CN105304895B - Electricity nano-electrode material of lithium containing lithium metal oxide and preparation method thereof - Google Patents
Electricity nano-electrode material of lithium containing lithium metal oxide and preparation method thereof Download PDFInfo
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- CN105304895B CN105304895B CN201510693752.5A CN201510693752A CN105304895B CN 105304895 B CN105304895 B CN 105304895B CN 201510693752 A CN201510693752 A CN 201510693752A CN 105304895 B CN105304895 B CN 105304895B
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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
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- 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
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- 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
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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
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- 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
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- H—ELECTRICITY
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- 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
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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
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses electricity nano-electrode material of lithium containing lithium metal oxide and preparation method thereof, the nanostructured metal oxides for being synthesized the low temperature such as hydro-thermal method, solvent-thermal method and sol-gal process by electrochemical method carry out prelithiation, so as to effectively reduce the temperature and required time of the crystal structure formation and development containing lithium metal oxide, Li in lithium-containing transition metal oxide can be effectively controlled+Ratio and mixing degree between/transition metal ions, and the nano-scale and structure of metal oxide can be kept.The present invention greatly reduces energy consumption among material preparation process, reduces cost, high efficiency and powerful lithium-containing transition metal oxide positive pole and negative material can be obtained simultaneously, therefore the electrochemistry prelithiation preparation method is the more green controllable method for preparing of a kind of nanometer of lithium-containing transition metal oxide nano structure electrode material.
Description
Technical field
The present invention relates to a kind of electricity nano-electrode material of lithium containing lithium metal oxide and its low temperature preparation method, more particularly to
A kind of electrochemistry prelithiation technology of preparing of lithium-containing transition metal oxide nano structure electrode material.
Background technology
It is quickly exhausted that mankind nowadays society is in the fossil energy such as highly energy-consuming stage, oil, natural gas, energy crisis and
Problem of environmental pollution getting worse, therefore the environment-friendly new energy technology such as solar energy, wind energy, biomass energy and tide energy is standby
Concerned, China is also building substantial amounts of solar energy, wind energy and tidal power factory more.But due to solar energy, wind energy
The electrode issued with tide energy is unstable, can not enter huge numbers of families and each enterprises and institutions by being incorporated to the public supply network of country
Unit, ultimately result in a large amount of generation of electricity by new energy factories and relevant device and material manufacturer loss or even close down.How this is solved
Key issue, by it is stable, cheap, conveniently in a manner of that these new energy electric power successfully are carried out into peak regulation is grid-connected and applied
It is always the focus of science and industrial circle concern and the focus of research in mobile electronic device and electric transportation instrument etc..
Lithium ion battery has energy density height compared to conventional batteries such as plumbic acid and ni-mhs, and power density is high, safety, cost
It is low, the characteristic such as environment-friendly, be considered high performance green energy-storing device, available for intelligent grid construction with assist solar energy,
The peak regulations such as wind energy, tide energy are grid-connected, and are 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 of battery, and the performance of electrode material governs the power of lithium ion battery always
With energy density.With the development of Large Copacity energy storage device and power-type lithium ion battery, align, negative material propose it is higher
Requirement.The application to high performance lithium ion battery anode material and research are concentrated mainly on spinel lithium manganate at present
(LiMn2O4), nickel manganese binary system [Li (NixMny)O2], cobalt manganese binary system [Li (CoxMny)O2] and nickel-cobalt-manganese ternary system [Li
(NixCoyMnz)O2Deng layered oxide and part polyanionic LiFePO 4 (LiFePO4), phosphoric acid vanadium lithium (Li3V2
(PO4)3) and fluorophosphoric acid system (such as LiV0.5Fe0.5PO4F) etc..Research to negative material is then concentrated mainly on lithium titanate
(Li4Ti5O12) and transition-metals and their oxides and advanced carbon material.Lithium-containing transition metal oxide is higher due to possessing
The features such as voltage platform, larger capacity and tap density, more outstanding multiplying power and cyclical stability, it is considered to be before most rich
Scape and the current most commonly used lithium ion battery electrode material of commercial Application.
