80 ℃ of temperature, reaction 24～120h filters, and fully washs with deionized water, at 20～100 ℃ of drying 24～60h, obtains stratiform vanadium manganese oxide anode material.
Adopt X-ray powder diffraction (XRD) to characterize product structure, infrared spectrum (IR) characterizes V and becomes bonded state with Mn in sample, the crystal morphology of transmission electron microscope (TEM) observation sample, grain size distribute, and x-ray photoelectron power spectrum (XPS) characterizes average valence and the relative amount of sample surfaces Mn and V.The content of vanadium and manganese element in employing inductive coupling plasma emission spectrograph (ICP) the mensuration product, its results of elemental analyses is shown in Table 1.The chemical composition that shows product meets Mn xV 2-xO 5 ± δNH 2O (wherein 0＜x≤0.66,0＜δ≤0.12,0＜n≤1.52), Mn (IV) are entrained in and form stratiform vanadium Mn oxide on the laminate.
Electrochemical property test is the result show: the stratiform vanadium Mn oxide that adopts the inventive method to prepare, and with pillared stratiform V 2O 5Compare, reversible specific capacity improves 10mAhg first -1, along with the increase of Mn doping, the lithium-inserting amount capacity reduces by 10～30% first.Stratiform vanadium Mn oxide is carried out charge and discharge cycles, and cycle performance improves a lot, and reversible capacity remains on 205mAhg after 20 charge and discharge cycles -1More than, capacity is unattenuated substantially.Compare with pillared vanadium oxide on the document, cycle performance and reversible specific capacity all increase.
Vanadium Mn oxide after the charge and discharge cycles is carried out structural characterization, and structures of samples does not change before and after the circulation.
Advantage of the present invention is: adopt oxide-reduction method provided by the invention can obtain to have the vanadium Mn oxide electrode material of layer structure, this electrode material laminate adopts Mn (IV) to mix, stable laminated structure preferably, thus higher specific capacity and excellent cycle performance in charge and discharge process, had.With stratiform MnO 2As oxidant and dopant, preparation technology is simple, helps stratiform V simultaneously 2O 5Generation.Compare with the pillared vanadium oxide of interlayer, stratiform vanadium Mn oxide structure in charge and discharge process that the laminate doping obtains is more stable, and chemical property has bigger raising.
Description of drawings:
Fig. 1 is the TEM figure of vanadium Mn oxide under embodiment 1 preparation condition.
Fig. 2 is the charging and discharging curve of the vanadium Mn oxide under embodiment 1 preparation condition.
Fig. 3 is preceding 20 the cycle charge-discharge specific capacities of the vanadium Mn oxide under embodiment 1 preparation condition.
Embodiment:
Embodiment 1
A. measure 93%H 2SO 45mL is diluted to the 40mL acid solution, takes by weighing V 2O 50.03mol oxalic acid 0.06mol successively joins in the sulfuric acid solution, 80 ℃ are heated to no gas and emit, and after reacting completely, obtain navy blue VOSO 4The aqueous solution.Reduce to room temperature, remove by filter a small amount of unreacted V 2O 5, obtain VOSO 4The aqueous solution, adding the suitable quantity of water constant volume is 100mL.
B. with KMnO 4At 600 ℃ of roasting 5h, 50 ℃/h of programming rate fully washs sample to colourless with deionized water after the roasting, and 70 ℃ of dry 24h obtain stratiform MnO 2
C. take by weighing 0.03mol MnO 2Join VOSO 4In the solution, to＜1, react 90h with the sulphur acid for adjusting pH value under 20 ℃, stirring condition, solution is become colorless by blueness.Deionized water fully washs to filtrate and becomes neutral, filters and obtains the dark brown oxide, at 70 ℃ of dry 12h, obtains Mn 0.13V 1.87O 4.931.43H 2O.
The vanadium Mn oxide that obtains is carried out XRD characterize, show that sample has layer structure, belong to monoclinic system, interlamellar spacing is 10.8 ; Adopt the pattern of tem observation sample, structure is seen Fig. 1, and sample has layer structure as seen from Figure 1.
ICP and XPS analyze its chemical composition and element valence, and the result shows that Mn and V exist with+5 valencys with+4 respectively.
Chemical property characterizes: the stratiform vanadium Mn oxide that obtains and commercially available acetylene black conductive agent and the polytetrafluoroethylene binding agent mass fraction by (85: 10: 5) is mixed, and suppress film forming, electrode film thickness is 100 μ m, is cut into 0.38cm 2Disk, in 120 ℃ of vacuum (＜1Pa) dry 24h.As to electrode, adopt Celgard 2400 barrier films, 1molL with metal lithium sheet -1LiClO 4EC+DEC (EC/DEC volume ratio 1: 1) solution be electrolyte, at dry argon gas glove box (H 2O＜1ppm, O 2＜be assembled into button cell in 1ppm), adopt cell tester to carry out electrochemical property test, operating voltage range is 2.0～4.0V (vs Li), and operating current is 0.1mA, and Electrochemical results sees Table 1.
After the electrochemistry loop ends, electrode film is carried out structural characterization, show that the structure of circulation front and back electrode material does not change by XRD.
Embodiment 2
Adopt with embodiment 1 steps A and B same procedure and prepare VOSO 4The aqueous solution and MnO 2
Take by weighing 0.045mol MnO 2Join VOSO 4In the solution, to＜1, react 80h with the sulphur acid for adjusting pH value under 30 ℃ of stirring conditions, solution is become colorless by blueness.Deionized water fully washs to filtrate and becomes neutral, filters and obtains the dark brown oxide, at 70 ℃ of dry 12h, obtains Mn 0.28V 1.72O 5.121.52H 2O.XRD shows that sample has layer structure, belongs to monoclinic system, and interlamellar spacing is 9.8 .
Adopt the condition identical to carry out electro-chemical test, the results are shown in Table 1 with embodiment 1.Structure through 20 circulation rear electrode material does not change.
Embodiment 3
A. measure 93%H 2SO 45mL is diluted to the 40mL acid solution, takes by weighing V 2O 50.03mol acetate 0.06mol successively joins in the sulfuric acid solution; 90 ℃ are heated to no gas and emit, and after reacting completely, obtain navy blue VOSO 4Solution.Reduce to room temperature, remove by filter a small amount of unreacted V 2O 5, obtain VOSO 4The aqueous solution, adding the suitable quantity of water constant volume is 100mL.
B. with embodiment 1.
C. take by weighing 0.06mol MnO 2Join VOSO 4In the solution, react 60h with the sulphur acid for adjusting pH value down to＜1,40 ℃ of stirring conditions, solution is become colorless by blueness.Deionized water fully washs to filtrate and becomes neutral, filters and obtains the dark brown oxide, at 70 ℃ of dry 12h, obtains Mn 0.66V 1.34O 4.961.41H 2O, XRD show that sample has layer structure, belong to monoclinic system, and interlamellar spacing is 9.6 .
Adopt the condition identical to carry out electro-chemical test, the results are shown in Table 1 with embodiment 1.Structure through 20 circulation rear electrode material does not change.
Comparative Examples 4
Adopt the method for document (1) to prepare pillared vanadium oxide K 0.16Mn 0.04V 2O 4.940.14H 2O.Adopt the condition identical to carry out electrochemical property test, the results are shown in Table 1 with embodiment 1.
The composition of table 1 electrode material and chemical property
Sample Chemical composition Reversible specific capacity mAhg -1
First 10 20
Embodiment 1 Mn 0.13V 1.87O 4.93·1.43H 2O 203.8 198.2 205.4
Embodiment 2 Mn 0.28V 1.72O 5.12·1.52H 2O 175.5 171.8 170.3
Embodiment 3 Mn 0.66V 1.34O 4.96·1.41H 2O 143.3 138.5 134.0
Comparative Examples 4 K 0.16Mn 0.04V 2O 4.94·0.14H 2O 190 178 165

