CN105304895A - Lithium-containing metal oxide lithium electricity nanoelectrode materials and preparation method thereof - Google Patents

Lithium-containing metal oxide lithium electricity nanoelectrode materials and preparation method thereof Download PDF

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CN105304895A
CN105304895A CN201510693752.5A CN201510693752A CN105304895A CN 105304895 A CN105304895 A CN 105304895A CN 201510693752 A CN201510693752 A CN 201510693752A CN 105304895 A CN105304895 A CN 105304895A
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metal oxide
lithium
transition metal
preparation
nano
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CN105304895B (en
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黄镇东
马延文
张坤
冯晓苗
刘瑞卿
李谊
林秀婧
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Nanjing Post and Telecommunication University
Nanjing University of Posts and Telecommunications
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M4/485—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
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 invention discloses lithium-containing metal oxide lithium electricity nanoelectrode materials and a preparation method thereof. Nanostructure metal oxide synthesized at low temperature through a water heating method, a solvent heating method, a sol-gel method and the like is subjected to pre-lithiation, and therefore the temperature at which a lithium-containing metal oxide crystal structure is formed and develops is effectively lowered, needed time is effectively shortened, the proportion and the mixed arranging degree of Li+ and transition metal ions in lithium-containing transition metal oxide can be effectively controlled, and the nanoscale and the structure of the metal oxide can be kept. Energy consumption in the material preparation process is greatly reduced, cost is reduced, meanwhile high-efficiency and high-rate lithium-containing transition metal oxide positive and negative materials can be obtained, and therefore the electrochemical pre-lithiation preparation method is an environment-friendly controlled preparation method of nano lithium-containing transition metal oxide nanostructure electrode materials.

Description

Containing lithium metal oxide lithium electricity nano-electrode material and preparation method thereof
Technical field
The present invention relates to a kind of containing lithium metal oxide lithium electricity nano-electrode material and low temperature preparation method thereof, particularly relate to a kind of electrochemistry prelithiation technology of preparing of lithium-containing transition metal oxide nano structure electrode material.
Background technology
Mankind nowadays society is in the highly energy-consuming stage; the fossil energy such as oil, natural gas is exhausted fast; energy crisis and problem of environmental pollution are day by day serious; therefore the environmental friendliness new energy technology such as solar energy, wind energy, biomass energy and tidal energy receives much concern, and how China also building a large amount of solar energy, wind energy and tidal power factory.But the electrode sent due to solar energy, wind energy and tidal energy is unstable, huge numbers of families and each enterprises and institutions cannot be entered by being incorporated to national public supply network, finally causing a large amount of generation of electricity by new energy factory and relevant device and manufacture of materials business loss even to close down.How to solve this key issue, with stable, cheap, conveniently mode successfully these new forms of energy electric power to be carried out peak regulation grid-connected and be applied to mobile electronic device and electric transportation instrument etc., be the focus of the focus paid close attention to of science and industrial circle and research always.
Lithium ion battery compares the conventional batteries such as plumbic acid and ni-mh, and to have energy density high, power density is high, safety, cost is low, the characteristics such as environmental friendliness, be considered high performance green energy-storing device, can be used for intelligent grid construction to assist the peak regulations such as solar energy, wind energy, tidal energy grid-connected, and be widely used as mobile electronic device, electric tool and electric car power supply etc.Lithium ion battery positive and negative electrode material is the important component part of battery, and the performance of electrode material governs power and the energy density of lithium ion battery always.Along with the development of Large Copacity energy storage device and power-type lithium ion battery, align, negative material has higher requirement.At present spinel lithium manganate (LiMn is mainly concentrated on to the application and research of high performance lithium ion battery anode material 2o 4), nickel manganese binary system [Li (Ni xmn y) O 2], cobalt manganese binary system [Li (Co xmn y) O 2] and nickel-cobalt-manganese ternary system [Li (Ni xco ymn z) O 2deng layered oxide and part polyanionic LiFePO 4 (LiFePO 4), phosphoric acid vanadium lithium (Li 3v 2(PO 4) 3) and fluorophosphoric acid system (as LiV 0.5fe 0.5pO 4f) etc.The research of anticathode material then mainly concentrates on lithium titanate (Li 4ti 5o 12) and transition-metals and their oxides and advanced material with carbon element.Lithium-containing transition metal oxide, owing to having the features such as higher voltage platform, larger capacity and tap density, comparatively outstanding multiplying power and cyclical stability, is considered to the richest prospect, is also current commercial Application lithium ion battery electrode material the most widely.