Lithium-containing transition metal oxide spinel lithium manganate (LiMn at this stage2O4), rich lithium LiMn2O4 (Li2MnO3), nickel manganese
Binary system [Li (NixMny)O2], nickel-cobalt-manganese ternary system [Li (NixCoyMnz)O2With lithium titanate (Li4Ti5O12) etc. mainly pass through
The precursor and lithium salts solid phase that sol-gal process and utilization synthesize the precipitation method or hydro-thermal method are compound, then by prolonged high temperature
Diffuse to form the high crystallizing and sintering temperature difference of crystal, wherein LiMn2O4, lithium titanate and stratiform nickel, cobalt and manganese oxide class compound
About 800,900,1000 DEG C.More than 10h sinters the precursor nanostructured for directly resulting in low temperature synthesis for a long time at high temperature
Avalanche and drastically the growing up of nano particle (into sub-micron even micron particles), cause Li in material crystal structure+/ transition
Wrong row's increase between metal ion, thus the electro-chemical activity of material is reduced, especially it is reduction of electrochemical reaction process
The effective rate of utilization of middle active material and the efficiency of the insertion of lithium ion and abjection, finally constrain lithium-containing transition metal oxide
Capacity play and high rate performance.
The content of the invention
Technical problem：
The defects of it is an object of the invention to overcome existing technology of preparing-lithium-containing transition metal oxide is in long-time high temperature
The nanostructured avalanche that occurs in sintering process, particle coarsening the problems such as poly- degree increase is melted between particle, solve restrict lithium from
A kind of key issue of the lithium-containing transition metal oxide electrode material capacity performance of sub- battery, high rate performance etc., there is provided Gao Rong
Amount, the preparation method of efficient power lithium-ion battery electrode material.
Technical method：
The technical scheme is that first with solvent-thermal method, hydro-thermal method and solution deposit (including sol-gal process)
Deng Low Temperature Wet chemistry method prepare out be available for Lithium-ion embeding and abjection transition metal oxide, hydroxide or carbonate receive
Rice structural compounds, recycling electrochemistry prelithiation technology, quantitative that lithium ion is inserted into transition metal oxide is intragranular
The transition state after lithiumation is prepared among lattice and contains lithium metal oxide, one finally is applied containing lithium metal oxide to transition state
Individual relatively low energy makes lithium ion and transition metal and oxygen atom occurs to reset and the transformation of lattice.
The specific preparation process of the electrochemical preparation method of the present invention-lithium containing lithium metal oxide electricity nano-electrode material
It is as follows：
A kind of preparation method of the electricity of lithium containing lithium metal oxide nano-electrode material, it is characterised in that by following steps structure
Into：
(1) preparation of nano-structural transition metal compound：Pass through solvent-thermal method or hydro-thermal method or solution deposit or molten
Sol-gel is prepared；
(2) electrochemistry lithiumation is used crosses metal compound electrode preparation：It will be prepared according to method shown in step (1)
Material uniformly mixes with conductive black and binding agent and is coated on copper foil surface, drying processing；
(3) electrochemistry lithiumation electricity consumption pond assembles：Lithium metal is is negative pole to electrode, with LiPF6, LiClO4Or LiTFSI
One type commercial li-ion battery electrolyte is electrolyte, is positive pole group by working electrode of the electrode prepared by step (2)
Dress up lithium ion battery；
(4) electrochemistry prelithiation：The battery that step (3) is installed carries out discharge process；
(5) dismounting of lithiumation battery and the cleaning of lithiated electrode：Battery roll after the lithiumation that step (4) is obtained
Open, passive electrode, then transiting product is obtained after cleaning-drying；
(6) Low Temperature Heat Treatment：Collect according to the transiting product obtained by step (5) under air or inert atmosphere protection
Room temperature is cooled to after 2~10h of process annealing at 400~600 DEG C, lithium-containing transition metal oxide is finally made.
The preparation method of the electricity nano-electrode material of lithium containing lithium metal oxide described above, it is characterised in that the step
Solvent-thermal method is in 1：The mixture of transition metal salt or transition metal salt and surfactant is dissolved in high boiling solvent,
After reacting 5-48h at 150-330 DEG C under closed or counterflow condition, nano-structural transition metal oxygen is obtained after cleaning-drying
Compound.
Hydro-thermal method is in the step 1：By by the mixture of transition metal salt or transition metal salt and surfactant
It is dissolved in the double solvents of water or water, after reacting 5-48h at 150-200 DEG C in confined conditions, is obtained after cleaning-drying
Nano-structural transition metal compound.
Solution deposit in the step 1 is：By the way that the salt containing transition metal is dissolved in into the aqueous solution or containing surface
In the aqueous solution of activating agent, then uniform transition metal salt solution is slowly dropped to the alkaline sedimentation agent solution prepared in advance
In, finally by under the conditions of 400-550 DEG C decomposition reaction 2-10h corresponding nano-structural transition metal oxide is made.
Sol-gal process in the step 1 is：Corresponding transition metal salt solution is slowly dropped to by citric acid and
Ethylene glycol solution in molar ratio 2:1 prepare colloidal sol in, the mol ratio of metal ion and citric acid between 0.5~1,
Dried at 100 DEG C and corresponding transition metal oxide nano particle is made after 2~24h is decomposed at 400~500 DEG C.
