CN105161679A - Lithium-rich cathode material and preparation method and application thereof - Google Patents

Lithium-rich cathode material and preparation method and application thereof Download PDF

Info

Publication number
CN105161679A
CN105161679A CN201510370957.XA CN201510370957A CN105161679A CN 105161679 A CN105161679 A CN 105161679A CN 201510370957 A CN201510370957 A CN 201510370957A CN 105161679 A CN105161679 A CN 105161679A
Authority
CN
China
Prior art keywords
lithium
preparation
anode material
rich anode
rich
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201510370957.XA
Other languages
Chinese (zh)
Other versions
CN105161679B (en
Inventor
郑春满
陈宇方
谢凯
王珲
韩喻
洪晓斌
盘毅
李德湛
李宇杰
许静
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
National University of Defense Technology
Original Assignee
National University of Defense Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by National University of Defense Technology filed Critical National University of Defense Technology
Priority to CN201510370957.XA priority Critical patent/CN105161679B/en
Publication of CN105161679A publication Critical patent/CN105161679A/en
Application granted granted Critical
Publication of CN105161679B publication Critical patent/CN105161679B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a lithium-rich cathode material and a preparation method and an application thereof. The lithium-rich cathode material has a core-shell structure, and is composed of a core material lithium-rich solid solution and a shell material of one of layered ternary material and spinel structure material with lithium ionic conductivity; the preparation method I comprises the following steps: preparation of the core material, preparation of the core material coated with a shell material precursor, presintering treatment of a core-shell structure material and high-temperature sintering treatment; and the method II comprises the following steps: preparation of the core-material precursor, preparation of a gradient structure precursor material, presintering treatment of the core-shell structure material, and high-temperature sintering treatment. The preparation method disclosed by the invention has the advantages of being simple in technical process, nontoxic, harmless, simple in raw materials, few in byproducts, suitable for large-scale production and the like; the prepared lithium-rich cathode material has a gradient structure; the functional effect is materialized by the structure; the core has high capacity characteristic; the cycling stability of the material can be improved by the surface; and the lithium-rich cathode material can be widely applied to a lithium-ion battery.

Description

Lithium-rich anode material and its preparation method and application
Technical field
The present invention relates to technical field of lithium ion, be specifically related to a kind of functional form nucleocapsid structure high-capacity lithium-rich cathode material, also relate to the preparation method of this positive electrode and the application in lithium ion battery.
Background technology
Along with the development of society and the progress of science and technology, lithium ion battery is widely used as energy resource system of new generation.Lithium ion battery, as electrical source of power, compares traditional oils electrical source of power, the advantages such as it has high security, pollution-free, makes lithium battery have power supply on vehicle application prospect, at present, successfully produces pure electric automobile both at home and abroad and extensively sells.
Nineteen ninety, Japanese Sony company proposes with LiCoO 2as the lithium rechargeable battery that positive electrode and graphite are formed as negative pole, but be subject to the restriction of its intrinsic crystal structure, LiCoO 2positive electrode can only give play to the theoretical capacity of 50%, and what then occur is that charge/discharge capacity is increased to 160 ~ 180mAh/g by the layered cathode material that main capacity is originated with Ni.Positive electrode system mainly based on ternary layered structure comprises LiNi xco ymn 1-x-yo 2, LiNi 0.8co 0.15al 0.05o 2.This kind of positive electrode improves charge/discharge capacity mainly through optimising and adjustment crystal structure, and reversible dischargeable capacity is the highest has reached 70% of theoretical capacity, is but still difficult to meet application demand.Therefore, to possess the positive electrode of the more high power capacity reversible removal lithium embedded of height of relative low price Simultaneous Stabilization circulation again significant in research.
Lithium-rich anode material is mainly made up of two-phase or multiphase solid solution possessing regular crystal structure, mostly adopts the mode of lamellar phase solid solution for improving structural compatibility.The lithium-rich anode material that layer structure solid solution is formed is all α-NaFeO 2laminar configuration, belongs to hexagonal crystal system.Wherein because the difference of ion arrangement and occupy-place can form special solid solution structure.Therefore this kind of positive electrode can by the characteristic regulating the phase composition in solid solution structure and ratio to regulate and control positive electrode.
The development of nearly 30 years of positive electrode experience has defined multiple synthetic methods such as comprising solid phase method, coprecipitation, sol-gal process, hydro thermal method and template, wherein solid phase method is difficult to regulate and control the distribution of material interior element, template is mainly used in synthesizing the positive electrode with special appearance, sol-gal process and water heat transfer gradient-structure technical process too complicated.
Summary of the invention
Technical problem to be solved by this invention overcomes deficiency of the prior art, a kind of charge and discharge cycles capacity and crystal structure is stablized, tap density is high lithium-rich anode material are provided, additionally provide a kind of technical process simple, nontoxic, raw material is simple, accessory substance is few, is applicable to the lithium-rich anode material preparation method of large-scale production, correspondingly additionally provides the application of lithium-rich anode material in lithium ion battery.