Present stage lithium-containing transition metal oxide spinel lithium manganate (LiMn 2o 4), rich lithium LiMn2O4 (Li 2mnO 3), nickel manganese binary system [Li (Ni xmn y) O 2], nickel-cobalt-manganese ternary system [Li (Ni xco ymn z) O 2with lithium titanate (Li 4ti 5o 12) etc. mainly by sol-gal process with utilize the precursor of the precipitation method or water heat transfer and lithium salts solid phase compound, form crystal through long High temperature diffusion again, wherein the high crystallizing and sintering temperature of LiMn2O4, lithium titanate and stratiform nickel, cobalt and manganese oxide compounds is about 800,900,1000 DEG C respectively.The at high temperature long-time sintering of more than the 10h avalanche of precursor nanostructure that directly causes low temperature to synthesize and sharply grow up (the becoming sub-micron even micron particles) of nano particle, cause Li in material crystal structure +mistake row between/transition metal ions increases, thus the electro-chemical activity of material is reduced, especially the efficiency reducing the effective rate of utilization of active material and the embedding of lithium ion in electrochemical reaction process and deviate from, the capacity finally constraining lithium-containing transition metal oxide plays and high rate performance.
Summary of the invention
Technical problem:
The problem such as molten poly-degree increase between the nanostructure avalanche that the defect-lithium-containing transition metal oxide that the object of the invention is to overcome existing technology of preparing occurs in long-time high-temperature sintering process, particle coarsening and particle, solve the key issue of the performance of restriction lithium ion battery lithium-containing transition metal oxide electrode material capacity, high rate performance etc., the preparation method of a kind of high power capacity, high efficiency power lithium-ion battery electrode material is provided.
Technical method:
First technical scheme of the present invention for utilize solvent-thermal method, the standby transition metal oxide going out can supply Lithium-ion embeding and deviate from of the Low Temperature Wet chemistry legal systems such as hydro thermal method and solution deposit (comprising sol-gal process), hydroxide or carbonate nanostructured chemicals, quantitative being inserted into by lithium ion of recycling electrochemistry prelithiation technology prepares the transition state after lithiumation in the middle of the intragranular lattice of transition metal oxide and contains lithium metal oxide, finally applying a lower energy to transition state containing lithium metal oxide makes lithium ion and transition metal and oxygen atom occur to reset and the transformation of lattice.
The present invention-as follows containing the concrete preparation process of the electrochemical preparation method of lithium metal oxide lithium electricity nano-electrode material:
Containing a preparation method for lithium metal oxide lithium electricity nano-electrode material, it is characterized in that being made up of following steps:
(1) preparation of nano-structural transition metal compound: obtained by solvent-thermal method or hydro thermal method or solution deposit or sol-gal process preparation;
(2) electrochemistry lithiumation transistion metal compound electrode preparation: the material prepared according to method step (1) Suo Shi and conductive black and binding agent Homogeneous phase mixing are coated on copper foil surface, then through super-dry process;
(3) electrochemistry lithiumation electricity consumption pond assembling: lithium metal is to electrode and negative pole, with LiPF 6, LiClO 4or a wherein class commercial li-ion battery electrolyte of LiTFSI is electrolyte, be that work electrode and positive pole are assembled into lithium ion battery with the electrode prepared by step (2);
(4) electrochemistry prelithiation: the battery that step (3) is installed is carried out discharge process;
(5) dismounting of lithiumation battery and the cleaning of lithiated electrode: the battery roll after the lithiumation obtain step (4) is opened, passive electrode, then obtains transiting product after cleaning-drying;
(6) Low Temperature Heat Treatment: collect the transiting product that obtains according to step (5) under air or inert atmosphere protection at 400 ~ 600 DEG C cool to room temperature, finally obtained lithium-containing transition metal oxide after process annealing 2 ~ 10h.
Preparation method containing lithium metal oxide lithium electricity nano-electrode material described above, it is characterized in that in described step 1, solvent-thermal method is: be dissolved in high boiling solvent by the mixture of transition metal salt or transition metal salt and surfactant, react 5-48h at 150-330 DEG C under airtight or counterflow condition after, after cleaning-drying, obtain nano-structural transition metal oxide.
In described step 1, hydro thermal method is: by being dissolved in the double solvents of water or water by the mixture of transition metal salt or transition metal salt and surfactant, after reacting 5-48h in confined conditions at 150-200 DEG C, after cleaning-drying, obtain nano-structural transition metal compound.
Solution deposit in described step 1 is: by the salt containing transition metal being dissolved in the aqueous solution or containing in the aqueous solution of surfactant, then uniform transition metal salt solution is slowly added drop-wise in the alkaline sedimentation agent solution prepared in advance, obtains corresponding nano-structural transition metal oxide finally by decomposition reaction 2-10h under 400-550 DEG C of condition.
Sol-gal process in described step 1 is: corresponding transition metal salt solution be slowly added drop-wise to by citric acid and the ethylene glycol solution colloidal sol that 2:1 prepares in molar ratio, the mol ratio of metal ion and citric acid, between 0.5 ~ 1, obtains corresponding transition metal oxide nano particle after decomposing 2 ~ 24h at 100 DEG C after drying at 400 ~ 500 DEG C.