The preparation method of the electricity nano-electrode material of lithium containing lithium metal oxide described above, it is characterised in that the solvent
High boiling solvent in hot method includes ethylene glycol or glycerine or tetraethylene glycol.
The preparation method of the electricity nano-electrode material of lithium containing lithium metal oxide described above, it is characterised in that the hydro-thermal
The double solvents of water in method is water and ethylene glycol or the double solvents of formic acid or formaldehyde.
The preparation method of the electricity nano-electrode material of lithium containing lithium metal oxide described above, it is characterised in that the precipitation
The concentration of transition metal salt in method is 0.1-2mol/L, and the mol ratio of the surfactant and transition metal ions is 0.5-
2, the concentration of the alkaline precipitating agent is 0.5-6mol/L, and the reaction temperature of precipitation reaction is -200 DEG C of room temperature, the reaction gas
Atmosphere is air or protective atmosphere, and the reaction time is 5-48h.
The preparation method of the electricity nano-electrode material of lithium containing lithium metal oxide described above, it is characterised in that the step
Binding agent in 2 includes carboxymethyl cellulose class, polyvinylidene fluoride alkenes, the nano structural material, conductive black and binding agent
Percentage by weight be：
Nano structural material 80%-96%
Conductive black 2%-10%
Binding agent 2%-10%.
A kind of electricity nano-electrode material of lithium containing lithium metal oxide, it is characterised in that its chemical formula is Li4M5O12Or
LixNyOx, wherein M is the one or more in Ti, V, Mn, Ni element, and N Ti, V, Mn, Ni, Co, Fe, Al, Mo, Sn, Ge are first
One or more in element, 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 need not carry out forming core and prolonged diffusion growth course at high temperature again, because
And the well-developed nanoscale of crystal structure and the lithium-containing transition metal oxide electrode material of structure can be obtained, final lifting
With the chemical property of upper electrode material.The present invention greatly reduces the energy consumption among material preparation process, thus reduces life
Cost is produced, and can effectively control the ratio between Li/ transition metal, the material of design synthesis heterogeneity structure, regulation and control
The chemical property of material, therefore the electrochemistry prelithiation low temperature preparation method is that a kind of nanometer lithium-containing transition metal oxide is received
The more green controllable method for preparing of rice structure electrode material.
Brief description of the drawings
Fig. 1 is β-MnO2(a) low power and (b) high power stereoscan photograph of nanometer rods.
Fig. 2 is the corresponding constant-current discharge curve of manganese bioxide electrochemical lithiumation process.
Fig. 3 is LiMn prepared by electrochemistry lithiumation method auxiliary2O4(a) low power and (b) high power ESEM of nanometer rods are shone
Piece；The LiMn of manganese dioxide nano-rod template assisted Solid-state method synthesis2O4(c) low power and (d) high power ESEM of nanometer rods are shone
Piece.
Fig. 4 is the forward and backward MnO of lithiumation2With the mangaic acid obtained after different temperatures (450 DEG C of blueness, 550 DEG C of pink colour) annealing
The X-ray diffraction style of lithium sample.
Fig. 5 a are (Ni1/3Co1/3Mn1/3)CO3The stereoscan photograph of nanoparticle precursor.
Fig. 5 b are lithium-containing transition metal oxide LiNi1/3Co1/3Mn1/3O2The stereoscan photograph of nanoparticle.
Embodiment
Introduction is illustrated to the present invention below by specific embodiment:
Embodiment 1：It is prepared by the electrochemistry lithiumation auxiliary of LiMn2O4 nanometer rods
1) prepared by the hydro-thermal of manganese dioxide nano-rod：
It is 1 by mol ratio：1 Mn (C2H3O2)2·4H2O and Na2S2O8It is dissolved in 80mL deionized waters, at the uniform velocity stirring half
It is made after hour, the 1mol/L aqueous solution, the homogeneous solution obtained is then transferred to being sealed with rustless steel container for 100ml
In good polytetrafluoroethylcontainer container, the hydro-thermal reaction 12h at 130 DEG C, furnace cooling to room temperature are placed in preheated drying box
Afterwards, using deionized water centrifuge washing three times, after absolute ethyl alcohol washed once again, 10h is dried at 80 DEG C, it is final to obtain as attached
β-the MnO that diameter shown in Fig. 2 is about 20~100nm2Nanometer rods.