For solving the problems of the technologies described above, the technical solution used in the present invention:
A kind of lithium-rich anode material, described lithium-rich anode material comprises rich lithium solid solution and has the material of lithium ion conduction ability, described in there is lithium ion conduction ability material be coated on described rich lithium solid solution surface and form nucleocapsid structure; The described material with lithium ion conduction ability is stratiform ternary material or spinel structure material.
In above-mentioned lithium-rich anode material, further, the chemical formula of the described lithium-rich anode material as nuclear material is: xLi 2mnO 3yLiNi x1mn y1co (1-x1-y1)o 2zLiNi x2mn y2co z2al x3o 2wherein 0<x<1/2,0<y<7/10,0<z<3/10,1/3≤x1≤1/2,1/3≤y1≤1/2,0≤x2≤4/5,0≤y2≤3/2,0≤z2≤1/6,0≤x3≤1/10.
In above-mentioned lithium-rich anode material, further, described rich lithium solid solution is Li 7/6mn 1/2ni 1/6co 1/6o 2.Preferred further, described Li 7/6mn 1/2ni 1/6co 1/6o 2rich lithium solid solution is by the Li of layer structure 2mnO 3and LiNi 1/3co 1/3mn 1/3o 2form.
In above-mentioned lithium-rich anode material, further, layered ternary material is LiNi 0.8co 0.15al 0.05o 2.
In above-mentioned lithium-rich anode material, further, described spinel structure material is LiNi 0.5mn 1.5o 4.
In above-mentioned lithium-rich anode material, preferably, the thickness described in the material of lithium ion conduction ability is 0.002 μm ~ 0.2 μm.
As a total technical conceive, present invention also offers a kind of preparation method of above-mentioned lithium-rich anode material, be specially cladding process after precipitation, after described precipitation, cladding process specifically comprises the following steps:
S1, nickel salt, cobalt salt, manganese salt are made into mixed solution A, then mixed solution A and precipitation reagent, complexing agent are carried out coprecipitation reaction, through ripening, prepare core material presoma;
S2, the core material presoma prepared by described step S1 mix with lithium source, then carry out high temperature sintering 10 ~ 24h with 700 ~ 900 DEG C and obtain core material;
S3, one or more in nickel salt, cobalt salt, aluminium salt, manganese salt are made into mixed solution B, then described mixed solution B and precipitation reagent, complexing agent are together joined in core material prepared by described step S2 and carry out coated coprecipitation reaction, through ripening, prepare the core material being coated with Shell Materials presoma;
S4, the core material being coated with Shell Materials presoma prepared by described step S3 mix with lithium source, then carry out high temperature sintering 10 ~ 24h with 700 ~ 900 DEG C, complete the preparation of described lithium-rich anode material.
Above-mentioned preparation method, preferably, step S2 is specially: the core material presoma prepared by described step S1 is heat-treated at 120 ~ 200 DEG C, the stoichiometric proportion of then pressing core material mixes with lithium source, mixed sample is warming up to 400 ~ 500 DEG C and carries out presintering process 10 ~ 20h; Sample after completing presintering process is warming up to 700 ~ 900 DEG C and carries out high temperature sintering process 10 ~ 24h, prepare core material.
Above-mentioned preparation method, preferably, step S4 is specially: the core material being coated with Shell Materials presoma prepared by described step S3 mixes with lithium source, then mixed sample is warming up to 400 ~ 500 DEG C and carries out presintering process 10 ~ 20h; Sample after completing presintering process is warming up to 700 ~ 900 DEG C under air atmosphere or oxygen atmosphere and carries out high temperature sintering process 10 ~ 24h, prepare lithium-rich anode material.
Above-mentioned preparation method, preferably, the heating rate of described presintering process is 0.5 ~ 5 DEG C/min; The heating rate of described high temperature sintering process is 0.5 ~ 5 DEG C/min.
In above-mentioned preparation method, further, described nickel salt comprises one or more in nickel nitrate, nickelous sulfate, nickel chloride; Described cobalt salt comprise in cobalt nitrate, cobaltous sulfate, cobalt chloride one or more; Described manganese salt comprise in manganese nitrate, manganese sulfate, manganese chloride one or more; Described aluminium salt comprise in aluminum nitrate, aluminum sulfate, aluminium chloride one or more; Described lithium source comprise in lithium hydroxide, lithium carbonate, lithium nitrate one or more.
In above-mentioned preparation method, further, the hydroxide of described precipitation reagent to be concentration be 0.05 ~ 5mol/L or concentration are the carbonate of 1 ~ 2mol/L.The concentration more preferably 1 ~ 2mol/L of hydroxide.Preferably, described hydroxide is one or both in NaOH, potassium hydroxide; Described carbonate is one or more in sodium carbonate, potash, carbonic hydroammonium.