The preparation method containing lithium metal oxide lithium electricity nano-electrode material described above, the high boiling solvent that it is characterized in that in described solvent-thermal method comprises ethylene glycol or glycerol or tetraethylene glycol.
Preparation method containing lithium metal oxide lithium electricity nano-electrode material described above, is characterized in that the double solvents of the water in described hydro thermal method is the double solvents of water and ethylene glycol or formic acid or formaldehyde.
Preparation method containing lithium metal oxide lithium electricity nano-electrode material described above; it is characterized in that the concentration of the transition metal salt in the described precipitation method is 0.1-2mol/L; the mol ratio of described surfactant and transition metal ions is 0.5-2; the concentration of described alkaline precipitating agent is 0.5-6mol/L; the reaction temperature of precipitation reaction is room temperature-200 DEG C; described reaction atmosphere is air or protective atmosphere, and the described reaction time is 5-48h.
Preparation method containing lithium metal oxide lithium electricity nano-electrode material described above, it is characterized in that the binding agent in described step 2 comprises carboxymethyl cellulose class, Kynoar class, the percentage by weight of described nano structural material, conductive black and binding agent is:
Nano structural material 80%-96%
Conductive black 2%-10%
Binding agent 2%-10%.
A kind of containing lithium metal oxide lithium electricity nano-electrode material, it is characterized in that its chemical formula is Li 4m 5o 12or Li xn yo x, wherein M is one or more in Ti, V, Mn, Ni element, and N is one or more in Ti, V, Mn, Ni, Co, Fe, Al, Mo, Sn, Ge element, and x is between 0.1-2, y=1 or 2, z=2 or 3 or 4.
Beneficial effect
Compared to conventional method, the present invention is without the need at high temperature carrying out forming core again and spreading growth course for a long time, thus can obtain the lithium-containing transition metal oxide electrode material of the well-developed nanoscale of crystal structure and structure, finally promote with the chemical property of upper electrode material.The present invention greatly reduces the energy consumption in the middle of material preparation process, thus production cost is reduced, and can ratio effectively between control Li/ transition metal, the material of design and synthesis heterogeneity structure, the chemical property of controlled material, therefore this electrochemistry prelithiation low temperature preparation method is the comparatively green controllable method for preparing of a kind of nanometer lithium-containing transition metal oxide nano structure electrode material.
Accompanying drawing explanation
Fig. 1 is β-MnO 2(a) low power of nanometer rods and (b) high power stereoscan photograph.
Fig. 2 is the corresponding constant-current discharge curve of manganese bioxide electrochemical lithiumation process.
Fig. 3 is the LiMn that electrochemistry lithiumation method assists preparation 2o 4(a) low power of nanometer rods and (b) high power stereoscan photograph; The LiMn of manganese dioxide nano-rod template assisted Solid-state method synthesis 2o 4(c) low power of nanometer rods and (d) high power stereoscan photograph.
Fig. 4 is the forward and backward MnO of lithiumation 2with the X-ray diffraction style of the LiMn2O4 sample obtained after different temperatures (blue 450 DEG C, pink colour 550 DEG C) annealing.
Fig. 5 a is (Ni 1/3co 1/3mn 1/3) CO 3the stereoscan photograph of Nano microsphere precursor.
Fig. 5 b is lithium-containing transition metal oxide LiNi 1/3co 1/3mn 1/3o 2the stereoscan photograph of Nano microsphere.
Embodiment
Below by specific embodiment, introduction is illustrated to the present invention:
Embodiment 1: the auxiliary preparation of electrochemistry lithiumation of LiMn2O4 nanometer rods
1) the hydro-thermal preparation of manganese dioxide nano-rod:
Be the Mn (C of 1:1 by mol ratio 2h 3o 2) 24H 2o and Na 2s 2o 8be dissolved in 80mL deionized water, obtained after at the uniform velocity stirring half an hour, the aqueous solution of 1mol/L, subsequently obtained homogeneous solution is transferred in the polytetrafluoroethylcontainer container with rustless steel container good seal of 100ml, be placed in preheated drying box hydro-thermal reaction 12h at 130 DEG C, after stove cool to room temperature, utilize deionized water centrifuge washing three times, absolute ethyl alcohol washs once again, dry 10h at 80 DEG C, and the final diameter obtained as shown in Figure 2 is about the β-MnO of 20 ~ 100nm 2nanometer rods.