2) prepared by manganese dioxide nano-rod electrode assembles with battery：
By β-MnO2Nanometer rods (90%) are uniformly mixed to prepare homogeneous with conductive black (5%) and binding agent (PVDF, 5%)
Slurry, then gained colloid is coated on copper foil surface, after drying 3h at 70 DEG C, continue to be dried in vacuo 5h at 90 DEG C, finally
Obtain the β-MnO of electrochemistry lithiumation2Nanorod electrodes.
Using lithium piece as to electrode (negative pole), with 1mol/LLiPF6EC+DEC solution be electrolyte, with manganese dioxide nano
Bar electrode is that working electrode (positive pole) is assembled into lithium ion battery in vacuum glove box.
3) electrochemistry lithiumation：0.1C (C is by theoretical capacity 157mAh/g) current density is used to pacifying according to step (2)
The battery of dress is discharged, by controlling discharge time electric discharge 10h β-MnO2Lattice in insert 0.5 Li+, lithiumation process institute
Corresponding typical discharge curve is as shown in Figure 3.
4) dismounting of lithiumation battery and the cleaning of lithiated electrode：Battery after the lithiumation that will be obtained according to step (3) is torn open
Dismantle, collect the electrode after the electrochemistry lithiumation of acquisition, washed using poly- ethyl carbonate (PC) and ethanol are successively each three times, 80
The MnO after corresponding lithiumation is obtained after drying 5h at DEG C2Transiting product.
5) Low Temperature Heat Treatment：Collect according to the transition metal oxide after the lithiumation obtained by step (4), hydroxide or
Person's carbonate transiting product is cooled to room temperature at 450~600 DEG C under air after 5~15h of process annealing, final to be made as attached
Lithium-containing transition metal oxide LiMn shown in Fig. 42O4.Accompanying drawing 5 is that the typical X- of LiMn2O4 prepared by electrochemistry lithiumation auxiliary is penetrated
Line diffraction pattern.
Embodiment 2：Porous LiNi1/3Co1/3Mn1/3O2It is prepared by the electrochemistry lithiumation auxiliary of nanoparticle
1)(Ni1/3Co1/3Mn1/3)CO3It is prepared by the hydro-thermal of nanoparticle：
It is 1 by mol ratio:1:1 Ni (C2H3O2)2·4H2O、Co(C2H3O2)2·4H2O and Mn (C2H3O2)2·4H2O is molten
Solution is in the mixed solution of 80mL deionized waters and ethylene glycol (volumetric mixture ratio is between 0.5~1.5), after at the uniform velocity stirring half an hour
0.2~0.8mol/L mixed solution is made, it is uniform by what is obtained after adding 0.016~0.064mol urea into solution
Solution is transferred in the 100ml polytetrafluoroethylcontainer container with rustless steel container good seal, be placed in preheated drying box in
10~24h of hydro-thermal reaction at 130~200 DEG C, after furnace cooling to room temperature, using deionized water centrifuge washing three times, anhydrous second
After alcohol washed once again, 10h is dried at 80 DEG C, it is final to obtain the (Ni that the diameter as shown in accompanying drawing 5a is about 2~25 μm1/3Co1/ 3Mn1/3)CO3Nanoparticle.
2)NiCoMnO4The preparation of nanoparticle:
Will be according to (Ni obtained by step (1)1/3Co1/3Mn1/3)CO3After nanoparticle retracts 2~8h at 350~550 DEG C
Obtain corresponding porous NiCoMnO4Nanoparticle.
3)NiCoMnO4Prepared by nanoparticle electrode assembles with battery：
By NiCoMnO4Nanoparticle (90%) is uniformly mixed to prepare with conductive black (5%) and binding agent (PVDF, 5%)
Homogeneous slurry, then gained colloid is coated on copper foil surface, after drying 3h at 70 DEG C, continue to be dried in vacuo 5h at 90 DEG C,
The final NiCoMnO for obtaining electrochemistry lithiumation4Nanoparticle electrode.
Using lithium piece as to electrode (negative pole), with 1mol/L LiPF6EC+DEC solution be electrolyte, with NiCoMnO4Nanometer
Microballoon electrode is that working electrode (positive pole) is assembled into lithium ion battery in vacuum glove box.
4) electrochemistry lithiumation：0.5C (C is theoretical capacity xxx mAh/g) current density is used to according to step (2) institute
The battery of installation is discharged, by controlling discharge time electric discharge 10h NiCoMnO43 Li are inserted in the lattice of nanoparticle+。
5) dismounting of lithiumation battery and the cleaning of lithiated electrode：Battery after the lithiumation that will be obtained according to step (3) is torn open
Dismantle, collect the electrode after the electrochemistry lithiumation of acquisition, washed using poly- ethyl carbonate (PC) and ethanol are successively each three times, 80
The NiCoMnO after corresponding lithiumation is obtained after drying 5h at DEG C4Nanoparticle transiting product.