In above-mentioned preparation method, further, the ammoniacal liquor of described complexing agent to be concentration be 0.02 ~ 2mol/L.The concentration more preferably 0.5 ~ 1mol/L of ammoniacal liquor.
In above-mentioned preparation method, further, in described mixed solution A, the concentration of metal cation is 0.5mol/L ~ 2mol/L; In described mixed solution B, the concentration of metal cation is 0.01mol/L ~ 0.05mol/L.
In above-mentioned preparation method, further, in described mixed solution A, the mol ratio of nickel salt, cobalt salt, manganese salt is 1/6 ~ 1/3: 0 ~ 1/6: 1/2 ~ 1.
In above-mentioned preparation method, further, described mixed solution B is mixed by nickel salt and manganese salt, and the mol ratio of described nickel salt and manganese salt is 0.3 ~ 0.5: 1.7 ~ 1.5.
As a total technical conceive, present invention also offers the preparation method of the above-mentioned lithium-rich anode material of similar another kind, be specially one coprecipitation, described one coprecipitation specifically comprises the following steps:
S1, nickel salt, cobalt salt, manganese salt are made into mixed solution A, then mixed solution A and precipitation reagent, complexing agent are carried out coprecipitation reaction, through ripening, prepare core material presoma;
S2, one or more in nickel salt, cobalt salt, aluminium salt, manganese salt are made into mixed solution B, described mixed solution B is joined in core material presoma prepared by described step S1 and carry out coated coprecipitation reaction, through ripening, prepare gradient-structure persursor material;
S3, the gradient-structure persursor material prepared by described step S2 mix with lithium source, then carry out high temperature sintering 10 ~ 24h with 750 ~ 950 DEG C, complete the preparation of described lithium-rich anode material.
Above-mentioned preparation method, preferably, step S3 is specially: the gradient-structure persursor material prepared by described step S2 is heat-treated at 150 ~ 200 DEG C, then be 1: 1.1 ~ 1.3 to mix with lithium source in molar ratio, mixed sample be warming up to 450 ~ 600 DEG C and carry out presintering process 10 ~ 20h; Sample after completing presintering process is warming up to 750 ~ 950 DEG C under air atmosphere or oxygen atmosphere and carries out high temperature sintering process 10 ~ 24h, prepare lithium-rich anode material.
In above-mentioned preparation method, preferably, the heating rate of described presintering process is 0.5 ~ 5 DEG C/min; The heating rate of described high temperature sintering process is 1 ~ 5 DEG C/min.
In above-mentioned preparation method, further, described nickel salt comprises one or more in nickel nitrate, nickelous sulfate, nickel chloride; Described cobalt salt comprise in cobalt nitrate, cobaltous sulfate, cobalt chloride one or more; Described manganese salt comprise in manganese nitrate, manganese sulfate, manganese chloride one or more; Described aluminium salt comprise in aluminum nitrate, aluminum sulfate, aluminium chloride one or more; Described lithium source comprise in lithium hydroxide, lithium carbonate, lithium nitrate one or more.
In above-mentioned preparation method, further, the hydroxide of described precipitation reagent to be concentration be 0.05 ~ 5mol/L or concentration are the carbonate of 1 ~ 2mol/L.The concentration more preferably 1 ~ 2mol/L of hydroxide.Preferably, described hydroxide is one or both in NaOH, potassium hydroxide; Described carbonate is one or more in sodium carbonate, potash, carbonic hydroammonium.
In above-mentioned preparation method, further, the ammoniacal liquor of described complexing agent to be concentration be 0.02 ~ 2mol/L.The concentration more preferably 0.5 ~ 1mol/L of ammoniacal liquor.
In above-mentioned preparation method, further, in described mixed solution A, the concentration of metal cation is 0.5mol/L ~ 2mol/L; In described mixed solution B, the concentration of metal cation is 0.01mol/L ~ 0.05mol/L.
In above-mentioned preparation method, further, in described mixed solution A, the mol ratio of nickel salt, cobalt salt, manganese salt is 1/6 ~ 1/3: 0 ~ 1/6: 1/2 ~ 1.
In above-mentioned preparation method, further, described mixed solution B is mixed by nickel salt and manganese salt, and the mol ratio of described nickel salt and manganese salt is 0.3 ~ 0.5: 1.7 ~ 1.5.
As a total inventive concept, the invention provides the application of lithium-rich anode material in lithium ion cell positive prepared by a kind of above-mentioned lithium-rich anode material or above-mentioned preparation method.
In above-mentioned application, the preparation method of described lithium ion cell positive comprises the following steps: by described lithium-rich anode material, conductive agent, binding agent according to mass ratio be 70 ~ 97: 2 ~ 10: 2 ~ 10 mixing, be mixed with slurry, then by even for described slurry blade coating on aluminium foil, compressing.