2) preparation of manganese dioxide nano-rod electrode is assembled with battery:
By β-MnO 2nanometer rods (90%) and conductive black (5%) and binding agent (PVDF, 5%) Homogeneous phase mixing obtains homogeneous slurry, again gained colloid is coated on copper foil surface, at 70 DEG C after dry 3h, continue vacuumize 5h at 90 DEG C, the final β-MnO obtaining electrochemistry lithiumation 2nanorod electrodes.
Be to electrode (negative pole) with lithium sheet, with 1mol/LLiPF 6eC+DEC solution be electrolyte, with manganese dioxide nano-rod electrode for work electrode (positive pole) is assembled into lithium ion battery in vacuum glove box.
3) electrochemistry lithiumation: adopt the current density of 0.1C (C is theoretical capacity 157mAh/g) to discharge to the battery installed according to step (2), by controlled discharge time electric discharge 10h β-MnO 2lattice in insert 0.5 Li +, the typical discharge curve corresponding to lithiumation process as shown in Figure 3.
4) dismounting of lithiumation battery and the cleaning of lithiated electrode: the battery roll after the lithiumation obtained according to step (3) is opened, collect the electrode after the electrochemistry lithiumation obtained, utilize poly-ethyl carbonate (PC) and ethanol successively each washing three times, at 80 DEG C, after dry 5h, obtain the MnO after corresponding lithiumation 2transiting product.
5) Low Temperature Heat Treatment: collect the transition metal oxide after the lithiumation obtained according to step (4), hydroxide or carbonate transiting product under air at 450 ~ 600 DEG C cool to room temperature after process annealing 5 ~ 15h, final obtained lithium-containing transition metal oxide LiMn as shown in Figure 4 2o 4.Accompanying drawing 5 assists the Typical X-ray diffraction style of the LiMn2O4 of preparation for electrochemistry lithiumation.
Embodiment 2: porous LiNi 1/3co 1/3mn 1/3o 2the auxiliary preparation of electrochemistry lithiumation of Nano microsphere
1) (Ni 1/3co 1/3mn 1/3) CO 3the hydro-thermal preparation of Nano microsphere:
Be the Ni (C of 1:1:1 by mol ratio 2h 3o 2) 24H 2o, Co (C 2h 3o 2) 24H 2o and Mn (C 2h 3o 2) 24H 2o is dissolved in the mixed solution (volumetric mixture ratio is between 0.5 ~ 1.5) of 80mL deionized water and ethylene glycol, the mixed solution of obtained 0.2 ~ 0.8mol/L after at the uniform velocity stirring half an hour, add 0.016 ~ 0.064mol urea in solution after, obtained homogeneous solution is transferred in the polytetrafluoroethylcontainer container with rustless steel container good seal of 100ml, be placed in preheated drying box hydro-thermal reaction 10 ~ 24h at 130 ~ 200 DEG C, after stove cool to room temperature, utilize deionized water centrifuge washing three times, absolute ethyl alcohol washs once again, dry 10h at 80 DEG C, final acquisition diameter as shown in accompanying drawing 5a is about the (Ni of 2 ~ 25 μm 1/3co 1/3mn 1/3) CO 3nano microsphere.
2) NiCoMnO 4the preparation of Nano microsphere:
Will according to the obtained (Ni of step (1) 1/3co 1/3mn 1/3) CO 3nano microsphere obtains corresponding porous NiCoMnO return 2 ~ 8h at 350 ~ 550 DEG C after 4nano microsphere.
3) NiCoMnO 4the preparation of Nano microsphere electrode is assembled with battery:
By NiCoMnO 4nano microsphere (90%) and conductive black (5%) and binding agent (PVDF, 5%) Homogeneous phase mixing obtains homogeneous slurry, again gained colloid is coated on copper foil surface, at 70 DEG C after dry 3h, continue vacuumize 5h at 90 DEG C, the final NiCoMnO obtaining electrochemistry lithiumation 4nano microsphere electrode.
Be to electrode (negative pole) with lithium sheet, with 1mol/LLiPF 6eC+DEC solution be electrolyte, with NiCoMnO 4nano microsphere electrode is that work electrode (positive pole) is assembled into lithium ion battery in vacuum glove box.
4) electrochemistry lithiumation: adopt the current density of 0.5C (C is theoretical capacity xxxmAh/g) to discharge to the battery installed according to step (2), by controlled discharge time electric discharge 10hNiCoMnO 43 Li are inserted in the lattice of Nano microsphere +.
5) dismounting of lithiumation battery and the cleaning of lithiated electrode: the battery roll after the lithiumation obtained according to step (3) is opened, collect the electrode after the electrochemistry lithiumation obtained, utilize poly-ethyl carbonate (PC) and ethanol successively each washing three times, at 80 DEG C, after dry 5h, obtain the NiCoMnO after corresponding lithiumation 4nano microsphere transiting product.