6) Low Temperature Heat Treatment：Collect according to the transition metal oxide after the lithiumation obtained by step (4), hydroxide or
Person's carbonate transiting product is cooled to room temperature at 450~600 DEG C under air after 10~15h of process annealing, final to be made such as
2~20 μm of lithium-containing transition metal oxide LiNi of diameter shown in accompanying drawing 5b1/3Co1/3Mn1/3O2Nanoparticle.
Embodiment 3：xLi2MnO3·(1-x)LiNi1/3Co1/3Mn1/3O2(0<x<1) the electrochemistry lithiumation auxiliary of nanoparticle
Prepare
1)(Ni(1-x)/3Co(1-x)/3Mn(1+2x)/3)CO3It is prepared by the hydro-thermal of nanoparticle：
It is (1-x) by mol ratio:(1-x):Ni (the C of (1+2x)2H3O2)2·4H2O、Co(C2H3O2)2·4H2O and Mn
(C2H3O2)2·4H2O is dissolved in the mixed solution (volumetric mixture ratio is between 0.5~1.5) of 80mL deionized waters and ethylene glycol,
0.2~0.8mol/L mixed solution is at the uniform velocity made after stirring half an hour, 0.016~0.064mol urea is added into solution
Afterwards, the homogeneous solution obtained is transferred in the 100ml polytetrafluoroethylcontainer container with rustless steel container good seal, be placed in pre-
In the good drying box of heat at 130~200 DEG C 10~24h of hydro-thermal reaction, after furnace cooling to room temperature, centrifuged using deionized water
Washing three times, after absolute ethyl alcohol washed once again, dries 10h, the final diameter that obtains is about 5~25 μm at 80 DEG C
(Ni(1-x)/3Co(1-x)/3Mn(1+2x)/3)CO3Nanoparticle.
2)Ni(1-x)Co(1-x)Mn(1+2x)O4The preparation of nanoparticle:
Will be according to (Ni obtained by step (1)(1-x)/3Co(1-x)/3Mn(1+2x)/3)CO3Nanoparticle moves back at 350~550 DEG C
Corresponding porous Ni is obtained after returning 2~8h(1-x)Co(1-x)Mn(1+2x)O4Nanoparticle.
3)Ni(1-x)Co(1-x)Mn(1+2x)O4Prepared by nanoparticle electrode assembles with battery：
By Ni(1-x)Co(1-x)Mn(1+2x)O4Nanoparticle (90%) and conductive black (5%) and binding agent (PVDF, 5%) are equal
It is even to be mixed to prepare homogeneous slurry, then gained colloid is coated on copper foil surface, after drying 3h at 70 DEG C, continue true at 90 DEG C
Sky dries 5h, the final Ni for obtaining electrochemistry lithiumation(1-x)Co(1-x)Mn(1+2x)O4Nanoparticle electrode.
Using lithium piece as to electrode (negative pole), with 1mol/L LiClO4PC solution be electrolyte, with Ni(1-x)Co(1-x)
Mn(1+2x)O4Nanoparticle electrode is that working electrode (positive pole) is assembled into lithium ion battery in vacuum glove box.
4) electrochemistry lithiumation：0.1C (C is theoretical capacity xxx mAh/g) current density is used to according to step (2) institute
The battery of installation is discharged, by controlling discharge time electric discharge 10h Ni(1-x)Co(1-x)Mn(1+2x)O4In the lattice of nanoparticle
Insert 3 Li+。
5) dismounting of lithiumation battery and the cleaning of lithiated electrode：Battery after the lithiumation that will be obtained according to step (3) is torn open
Dismantle, collect the electrode after the electrochemistry lithiumation of acquisition, washed using poly- ethyl carbonate (PC) and ethanol are successively each three times, 80
The Ni after corresponding lithiumation is obtained after drying 5h at DEG C(1-x)Co(1-x)Mn(1+2x)O4Nanoparticle transiting product.
6) Low Temperature Heat Treatment：Collect according to the transition metal oxide after the lithiumation obtained by step (4), hydroxide or
Person's carbonate transiting product is cooled to room temperature at 450~600 DEG C under air after 10~15h of process annealing, final to be made straight
The rich lithium transition-metal oxide xLi in 2~20 μm of footpath2MnO3·(1-x)LiNi1/3Co1/3Mn1/3O2(0<x<1) nanoparticle.