In preparation method of the present invention, described coated coprecipitation reaction carries out under the water-bath system of 50 ~ 60 DEG C, keeping reaction system to be in constant speed stirs in (rotating speed is 500 ~ 700rpm), carries out adjustment make system pH maintain between 10 ~ 11.5 by the flow velocity regulating and controlling precipitation reagent; The liquid feeding speed of each raw material is 1 ~ 5ml/min.
In preparation method of the present invention, the normal rates in described gradient-structure persursor material and lithium source is 1: 1.1 ~ 1.3, for ensureing to replenish the loss because of the Li source of causing of volatilizing of lithium in high temperature sintering heat treatment process, therefore add Li source on stoichiometric proportion excessive 3%.
Compared with prior art, the invention has the advantages that:
(1) the invention provides a kind of lithium-rich anode material, there is the rich lithium solid solution of high capacity characteristics as inner nuclear material, there is the stratiform ternary material of lithium ion conduction ability, spinel structure material as Shell Materials.Wherein rich lithium solid solution chooses two kinds of layer structures and Li 2mnO 3and LiNi 1/3co 1/3mn 1/3o 2form, the difference due to this two kinds of layer structure intermediate ions arrangement hinders the transmission of lithium ion in this solid solution structure to a certain extent, makes the high capacity characteristics of this structure be difficult to bring into play under comparatively high magnification condition.The application mainly adopts the coated rich lithium solid solution of spinel structure positive electrode, stratiform ternary material, because spinel structure material and stratiform ternary material have good high rate performance, its high rate performance can be significantly improved, make the advantages such as the lithium-rich anode material prepared has functional strong, charge and discharge cycles capacity and crystal structure is stable, material circulation stability is high, tap density is high.
(2) the invention provides a kind of rear coated method of precipitation that adopts and prepare lithium-rich anode material, the calcining of core material presoma is formed core material, then Shell Materials is coated on core material surface, by regulating and controlling the relation of homogeneous nucleation and heterogeneous nucleation, guarantee that post precipitation reaction carries out on core material, make the lithium-rich anode material prepared have coated densification and coating content advantages of higher.Simultaneously, the lithium-rich anode material that after adopting precipitation prepared by method for coating, on the one hand, ensure that second particle presents gradient-structure characteristic, also define the gradient-structure of primary particle to a certain extent simultaneously, be conducive to playing core material height like this and hold characteristic, the high stable of Shell Materials and fast ionic transport properties; On the other hand, the Nomenclature Composition and Structure of Complexes be conducive to by regulating and controlling gradient-structure carrys out the performance of optimal design and regulation and control gradient-structure.The present invention, mainly through the relation regulating the real-time concentration of liquid feeding speed and reaction system to regulate and control homogeneous nucleation and heterogeneous nucleation, further increases tap density.
(3) the invention provides a kind of method adopting one coprecipitation to prepare lithium-rich anode material, the controllable distribution of material component and Elemental redistribution can be realized, and utilizing sintering process to be formed the lithium-rich anode material with certain Elemental redistribution gradient, technical process is simple, nontoxic simultaneously, raw material is simple, accessory substance is few, be applicable to suitability for industrialized production.
(4) the invention provides a kind of lithium-rich anode material and prepare the application in lithium ion battery, make full use of in the lithium-rich anode material of gradient-structure, core material has high capacity characteristics, surface crust material can improve the characteristic of core material cyclical stability, makes that the lithium ion battery battery capacity for preparing is high, relative low price.
Accompanying drawing explanation
For making the object of the embodiment of the present invention, technical scheme and advantage clearly, below in conjunction with the accompanying drawing in the embodiment of the present invention, clear, complete description is carried out to the technical scheme in the embodiment of the present invention.
Fig. 1 is the structural representation of lithium-rich anode material of the present invention.
Fig. 2 is the transmission electron microscope picture of the coated lithium-rich anode material of spinel structure prepared by the embodiment of the present invention 1.
Fig. 3 is the XRD spectra of the coated lithium-rich anode material of spinel structure prepared by the embodiment of the present invention 1.
Fig. 4 is the coated lithium-rich anode material different multiplying discharge cycles performance map of spinel structure prepared by the embodiment of the present invention 1.
Fig. 5 is the transmission electron microscope picture of the coated lithium-rich anode material of spinel structure prepared by the embodiment of the present invention 2.
Fig. 6 is the XRD spectra of the coated lithium-rich anode material of spinel structure prepared by the embodiment of the present invention 2.
Fig. 7 is the comparison diagram of not coated lithium-rich anode material different multiplying discharge cycles performance prepared by the coated lithium-rich anode material of spinel structure prepared of the embodiment of the present invention 2 and comparative example 1.
Fig. 8 is the XRD spectra of the coated lithium-rich anode material of NCA prepared by the embodiment of the present invention 3.
The comparison diagram of Fig. 9 not coated lithium-rich anode material 0.1C circulation volume that to be the coated lithium-rich anode material of NCA prepared of the embodiment of the present invention 3 prepare with comparative example 1 and the mean voltage that discharges.