6) Low Temperature Heat Treatment: collect the transition metal oxide after the lithiumation obtained according to step (4), hydroxide or carbonate transiting product under air at 450 ~ 600 DEG C cool to room temperature after process annealing 10 ~ 15h, final obtained diameter 2 ~ 20 μm of lithium-containing transition metal oxide LiNi as shown in fig. 5b 1/3co 1/3mn 1/3o 2nano microsphere.
Embodiment 3:xLi 2mnO 3(1-x) LiNi 1/3co 1/3mn 1/3o 2(0<x<1) the auxiliary preparation of the electrochemistry lithiumation of Nano microsphere
1) (Ni (1-x)/3co (1-x)/3mn (1+2x)/3) CO 3the hydro-thermal preparation of Nano microsphere:
Be (1-x) by mol ratio: (1-x): the Ni (C of (1+2x) 2h 3o 2) 24H 2o, Co (C 2h 3o 2) 24H 2o and Mn (C 2h 3o 2) 24H 2o is dissolved in the mixed solution (volumetric mixture ratio is between 0.5 ~ 1.5) of 80mL deionized water and ethylene glycol, the mixed solution of obtained 0.2 ~ 0.8mol/L after at the uniform velocity stirring half an hour, add 0.016 ~ 0.064mol urea in solution after, obtained homogeneous solution is transferred in the polytetrafluoroethylcontainer container with rustless steel container good seal of 100ml, be placed in preheated drying box hydro-thermal reaction 10 ~ 24h at 130 ~ 200 DEG C, after stove cool to room temperature, utilize deionized water centrifuge washing three times, absolute ethyl alcohol washs once again, dry 10h at 80 DEG C, final acquisition diameter is about the (Ni of 5 ~ 25 μm (1-x)/3co (1-x)/3mn (1+2x)/3) CO 3nano microsphere.
2) Ni (1-x)co (1-x)mn (1+2x)o 4the preparation of Nano microsphere:
Will according to the obtained (Ni of step (1) (1-x)/3co (1-x)/3mn (1+2x)/3) CO 3nano microsphere obtains corresponding porous Ni return 2 ~ 8h at 350 ~ 550 DEG C after (1-x)co (1-x)mn (1+2x)o 4nano microsphere.
3) Ni (1-x)co (1-x)mn (1+2x)o 4the preparation of Nano microsphere electrode is assembled with battery:
By Ni (1-x)co (1-x)mn (1+2x)o 4nano microsphere (90%) and conductive black (5%) and binding agent (PVDF, 5%) Homogeneous phase mixing obtains homogeneous slurry, again gained colloid is coated on copper foil surface, at 70 DEG C after dry 3h, continue vacuumize 5h at 90 DEG C, the final Ni obtaining electrochemistry lithiumation (1-x)co (1-x)mn (1+2x)o 4nano microsphere electrode.
Be to electrode (negative pole) with lithium sheet, with 1mol/LLiClO 4pC solution be electrolyte, with Ni (1-x)co (1-x)mn (1+2x)o 4nano microsphere electrode is that work electrode (positive pole) is assembled into lithium ion battery in vacuum glove box.
4) electrochemistry lithiumation: adopt the current density of 0.1C (C is theoretical capacity xxxmAh/g) to discharge to the battery installed according to step (2), by controlled discharge time electric discharge 10hNi (1-x)co (1-x)mn (1+2x)o 43 Li are inserted in the lattice of Nano microsphere +.
5) dismounting of lithiumation battery and the cleaning of lithiated electrode: the battery roll after the lithiumation obtained according to step (3) is opened, collect the electrode after the electrochemistry lithiumation obtained, utilize poly-ethyl carbonate (PC) and ethanol successively each washing three times, at 80 DEG C, after dry 5h, obtain the Ni after corresponding lithiumation (1-x)co (1-x)mn (1+2x)o 4nano microsphere transiting product.
6) Low Temperature Heat Treatment: collect the transition metal oxide after the lithiumation obtained according to step (4), hydroxide or carbonate transiting product under air at 450 ~ 600 DEG C cool to room temperature after process annealing 10 ~ 15h, the final obtained rich lithium transition-metal oxide xLi of diameter 2 ~ 20 μm 2mnO 3(1-x) LiNi 1/3co 1/3mn 1/3o 2(0<x<1) Nano microsphere.