Embodiment 4：xLi2MnO3·(1-x)LiNi1/2Mn1/2O2The electrochemistry lithiumation auxiliary of (x is between 0~1) nanoparticle
Prepare
1)(Ni(1-x)/2Mn(1+x)/2)CO3The solvent hot preparation of nanoparticle：
It is (1-x) by mol ratio:Ni (the C of (1+x)2H3O2)2·4H2O and Mn (C2H3O2)2·4H2O is dissolved in 80mL and gone
In the mixed solution of ion ethylene glycol, the mixed solution of obtained 0.2~0.8mol/L after half an hour is at the uniform velocity stirred, is added into solution
After adding 0.016~0.064mol urea, the homogeneous solution obtained is transferred to 100ml gathering with rustless steel container good seal
In tetrafluoroethene container, 10~24h of hydro-thermal reaction at 130~200 DEG C, furnace cooling to room are placed in preheated drying box
Wen Hou, after absolute ethyl alcohol washed once again, 10h is dried at 80 DEG C using deionized water centrifuge washing three times, it is final to obtain directly
Footpath is about 5~25 μm of (Ni(1-x)/2Mn(1+x)/2)CO3Nanoparticle.
2)Ni(1-x)Co(1-x)Mn(1+2x)O4The preparation of nanoparticle:
Will be according to (Ni obtained by step (1)(1-x)/2Mn(1+x)/2)CO3Nanoparticle retracts 2~8h at 350~550 DEG C
Corresponding porous (Ni is obtained afterwards(1-x)Mn(1+x))3O4Nanoparticle.
3)(Ni(1-x)Mn(1+x))3O4Prepared by nanoparticle electrode assembles with battery：
By (Ni(1-x)Mn(1+x))3O4Nanoparticle (90%) and conductive black (5%) and binding agent (PVDF, 5%) are uniform
Homogeneous slurry is mixed to prepare, then gained colloid is coated on copper foil surface, after drying 3h at 70 DEG C, continues the vacuum at 90 DEG C
Dry 5h, the final Ni for obtaining electrochemistry lithiumation(1-x)Co(1-x)Mn(1+2x)O4Nanoparticle electrode.
Using lithium piece as to electrode (negative pole), with 1mol/L LiClO4PC solution be electrolyte, with (Ni(1-x)Mn(1+x))3O4Nanoparticle electrode is that working electrode (positive pole) is assembled into lithium ion battery in vacuum glove box.
4) electrochemistry lithiumation：The battery installed according to step (2) is carried out using 50~1000mA/g current density
Electric discharge, by controlling discharge time 0.5~10h of electric discharge (Ni(1-x)Mn(1+x))3O43 Li are inserted in the lattice of nanoparticle+。
5) dismounting of lithiumation battery and the cleaning of lithiated electrode：Battery after the lithiumation that will be obtained according to step (3) is torn open
Dismantle, collect the electrode after the electrochemistry lithiumation of acquisition, washed using poly- ethyl carbonate (PC) and ethanol are successively each three times, 80
(the Ni after corresponding lithiumation is obtained after drying 5h at DEG C(1-x)Mn(1+x))3O4Nanoparticle transiting product.
6) Low Temperature Heat Treatment：Collect according to the transition metal oxide after the lithiumation obtained by step (4), hydroxide or
Person's carbonate transiting product is cooled to room temperature under air at 450~600 DEG C after 10~15h of process annealing, finally be made 2~
20 μm of rich lithium transition-metal oxide xLi2MnO3·(1-x)LiNi1/2Mn1/2O2Nanoparticle.
Embodiment 5：xLi2MnO3·(1-x)LiNi1/2Mn3/2O4The electrochemistry lithiumation auxiliary of (x is between 0~1) nanoparticle
Prepare
1)(Ni(1-x)/2Mn(3-x)/2)(OH)2It is prepared by the coprecipitation of nanoparticle：
It is (1-x) by mol ratio:Ni (the C of (3-x)2H3O2)2·4H2O and Mn (C2H3O2)2·4H2O is dissolved in 80mL and gone
In the mixed solution of ion ethylene glycol, the mixed solution that 0.2~0.8mol/L is made after half an hour is at the uniform velocity stirred, 1000~
Under 1500 turns/min stir speed (S.S.), 1~5mol sodium hydroxides or potassium hydroxide solution are added into solution, by what is obtained
Homogeneous solution is transferred in the 100ml polytetrafluoroethylcontainer container with rustless steel container good seal, is placed in preheated drying box
In at 130~200 DEG C 10~24h of hydro-thermal reaction, after furnace cooling to room temperature, using deionized water centrifuge washing three times, nothing
After water-ethanol washed once again, 10h is dried at 80 DEG C, it is final to obtain the (Ni that diameter is about 5~25 μm(1-x)/2Mn(3-x)/2)
(OH)2Nanoparticle.