Figure 10 is the XRD spectra of the coated lithium-rich anode material of NCA prepared by the embodiment of the present invention 4.
Figure 11 not coated lithium-rich anode material 0.1C circulation volume that to be the coated lithium-rich anode material of NCA prepared of the embodiment of the present invention 4 prepare with comparative example 1 with discharge in the comparison diagram of pressing.
Figure 12 is the XRD spectra of the not coated lithium-rich anode material of preparation in comparative example 1.
Embodiment
Below in conjunction with Figure of description and concrete preferred embodiment, the invention will be further described, but protection range not thereby limiting the invention.
The material adopted in following examples and instrument are commercially available.
embodiment 1:
See Fig. 1: a kind of lithium-rich anode material of the present invention, its general formula is expressed as:
XLi 2mnO 3yLiNi x1mn y1co (1-x1-y1)o 2zLiNi x2mn y2co z2al x3o 2, wherein x=27/100, y=63/100, z=1/10, x1=1/3, y1=1/3, x2=1/2, y2=3/2, z2=0, x3=0.
This lithium-rich anode material comprises rich lithium solid solution (core A) and has the material (shell B) of lithium ion conduction ability, and the material with lithium ion conduction ability is coated on rich lithium solid solution surface and forms nucleocapsid structure; The material with lithium ion conduction ability is spinel structure material.
In the lithium-rich anode material of the present embodiment, rich lithium solid solution (i.e. core material) is graininess, rich lithium solid solution is the second particle piled up by primary particle, the particle diameter of primary particle is about 0.1 μm ~ 0.3 μm, in coprecipitation process, pile up composition second particle particle diameter within the scope of 4 μm ~ 6 μm, its chemical formula is Li 7/6mn 1/2ni 1/6co 1/6o 2.The chemical formula of spinel structure material (i.e. Shell Materials) is LiNi 0.5mn 1.5o 4, thickness is 0.002 μm ~ 0.01 μm.
A preparation method for lithium-rich anode material in above-mentioned the present embodiment, comprises the following steps:
(1) preparation raw material solution:
1.1, be 1/6: 1/6: 1/2 by the mol ratio of Ni: Co: Mn, get nickelous sulfate, cobaltous sulfate, manganese sulfate be made into mixed solution A, in this mixed solution A, the concentration of metal cation is 1mol/L.
In above-mentioned steps 1.1, in mixed solution A, the concentration of metal cation is that 0.5mol/L ~ 2mol/L all can implement; The mol ratio of Ni: Co: Mn is 1/6 ~ 1/3: 0 ~ 1/6: 1/2 ~ 1 all can to implement.
1.2, be get NiSO at 0.5: 1.5 by the mol ratio of Ni: Mn 46H 2o, MnSO 4h 2o is made into mixed solution B, and in this mixed solution B, the concentration of metal cation is 0.05mol/L.
In above-mentioned steps 1.2, in mixed solution B, the concentration of metal cation is that 0.01mol/L ~ 0.05mol/L all can implement; The mol ratio of Ni: Mn is 0.3 ~ 0.5: 1.7 ~ 1.5 all can to implement.
(2) core material is prepared:
2.1, first add in there-necked flask account for reaction vessel volume 20% 0.5mol/L ammoniacal liquor as end liquid, the mixed solution A of preparation in step 1.1 and the NaOH solution (precipitation reagent) of 1mol/L, the ammonia spirit (complexing agent) of 0.5mol/L are added in reaction system (there-necked flask) by peristaltic pump, under the water-bath of 60 DEG C, carry out coprecipitation reaction obtain mixed solution, the liquid feeding speed of each raw material is 5ml/min, rotating speed is 500rpm, and the flow velocity by regulating and controlling precipitation reagent in course of reaction regulates the pH value of reaction system to be 11.
In above-mentioned steps 2.1, the liquid feeding speed of each raw material is that 2 ~ 5ml/min all can implement, and the pH value of reaction system is 10 ~ 11.5 all can to implement.
2.2, the mixed solution obtained by coprecipitation reaction in step 2.1 stirs with the rotating speed constant speed of 700rpm in the water-bath of 60 DEG C, ripening 12h.Then filter, wash after at 80 DEG C vacuumize 12h, obtain the core material presoma that particle diameter is 4 μm ~ 6 μm.
2.3, the core material presoma heat treatment 10h at 200 DEG C will obtained after oven dry in step 2.2, then adopt the mode of wet grinding blended with lithium hydroxide according to the ratio (be in molar ratio 1: 1.1 ~ 1.3 mix all can implement) with lithium hydroxide that mol ratio is 1: 1.255, to be driedly be placed in Muffle furnace, 500 DEG C of presintering process 10h are warming up in air atmosphere with the programming rate of 5 DEG C/min, be warming up to 900 DEG C of high temperature sintering process 15h with the programming rate of 5 DEG C/min subsequently, obtain the core material that particle diameter is 4 μm ~ 6 μm.