Embodiment 4:xLi 2mnO 3(1-x) LiNi 1/2mn 1/2o 2the auxiliary preparation of electrochemistry lithiumation of (x is between 0 ~ 1) Nano microsphere
1) (Ni (1-x)/2mn (1+x)/2) CO 3the solvent heat preparation of Nano microsphere:
Be (1-x) by mol ratio: the Ni (C of (1+x) 2h 3o 2) 24H 2o and Mn (C 2h 3o 2) 24H 2o is dissolved in the mixed solution of 80mL deionization ethylene glycol, the mixed solution of obtained 0.2 ~ 0.8mol/L after at the uniform velocity stirring half an hour, add 0.016 ~ 0.064mol urea in solution after, obtained homogeneous solution is transferred in the polytetrafluoroethylcontainer container with rustless steel container good seal of 100ml, be placed in preheated drying box hydro-thermal reaction 10 ~ 24h at 130 ~ 200 DEG C, after stove cool to room temperature, utilize deionized water centrifuge washing three times, absolute ethyl alcohol washs once again, dry 10h at 80 DEG C, final acquisition diameter is about the (Ni of 5 ~ 25 μm (1-x)/2mn (1+x)/2) CO 3nano microsphere.
2) Ni (1-x)co (1-x)mn (1+2x)o 4the preparation of Nano microsphere:
Will according to the obtained (Ni of step (1) (1-x)/2mn (1+x)/2) CO 3nano microsphere obtains corresponding porous (Ni return 2 ~ 8h at 350 ~ 550 DEG C after (1-x)mn (1+x)) 3o 4nano microsphere.
3) (Ni (1-x)mn (1+x)) 3o 4the preparation of Nano microsphere electrode is assembled with battery:
By (Ni (1-x)mn (1+x)) 3o 4nano microsphere (90%) and conductive black (5%) and binding agent (PVDF, 5%) Homogeneous phase mixing obtains homogeneous slurry, again gained colloid is coated on copper foil surface, at 70 DEG C after dry 3h, continue vacuumize 5h at 90 DEG C, the final Ni obtaining electrochemistry lithiumation (1-x)co (1-x)mn (1+2x)o 4nano microsphere electrode.
Be to electrode (negative pole) with lithium sheet, with 1mol/LLiClO 4pC solution be electrolyte, with (Ni (1-x)mn (1+x)) 3o 4nano microsphere electrode is that work electrode (positive pole) is assembled into lithium ion battery in vacuum glove box.
4) electrochemistry lithiumation: adopt the current density of 50 ~ 1000mA/g to discharge to the battery installed according to step (2), by controlled discharge time electric discharge 0.5 ~ 10h (Ni (1-x)mn (1+x)) 3o 43 Li are inserted in the lattice of Nano microsphere +.
5) dismounting of lithiumation battery and the cleaning of lithiated electrode: the battery roll after the lithiumation obtained according to step (3) is opened, collect the electrode after the electrochemistry lithiumation obtained, utilize poly-ethyl carbonate (PC) and ethanol successively each washing three times, at 80 DEG C, after dry 5h, obtain (the Ni after corresponding lithiumation (1-x)mn (1+x)) 3o 4nano microsphere transiting product.
6) Low Temperature Heat Treatment: collect the transition metal oxide after the lithiumation obtained according to step (4), hydroxide or carbonate transiting product under air at 450 ~ 600 DEG C cool to room temperature after process annealing 10 ~ 15h, finally obtained 2 ~ 20 μm of rich lithium transition-metal oxide xLi 2mnO 3(1-x) LiNi 1/2mn 1/2o 2nano microsphere.
Embodiment 5:xLi 2mnO 3(1-x) LiNi 1/2mn 3/2o 4the auxiliary preparation of electrochemistry lithiumation of (x is between 0 ~ 1) Nano microsphere
1) (Ni (1-x)/2mn (3-x)/2) (OH) 2the coprecipitation preparation of Nano microsphere:
Be (1-x) by mol ratio: the Ni (C of (3-x) 2h 3o 2) 24H 2o and Mn (C 2h 3o 2) 24H 2o is dissolved in the mixed solution of 80mL deionization ethylene glycol, the mixed solution of obtained 0.2 ~ 0.8mol/L after at the uniform velocity stirring half an hour, under the stir speed (S.S.) of 1000 ~ 1500 turns/min, 1 ~ 5mol NaOH or potassium hydroxide solution is added in solution, obtained homogeneous solution is transferred in the polytetrafluoroethylcontainer container with rustless steel container good seal of 100ml, be placed in preheated drying box hydro-thermal reaction 10 ~ 24h at 130 ~ 200 DEG C, after stove cool to room temperature, utilize deionized water centrifuge washing three times, absolute ethyl alcohol washs once again, dry 10h at 80 DEG C, final acquisition diameter is about the (Ni of 5 ~ 25 μm (1-x)/2mn (3-x)/2) (OH) 2nano microsphere.
2) (Ni (1-x)/2mn (3-2x)/2) 3o 4the preparation of Nano microsphere:
Will according to the obtained (Ni of step (1) (1-x)/2mn (3-x)/2) (OH) 2nano microsphere obtains corresponding porous (Ni return 2 ~ 8h at 350 ~ 550 DEG C after (1-x)/2mn (3-x)/2) 3o 4nano microsphere.