2)(Ni(1-x)/2Mn(3-2x)/2)3O4The preparation of nanoparticle:
Will be according to (Ni obtained by step (1)(1-x)/2Mn(3-x)/2)(OH)2Nanoparticle retracts 2 at 350~550 DEG C~
Corresponding porous (Ni is obtained after 8h(1-x)/2Mn(3-x)/2)3O4Nanoparticle.
3)(Ni(1-x)/2Mn(3-x)/2)3O4Prepared by nanoparticle electrode assembles with battery：
By (Ni(1-x)/2Mn(3-x)/2)3O4Nanoparticle (90%) and conductive black (5%) and binding agent (PVDF, 5%) are equal
It is even to be mixed to prepare homogeneous slurry, then gained colloid is coated on copper foil surface, after drying 3h at 70 DEG C, continue true at 90 DEG C
Sky dries 5h, the final (Ni for obtaining electrochemistry lithiumation(1-x)/2Mn(3-x)/2)3O4Nanoparticle electrode.
Using lithium piece as to electrode (negative pole), with 1mol/L LiClO4PC solution be electrolyte, with (Ni(1-x)/ 2Mn(3-x)/2)3O4Nanoparticle electrode is that working electrode (positive pole) is assembled into lithium ion battery in vacuum glove box.
4) electrochemistry lithiumation：The battery installed according to step (2) is carried out using 50~1000mA/g current density
Electric discharge, by controlling discharge time 0.5~10h of electric discharge (Ni(1-x)/2Mn(3-x)/2)3O43 Li are inserted in the lattice of nanoparticle+。
5) dismounting of lithiumation battery and the cleaning of lithiated electrode：Battery after the lithiumation that will be obtained according to step (3) is torn open
Dismantle, collect the electrode after the electrochemistry lithiumation of acquisition, washed using poly- ethyl carbonate (PC) and ethanol are successively each three times, 80
(the Ni after corresponding lithiumation is obtained after drying 5h at DEG C(1-x)Mn(1+x))3O4Nanoparticle transiting product.
6) Low Temperature Heat Treatment：Collect according to the transition metal oxide after the lithiumation obtained by step (4), hydroxide or
Person's carbonate transiting product is cooled to room temperature at 450~600 DEG C under air after 10~15h of process annealing, final that richness is made
Lithium transition-metal oxide xLi2MnO3·(1-x)LiNi1/2Mn3/2O4Nanoparticle.
Embodiment 6：Li4Ti5O12It is prepared by the electrochemistry lithiumation auxiliary of nanosphere
1)TiO2The preparation of nanosphere:10~20ml tetrabutyl titanates are dissolved in 150~250ml absolute ethyl alcohols first
In, the clear solution obtained is added dropwise in 1.5~2.0g cetylamine solution by uniform stirring after 30 minutes.Then by 2~
10ml NH3·H2O (25%) is added dropwise in the mixed solution obtained before this.By the magnetic agitation of 1~3 hour, thoroughly
Bright solution be gradually transformed into milky troubled liquor at 80~120 DEG C dry 24 hours after obtain diameter 300~
600nmTiO2White nanosphere.
2)TiO2Prepared by nanometer ball electrode assembles with battery：
By TiO2Nanosphere (90%) is uniformly mixed to prepare homogeneous slurry with conductive black (5%) and binding agent (PVDF, 5%)
Material, then gained colloid is coated on copper foil surface, after drying 3h at 70 DEG C, continue to be dried in vacuo 5h at 90 DEG C, finally obtain
Obtain the TiO of electrochemistry lithiumation2Nanometer ball electrode.
Using lithium piece as to electrode (negative pole), with 1mol/L LiClO4PC solution be electrolyte, with TiO2Nanometer ball electrode
Lithium ion battery is assembled into vacuum glove box for working electrode (positive pole).
3) electrochemistry lithiumation：The battery installed according to step (2) is carried out using 50~1000mA/g current density
Electric discharge, by controlling discharge time 0.5~10h of electric discharge TiO20.8 Li is inserted in the lattice of nanosphere+。
4) dismounting of lithiumation battery and the cleaning of lithiated electrode：Battery after the lithiumation that will be obtained according to step (3) is torn open
Dismantle, collect the electrode after the electrochemistry lithiumation of acquisition, washed using poly- ethyl carbonate (PC) and ethanol are successively each three times, 80
The TiO after corresponding lithiumation is obtained after drying 5h at DEG C2Nanosphere transiting product.
5) Low Temperature Heat Treatment：Collect according to the transition metal oxide after the lithiumation obtained by step (4), hydroxide or
Person's carbonate transiting product is cooled under air or inert atmosphere protection at 450~600 DEG C after 10~15h of process annealing
Room temperature, 200~500nmLi is finally made4Ti5O12Nanosphere.