Claims (2)

1. anode material for lithium-ion batteries stratiform vanadium Mn oxide, its chemical formula is:
Mn xV 2-xO 5±δ·nH 2O
0＜x≤0.66,0＜δ≤0.12,0＜n≤1.52 wherein;
The structure of this oxide is a monoclinic system, and interlamellar spacing is 9～11 , and c direction of principal axis grain size is at 10～200nm, and Mn and V exist with+5 valencys with+4 respectively.
2. the preparation method of an anode material for lithium-ion batteries stratiform vanadium Mn oxide, concrete steps are as follows:
A. press V 2O 5With the sulfuric acid mol ratio be 1～10: 1 ratio, with orthohormbic structure V 2O 5Join in the sulfuric acid solution, be heated to 40～100 ℃, add the reducing agent of scheduled volume again, at 40～100 ℃ of heating 1～10h, it is reacted completely, the solution that obtains is cooled to room temperature, remove by filter wherein a small amount of insoluble matter, filtrate is VOSO 4Solution;
Wherein reducing agent is H 2Any in S, sulfurous acid, oxalic acid, tartaric acid, formic acid, the acetate, the reducing agent consumption is by with V in the above-mentioned solution 2O 5V (V) be reduced to the needed amount of V (IV);
B. will analyze pure potassium permanganate and put into crucible, in electric furnace, be warming up to 400～800 ℃ with the speed of 10～100 ℃/h, keep 5～10h, reduce to room temperature, fully wash with deionized water, filter, filter cake obtains stratiform δ-MnO at 20～100 ℃ of drying 10～60h 2
C. the VOSO that steps A is obtained 4Solution is transferred in the reaction vessel that band stirs, and is 0.1～2: 1 ratio in the Mn/V mol ratio, stratiform δ-MnO that step B is obtained 2Be added to VOSO 4In the solution, under 20～80 ℃ of temperature, reaction 24～120h filters, and fully washs with deionized water, at 20～100 ℃ of drying 24～60h, obtains stratiform vanadium manganese oxide anode material.
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EP2081242A4 (en) * 2006-11-10 2011-11-30 Fuji Heavy Ind Ltd Electrode material, electrode material manufacturing method and nonaqueous lithium secondary battery
EP2104174A4 (en) * 2006-11-10 2011-12-07 Fuji Heavy Ind Ltd Lithium-ion secondary battery
EP2638581A2 (en) 2010-10-15 2013-09-18 University Of Washington Through Its Center For Commercialization V2o5 electrodes with high power and energy densities
US9997778B2 (en) 2012-11-05 2018-06-12 University Of Washington Through Its Center For Commercialization Polycrystalline vanadium oxide nanosheets
CN103208619B (en) * 2013-03-13 2015-02-04 武汉理工大学 Potassium ion embedded type vanadium pentoxide nanowire and preparation method thereof and application thereof
CN103757401A (en) * 2013-12-29 2014-04-30 四川师范大学 Leaching method of waste battery electrode mixed material
CN103757318A (en) * 2013-12-29 2014-04-30 四川师范大学 Method for leaching positive-negative pole material mixture of waste nickel-metal hydride battery
CN103757263B (en) * 2013-12-29 2016-02-24 四川师范大学 The leaching method of anode material of used nickel cadmium battery
CN105154980B (en) * 2015-06-19 2017-08-11 福州大学 A kind of anode material of lithium battery and preparation method thereof

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CN1298210A (en) * 1999-11-30 2001-06-06 中国科学院成都有机化学研究所 Cathode material for lithium ion battery and its making process

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