3) (Ni (1-x)/2mn (3-x)/2) 3o 4the preparation of Nano microsphere electrode is assembled with battery:
By (Ni (1-x)/2mn (3-x)/2) 3o 4nano microsphere (90%) and conductive black (5%) and binding agent (PVDF, 5%) Homogeneous phase mixing obtains homogeneous slurry, again gained colloid is coated on copper foil surface, at 70 DEG C after dry 3h, continue vacuumize 5h at 90 DEG C, the final (Ni obtaining electrochemistry lithiumation (1-x)/2mn (3-x)/2) 3o 4nano microsphere electrode.
Be to electrode (negative pole) with lithium sheet, with 1mol/LLiClO 4pC solution be electrolyte, with (Ni (1-x)/2mn (3-x)/2) 3o 4nano microsphere electrode is that work electrode (positive pole) is assembled into lithium ion battery in vacuum glove box.
4) electrochemistry lithiumation: adopt the current density of 50 ~ 1000mA/g to discharge to the battery installed according to step (2), by controlled discharge time electric discharge 0.5 ~ 10h (Ni (1-x)/2mn (3-x)/2) 3o 43 Li are inserted in the lattice of Nano microsphere +.
5) dismounting of lithiumation battery and the cleaning of lithiated electrode: the battery roll after the lithiumation obtained according to step (3) is opened, collect the electrode after the electrochemistry lithiumation obtained, utilize poly-ethyl carbonate (PC) and ethanol successively each washing three times, at 80 DEG C, after dry 5h, obtain (the Ni after corresponding lithiumation (1-x)mn (1+x)) 3o 4nano microsphere transiting product.
6) Low Temperature Heat Treatment: collect the transition metal oxide after the lithiumation obtained according to step (4), hydroxide or carbonate transiting product under air at 450 ~ 600 DEG C cool to room temperature after process annealing 10 ~ 15h, final obtained rich lithium transition-metal oxide xLi 2mnO 3(1-x) LiNi 1/2mn 3/2o 4nano microsphere.
Embodiment 6:Li 4ti 5o 12the auxiliary preparation of electrochemistry lithiumation of nanosphere
1) TiO 2the preparation of nanosphere: be first dissolved in 150 ~ 250ml absolute ethyl alcohol by 10 ~ 20ml tetrabutyl titanate, obtained clear solution, after 30 minutes, drops in 1.5 ~ 2.0g cetylamine solution by uniform stirring.Subsequently by 2 ~ 10mlNH 3h 2o (25%) dropwise joins in mixed solution obtained before this.Through the magnetic agitation of 1 ~ 3 hour, clear solution was transformed into milky troubled liquor gradually. at 80 ~ 120 DEG C, obtain diameter 300 ~ 600nmTiO after dry 24 hours 2white nanosphere.
2) TiO 2the preparation of nanosphere electrode is assembled with battery:
By TiO 2nanosphere (90%) and conductive black (5%) and binding agent (PVDF, 5%) Homogeneous phase mixing obtains homogeneous slurry, again gained colloid is coated on copper foil surface, at 70 DEG C after dry 3h, continue vacuumize 5h at 90 DEG C, the final TiO obtaining electrochemistry lithiumation 2nanosphere electrode.
Be to electrode (negative pole) with lithium sheet, with 1mol/LLiClO 4pC solution be electrolyte, with TiO 2nanosphere electrode is that work electrode (positive pole) is assembled into lithium ion battery in vacuum glove box.
3) electrochemistry lithiumation: adopt the current density of 50 ~ 1000mA/g to discharge to the battery installed according to step (2), by controlled discharge time electric discharge 0.5 ~ 10hTiO 20.8 Li is inserted in the lattice of nanosphere +.
4) dismounting of lithiumation battery and the cleaning of lithiated electrode: the battery roll after the lithiumation obtained according to step (3) is opened, collect the electrode after the electrochemistry lithiumation obtained, utilize poly-ethyl carbonate (PC) and ethanol successively each washing three times, at 80 DEG C, after dry 5h, obtain the TiO after corresponding lithiumation 2nanosphere transiting product.
5) Low Temperature Heat Treatment: collect the transition metal oxide after the lithiumation obtained according to step (4), hydroxide or carbonate transiting product under air or inert atmosphere protection at 450 ~ 600 DEG C cool to room temperature after process annealing 10 ~ 15h, finally obtained 200 ~ 500nmLi 4ti 5o 12nanosphere.
Embodiments of the invention are only of the present invention and illustrate, and can not limit the present invention.