In above-mentioned steps 2.3, be warming up to 700 ~ 900 DEG C with the programming rate of 0.5 ~ 5 DEG C/min and carry out high temperature sintering and all can implement, the time of high temperature sintering is that 10 ~ 24h all can implement.
(3) Shell Materials is coated on core material:
3.1, core material prepared by step 2.3 is placed in reaction unit, keep Keep agitation, then the ammoniacal liquor (complexing agent) of mixed solution B and 0.2mol/L step 1.2 prepared by peristaltic pump and the NaOH solution (precipitation reagent) of 0.5mol/L are together added in reaction unit, under the water-bath system of 60 DEG C, carry out coated coprecipitation reaction obtain suspension solution, in keeping reaction system to stir with the rotating speed constant speed of 700rpm, carry out adjustment by the flow velocity regulating and controlling precipitation reagent and make system pH maintain about 11.
In above-mentioned steps 3.1, the concentration of NaOH solution is that 0.05 ~ 5mol/L all can implement, and precipitation reagent also can be replaced the carbonate that concentration is 1 ~ 2mol/L, and carbonate is the one in sodium carbonate, potash, carbonic hydroammonium.The concentration of ammoniacal liquor is that 0.02 ~ 2mol/L all can implement.
3.2, the suspension solution obtained after being completed by coprecipitation reaction coated in step 3.1 keeps 700rpm constant speed to stir in the water-bath system of 60 DEG C, carries out ripening 24h, obtains the core material being coated with Shell Materials presoma.
(4) lithium-rich anode material is prepared:
4.1, the core material being coated with Shell Materials presoma step 3.2 prepared carries out vacuumize 24h at 80 DEG C, then in molar ratio with LiOH carry out flood mixed lithium obtain mixture at 1: 1.
4.2, mixture drying step 4.1 prepared is placed in Muffle furnace, is warming up to 500 DEG C of presintering process 15h in air atmosphere, obtains presintering product with the programming rate of 0.5 DEG C/min.
In above-mentioned steps 4.2, heating rate is that 0.5 ~ 5 DEG C/min all can implement; Pre-sintering temperature is 400 ~ 500 DEG C all can be implemented; The presintering processing time is that 10 ~ 20h all can implement.
4.3, presintering product step 4.2 prepared is warming up to 800 DEG C of high temperature sintering process 15h with the programming rate of 2 DEG C/min, obtains the lithium-rich anode material that spinel structure is coated.
In above-mentioned steps 4.3, the heating rate of high temperature sintering is 0.5 ~ 5 DEG C/min, and the temperature of high temperature sintering is 700 ~ 900 DEG C, and the time of high temperature sintering is that 10 ~ 24h all can implement.
The lithium-rich anode material that the present embodiment preparation method prepares can be used for the positive pole preparing lithium ion battery.Its preparation method can adopt the preparation method of the lithium ion cell positive of this area routine to prepare, in the present invention, the preparation method of the positive pole in this lithium ion battery comprises the following steps: by lithium-rich anode material, conductive agent, binding agent mixing, add solvent and make slurry, then by even for slurry blade coating on aluminium foil, compressing; Wherein the mass ratio of lithium-rich anode material, conductive agent, binding agent to be 93: 5: 2(mass ratio be 70 ~ 97: 2 ~ 10: 2 ~ 10 all can implement).
Meanwhile, conductive agent, adhesive all adopt this area conventional conductive agent, adhesive, and the conductive agent that the present embodiment is selected is conductive black, and adhesive is Kynoar (PVDF).Solvent can be any solvent dissolving lithium-rich anode material, conductive electrode and binding agent, and the solvent that the present embodiment adopts is 1-METHYLPYRROLIDONE.
The high-capacity lithium-rich cathode material of embodiment 1 is characterized:
Fig. 2 is the transmission electron microscope picture of the coated lithium-rich anode material of spinel structure prepared by the embodiment of the present invention 1, and result shows on lithium-rich anode material, define fine and close coated shell.
Fig. 3 is the XRD spectra of the coated lithium-rich anode material of spinel structure prepared by the embodiment of the present invention 1.X-ray diffraction (XRD) analysis shows that the main crystal formation of product is α-NaFeO 2laminar configuration, space group is R-3m, obvious spinel structure characteristic diffraction peak is it can also be seen that from diffraction pattern, absolutely prove the crystal structure defining spinelle and layer structure and coexist, there is superlattice peak at 20 ~ 25 ° in XRD collection of illustrative plates simultaneously, absolutely prove that stratiform crystalline phase still remains unchanged with rich lithium after coated process.
