CN100373668C - Lithium-ion battery cathode material layered vanadium manganese oxide and preparation method thereof - Google Patents
Lithium-ion battery cathode material layered vanadium manganese oxide and preparation method thereof Download PDFInfo
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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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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 12
- FKBGOUXGDAMMHP-UHFFFAOYSA-N [V+5].[O-2].[Mn+2] Chemical compound [V+5].[O-2].[Mn+2] FKBGOUXGDAMMHP-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000010406 cathode material Substances 0.000 title claims abstract 5
- 239000011572 manganese Substances 0.000 claims abstract description 45
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 239000007774 positive electrode material Substances 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 239000011229 interlayer Substances 0.000 claims description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims 2
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims 2
- 235000011054 acetic acid Nutrition 0.000 claims 1
- 238000005485 electric heating Methods 0.000 claims 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 5
- 238000007599 discharging Methods 0.000 abstract description 2
- 238000006479 redox reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 18
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 16
- 239000007772 electrode material Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 239000010405 anode material Substances 0.000 description 8
- 238000000634 powder X-ray diffraction Methods 0.000 description 8
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 230000002441 reversible effect Effects 0.000 description 6
- 229910001935 vanadium oxide Inorganic materials 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- STUKNTHDFYCZOR-UHFFFAOYSA-N [Ba+2].[O-2].[Li+] Chemical compound [Ba+2].[O-2].[Li+] STUKNTHDFYCZOR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical class [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- -1 tetramethyl amine Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000628 Ferrovanadium Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明涉及一种锂离子电池正极材料层状钒锰氧化物及其制备方法。该层状钒锰氧化物的化学组成式为MnxV2-xO5±δ·nH2O，其中0＜x≤0.66，0＜δ≤0.12，1.40＜n≤1.52，具有层状单斜结构，层间距为9～11。其制备方法是先用还原剂在硫酸溶液中将V2O5还原为VOSO4，再通过MnO2与VOSO4发生氧化还原反应，得到Mn(IV)掺杂在V2O5层板上的层状钒锰氧化物。该层状钒锰氧化物正极材料在充放电循环过程中，锂离子Li+能够可逆脱嵌，充放电循环20次后容量保持在205mAh·g-1以上。本发明制备的正极材料结构稳定，容量较大，并且在充放电循环过程中容量基本不衰减，对电池的电化学性能有更大提高。The invention relates to a layered vanadium manganese oxide, a cathode material of a lithium ion battery, and a preparation method thereof. The chemical composition formula of the layered vanadium manganese oxide is Mn x V 2-x O 5±δ ·nH 2 O, where 0<x≤0.66, 0<δ≤0.12, 1.40<n≤1.52, and has layered single Inclined structure, the layer spacing is 9-11. The preparation method is to reduce V 2 O 5 to VOSO 4 in a sulfuric acid solution with a reducing agent, and then undergo a redox reaction between MnO 2 and VOSO 4 to obtain Mn(IV)-doped V 2 O 5 laminates. layered vanadium manganese oxide. The layered vanadium manganese oxide positive electrode material can reversibly deintercalate lithium ions Li + during charge and discharge cycles, and the capacity remains above 205mAh·g -1 after 20 charge and discharge cycles. The cathode material prepared by the invention has a stable structure and a large capacity, and the capacity basically does not attenuate during the charging and discharging cycle process, and the electrochemical performance of the battery is greatly improved.
Description
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.
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 |
| |
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 |
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| WO2012051619A2 (en) | 2010-10-15 | 2012-04-19 | 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 |
| 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 |
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| CN105154980B (en) * | 2015-06-19 | 2017-08-11 | 福州大学 | A kind of anode material of lithium battery and preparation method thereof |
| CN115000531B (en) * | 2022-05-18 | 2025-06-17 | 北京大学深圳研究生院 | Aqueous zinc ion battery |
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