Claims (7)

1., containing a preparation method for lithium metal oxide lithium electricity nano-electrode material, it is characterized in that, described method comprises the steps:
(1) preparation of nano-structural transition metal compound: obtained by solvent-thermal method or hydro thermal method or solution deposit or sol-gal process preparation;
(2) electrochemistry lithiumation transistion metal compound electrode preparation: the material prepared according to method step (1) Suo Shi and conductive black and binding agent Homogeneous phase mixing are coated on copper foil surface, then through super-dry process;
(3) electrochemistry lithiumation electricity consumption pond assembling: be to electrode and negative pole with lithium metal, with LiPF 6or LiClO 4or the wherein class commercial li-ion battery electrolyte in LiTFSI is electrolyte, be that work electrode and positive pole are assembled into lithium ion battery with the electrode prepared by step (2);
(4) electrochemistry prelithiation: the battery that step (3) is installed is carried out discharge process;
(5) dismounting of lithiumation battery and the cleaning of lithiated electrode: the battery roll after the lithiumation obtain step (4) is opened, passive electrode, then obtains transiting product after cleaning-drying;
(6) Low Temperature Heat Treatment: collect the transiting product that obtains according to step (5) under air or inert atmosphere protection at 400 ~ 600 DEG C cool to room temperature, finally obtained lithium-containing transition metal oxide after process annealing 2 ~ 10h.
2. the preparation method containing lithium metal oxide lithium electricity nano-electrode material according to claim 1, it is characterized in that in described step 1, solvent-thermal method is: be dissolved in high boiling solvent by the mixture of transition metal salt or transition metal salt and surfactant, react 5-48h at 150-330 DEG C under airtight or counterflow condition after, after cleaning-drying, obtain nano-structural transition metal oxide;
In described step 1, hydro thermal method is: by being dissolved in the double solvents of water or water by the mixture of transition metal salt or transition metal salt and surfactant, after reacting 5-48h in confined conditions at 150-200 DEG C, after cleaning-drying, obtain nano-structural transition metal compound;
Solution deposit in described step 1 is: by the salt containing transition metal being dissolved in the aqueous solution or containing in the aqueous solution of surfactant, then uniform transition metal salt solution is slowly added drop-wise in the alkaline sedimentation agent solution prepared in advance, obtains corresponding nano-structural transition metal oxide finally by decomposition reaction 2-10h under 400-550 DEG C of condition;
Sol-gal process in described step 1 is: corresponding transition metal salt solution be slowly added drop-wise to by citric acid and the ethylene glycol solution colloidal sol that 2:1 prepares in molar ratio, the mol ratio of metal ion and citric acid, between 0.5 ~ 1, obtains corresponding transition metal oxide nano particle after decomposing 2 ~ 24h at 100 DEG C after drying at 400 ~ 500 DEG C.
3. the preparation method containing lithium metal oxide lithium electricity nano-electrode material according to claim 1 and 2, the high boiling solvent that it is characterized in that in described solvent-thermal method comprises ethylene glycol or glycerol or tetraethylene glycol.
4. the preparation method containing lithium metal oxide lithium electricity nano-electrode material according to claim 1 and 2, is characterized in that the double solvents of the water in described hydro thermal method is the double solvents of water and ethylene glycol or formic acid or formaldehyde.
5. the preparation method containing lithium metal oxide lithium electricity nano-electrode material according to claim 1 and 2; it is characterized in that the concentration of the transition metal salt in the described precipitation method is 0.1-2mol/L; the mol ratio of described surfactant and transition metal ions is 0.5-2; the concentration of described alkaline precipitating agent is 0.5-6mol/L; the reaction temperature of precipitation reaction is room temperature-200 DEG C; described reaction atmosphere is air or protective atmosphere, and the described reaction time is 5-48h.
6. the preparation method containing lithium metal oxide lithium electricity nano-electrode material according to claim 1, it is characterized in that the binding agent in described step 2 comprises carboxymethyl cellulose class, Kynoar class, the percentage by weight of described nano structural material, conductive black and binding agent is:
Nano structural material 80%-96%
Conductive black 2%-10%
Binding agent 2%-10%.
7. the one drawn according to claim 1 preparation method contains lithium metal oxide lithium electricity nano-electrode material, is characterised in that its chemical formula is Li 4m 5o 12or Li xn yo x, wherein M is one or more in Ti, V, Mn, Ni element, and N is one or more in Ti, V, Mn, Ni, Co, Fe, Al, Mo, Sn, Ge element, and x is between 0.1-2, y=1 or 2, z=2 or 3 or 4.
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CN108832137A (en) * 2018-06-25 2018-11-16 太原理工大学 N dopen Nano carbon ball loads NiCoMnO4Nanometer grain preparation method
CN110327930A (en) * 2019-06-20 2019-10-15 武汉理工大学 Low crystallization classification hydroxy nickel oxide nano-chip arrays and its preparation method and application
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CN108649239A (en) * 2018-05-14 2018-10-12 陕西科技大学 A method of regulation and control oxide type elctro-catalyst crystal lattice stress
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