Fig. 4 is the coated lithium-rich anode material different multiplying discharge cycles performance map of spinel structure prepared by the embodiment of the present invention 1.Electro-chemical test shows, under 0.2C multiplying power, carry out charge-discharge test, and discharge capacity is 235mAhg first -1, after 50 circulations, still keep 230mAhg -1capacity, illustrate that this material has good high rate performance, spinelle shell structurre can significantly improve its high rate performance.
embodiment 2
A kind of lithium-rich anode material of the present invention, its general formula is expressed as:
XLi 2mnO 3yLiNi x1mn y1co (1-x1-y1)o 2zLiNi x2mn y2co z2al x3o 2, wherein x=27/100, y=63/100, z=1/10, x1=1/3, y1=1/3, x2=1/2, y2=3/2, z2=0, x3=0.
This lithium-rich anode material comprises rich lithium solid solution (core A) and has the material (shell B) of lithium ion conduction ability, and the material with lithium ion conduction ability is coated on rich lithium solid solution surface and forms nucleocapsid structure; The material with lithium ion conduction ability is spinel structure material.
In the lithium-rich anode material of the present embodiment, rich lithium solid solution is the second particle piled up by primary particle, and the particle diameter of primary particle is about 0.1 μm ~ 0.3 μm, piles up composition second particle particle diameter in coprecipitation process within the scope of 4 μm ~ 6 μm.Its chemical formula is Li 7/6mn 1/2ni 1/6co 1/6o 2.The chemical formula of spinel structure material (i.e. Shell Materials) is LiNi 0.5mn 1.5o 4, thickness is at 0.002 μm ~ 0.01 μm.
A preparation method for lithium-rich anode material in above-mentioned the present embodiment, comprises the following steps:
(1) preparation raw material solution:
1.1, be 1/6: 1/6: 1/2 by the mol ratio of Ni: Co: Mn, get nickelous sulfate, cobaltous sulfate, manganese sulfate be made into mixed solution A, in this mixed solution A, the concentration of metal cation is 1mol/L.
1.2, be get NiSO at 1: 3 by the mol ratio of Ni: Mn 46H 2o, MnSO 4h 2o is made into mixed solution B, and in this mixed solution B, the concentration of metal cation is 0.015mol/L.
(2) core material is prepared:
2.1, first add in there-necked flask account for reaction vessel volume 20% 0.5mol/L ammoniacal liquor as end liquid, then the mixed solution A of preparation in step 1.1 and the NaOH solution (precipitation reagent) of 1mol/L, the ammonia spirit (complexing agent) of 0.5mol/L are added in reaction system (there-necked flask) by peristaltic pump, under the water-bath of 60 DEG C, carry out coprecipitation reaction obtain mixed solution, controlling rotating speed in coprecipitation reaction process is 500rpm, the liquid feeding speed of each raw material is 5mol/L, and the flow velocity by regulating and controlling precipitation reagent in course of reaction regulates the pH value of reaction system to be 11.
2.2, the mixed solution obtained by coprecipitation reaction in step 2.1 stirs with 500rpm rotating speed constant speed in the water-bath of 60 DEG C, carries out ripening 12h.Then filter, wash be placed on 80 DEG C vacuum drying oven in dry 12h(vacuumize 12 ~ 24h at 80 ~ 110 DEG C, all can implement), obtain the core material presoma (now forming the primary particle of core material) that particle diameter is 4 μm ~ 6 μm.
2.3, by the core material presoma heat treatment 10h at 200 DEG C obtained after oven dry in step 2.2, then adopt the mode of wet grinding blended with lithium hydroxide according to the ratio that mol ratio is 1: 1.255, to be driedly be placed in Muffle furnace, 500 DEG C of presintering process 10h are warming up in air atmosphere with the programming rate of 5 DEG C/min, be warming up to 900 DEG C with the programming rate of 5 DEG C/min subsequently to carry out high temperature sintering 15h(and be warming up to 700 ~ 900 DEG C of high temperature sintering process 10 ~ 24h with the programming rate of 0.5 ~ 5 DEG C/min, all can implement), obtain the core material (now forming the second particle of core material) that particle diameter is 4 μm ~ 6 μm.
(3) Shell Materials is coated on core material:
3.1, core material prepared by step 2.3 is placed in reaction unit, keep Keep agitation, the ammoniacal liquor (complexing agent) of mixed solution B and the 0.5mol/L then prepared by step 1.2 by peristaltic pump and 1mol/L NaOH solution (precipitation reagent) together add in reaction unit, under the water-bath system of 60 DEG C, carry out coated coprecipitation reaction obtain suspension solution, in keeping reaction system to stir with the rotating speed constant speed of 700rpm, the liquid feeding speed of each raw material is 0.5ml/min, carries out adjustment make system pH maintain 11 by the flow velocity regulating and controlling precipitation reagent.
3.2, the suspension solution obtained after being completed by coprecipitation reaction coated in step 3.1 keeps 700rpm constant speed to stir in the water-bath system of 60 DEG C, carries out ripening 12h, obtains the core material being coated with Shell Materials presoma.
(4) lithium-rich anode material is prepared:
4.1, prepared by step 3.2 be coated with the core material cooling of Shell Materials presoma after, carry out filtering and carrying out washing treatment, at 60 DEG C, carry out vacuumize 24h, then carry out flood mixed lithium at 1: 1 in molar ratio with LiOH, obtain mixture.