Embodiments of the invention are only the present invention for example, and can not limit the present invention.
Claims (2)
1. a kind of preparation method of the electricity of lithium containing lithium metal oxide nano-electrode material, it is characterised in that methods described is included such as
Lower step：
(1) preparation of nano-structural transition metal compound：Coagulated by solvent-thermal method or hydro-thermal method or solution deposit or colloidal sol
Glue method is prepared；
(2) electrochemistry lithiumation is used crosses metal compound electrode preparation：The material that will be prepared according to method shown in step (1)
Uniformly mixed with conductive black and binding agent and be coated on copper foil surface, drying processing；
(3) electrochemistry lithiumation electricity consumption pond assembles：Using lithium metal to be negative pole to electrode, with LiPF6Or LiClO4Or in LiTFSI
One type commercial li-ion battery electrolyte is electrolyte, is positive pole group by working electrode of the electrode prepared by step (2)
Dress up lithium ion battery；
(4) electrochemistry prelithiation：The battery that step (3) is installed carries out discharge process；
(5) dismounting of lithiumation battery and the cleaning of lithiated electrode：Battery roll after the lithiumation that step (4) is obtained is opened, and is received
Colelctor electrode, then transiting product is obtained after cleaning-drying；
(6) Low Temperature Heat Treatment：Collect according to the transiting product obtained by step (5) under air or inert atmosphere protection
Room temperature is cooled at 400~600 DEG C after 2~10h of process annealing, lithium-containing transition metal oxide is finally made；
Solvent-thermal method is in the step 1：The mixture of transition metal salt or transition metal salt and surfactant is dissolved in
In high boiling solvent, after reacting 5-48h at 150-330 DEG C under closed or counterflow condition, nanometer is obtained after cleaning-drying
Structural transition metal oxide；
Hydro-thermal method is in the step 1：By the way that the mixture of transition metal salt or transition metal salt and surfactant is dissolved
In the double solvents of water or water, after reacting 5-48h at 150-200 DEG C in confined conditions, nanometer is obtained after cleaning-drying
Structural transition metallic compound；
Solution deposit in the step 1 is：By the way that the salt containing transition metal is dissolved in into the aqueous solution or containing surface-active
In the aqueous solution of agent, then uniform transition metal salt solution is slowly dropped in the alkaline sedimentation agent solution prepared in advance,
Finally by under the conditions of 400-550 DEG C decomposition reaction 2-10h corresponding nano-structural transition metal oxide is made；
Sol-gal process in the step 1 is：Corresponding transition metal salt solution is slowly dropped to by citric acid and second two
Alcoholic solution in molar ratio 2:In 1 colloidal sol prepared, the mol ratio of metal ion and citric acid is between 0.5~1, at 100 DEG C
Corresponding transition metal oxide nano particle is made after 2~24h is decomposed at 400~500 DEG C in lower drying；
High boiling solvent in the solvent-thermal method includes ethylene glycol or glycerine or tetraethylene glycol；
The double solvents of water in the hydro-thermal method is water and ethylene glycol or the double solvents of formic acid or formaldehyde；
The concentration of transition metal salt in the precipitation method is 0.1-2mol/L, the surfactant and transition metal ions
Mol ratio is 0.5-2, and the concentration of the alkaline precipitating agent is 0.5-6mol/L, and the reaction temperature of precipitation reaction is room temperature -200
DEG C, the reaction atmosphere is air or protective atmosphere, and the reaction time is 5-48h；
Binding agent in the step 2 includes carboxymethyl cellulose class, polyvinylidene fluoride alkenes, the nano structural material, conduction
The percentage by weight of carbon black and binding agent is：
Nano structural material 80%-96%
Conductive black 2%-10%
Binding agent 2%-10%.
2. one kind lithium containing the lithium metal oxide electricity nano-electrode material drawn according to claim 1 preparation method, is characterised by
Its chemical formula is Li4M5O12Or LixNyOx, wherein M be Ti, V, Mn, Ni element in one or more, N Ti, V, Mn, Ni,
One or more in Co, Fe, Al, Mo, Sn, Ge element, x is between 0.1-2, y=1 or 2, z=2 or 3 or 4.
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| CN103915262A (en) * | 2013-01-04 | 2014-07-09 | 深圳清华大学研究院 | Method for lithium pre-embedment of negative electrode of lithium ion capacitor |
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| CN103915262A (en) * | 2013-01-04 | 2014-07-09 | 深圳清华大学研究院 | Method for lithium pre-embedment of negative electrode of lithium ion capacitor |
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