4.2, mixture drying step 4.1 prepared is placed in Muffle furnace, in atmosphere under atmosphere, is warming up to 500 DEG C of presintering process 10h, obtains presintering product with the programming rate of 0.5 DEG C/min.
4.3, the presintering product that step 4.2 prepared to heat up high temperature sintering process 10h at 800 DEG C with the programming rate of 2 DEG C/min, obtains the lithium-rich anode material that spinel structure is coated.
The high-capacity lithium-rich cathode material of embodiment 2 is characterized:
Fig. 5 is the transmission electron microscope picture of the coated lithium-rich anode material of spinel structure prepared by the embodiment of the present invention 2.TEM result shows, defines the fine and close coating layer of the spinel structure be made up of nano particle on lithium-rich anode material surface.
Fig. 6 is the XRD spectra of the coated lithium-rich anode material of spinel structure prepared by the embodiment of the present invention 2.X-ray diffraction (XRD) analysis shows that the main crystal formation of product is α-NaFeO 2laminar configuration, space group is R-3m, obvious spinel structure characteristic diffraction peak is it can also be seen that from diffraction pattern, absolutely prove the crystal structure defining spinelle and layer structure and coexist, there is superlattice peak at 20 ~ 25 ° in XRD collection of illustrative plates simultaneously, absolutely prove that stratiform crystalline phase still remains unchanged with rich lithium after coated process.
Fig. 7 is the comparison diagram of not coated lithium-rich anode material different multiplying discharge cycles performance prepared by the coated lithium-rich anode material of spinel structure prepared of the embodiment of the present invention 2 and comparative example 1.Electro-chemical test shows, under 0.2C multiplying power, carry out charge-discharge test, and discharge capacity is 241mAhg first -1, 0.5C multiplying power discharging capacity can reach 241mAhg -1, illustrate that this material has good high rate performance, spinelle shell structurre can significantly improve its high rate performance.
embodiment 3
A kind of lithium-rich anode material of the present invention, its general formula is expressed as:
XLi 2mnO 3yLiNi x1mn y1co (1-x1-y1)o 2zLiNi x2mn y2co z2al x3o 2, wherein x=27/100, y=63/100, z=1/10, x1=1/3, y1=1/3, x2=4/5, y2=0, z2=3/20, x3=0.05.
This lithium-rich anode material comprises rich lithium solid solution (core A) and has the material (shell B) of lithium ion conduction ability, and the material with lithium ion conduction ability is coated on rich lithium solid solution surface and forms nucleocapsid structure; The material with lithium ion conduction ability is stratiform ternary material.
In the lithium-rich anode material of the present embodiment, rich lithium solid solution is the second particle piled up by primary particle, and the particle diameter of primary particle is about 0.1 μm ~ 0.3 μm, piles up composition second particle particle diameter in coprecipitation process within the scope of 4 μm ~ 6 μm.Its chemical formula is Li 7/6mn 1/2ni 1/6co 1/6o 2.Stratiform ternary material (i.e. Shell Materials) is LiNi 0.8co 0.15al 0.05o 2(NCA), thickness is at 0.002 μm ~ 0.01 μm.
(1) preparation raw material solution:
1.1, be 1/6: 1/6: 1/2 by the mol ratio of Ni: Co: Mn, get nickelous sulfate, cobaltous sulfate, manganese sulfate be made into mixed solution A, in this mixed solution A, the concentration of metal cation is 1mol/L.
In the step 1.1 of embodiment 3, in mixed solution A, the concentration of metal cation is that 0.5mol/L ~ 2mol/L all can implement; The mol ratio of Ni: Co: Mn is 1/6 ~ 1/3: 0 ~ 1/6: 1/2 ~ 1 all can to implement.
1.2, be 80: 15: 5 by the mol ratio of Ni: Co: Al, get NiSO 46H 2o, CoSO 46H 2o, MnSO 4h 2o, Al (NO 3) 39H 2o is made into mixed solution B, and in this mixed solution B, the concentration of metal cation is 0.025mol/L.
In the step 1.2 of embodiment 3, in mixed solution B, the concentration of metal cation is that 0.01mol/L ~ 0.05mol/L all can implement, and the mol ratio of Ni: Co: Al is 80 ~ 87.5: 10 ~ 15: 2 ~ 5 all can to implement.
(2) gradient-structure persursor material is prepared:
2.1, first add in there-necked flask account for reaction vessel volume 20% 0.5mol/L ammoniacal liquor as end liquid, then the mixed solution A of preparation in step 1.1 and the NaOH solution (precipitation reagent) of 1mol/L, the ammonia spirit (complexing agent) of 0.5mol/L are added in reaction system (there-necked flask) by peristaltic pump, under the water-bath of 60 DEG C, carry out coprecipitation reaction obtain mixed solution, controlling rotating speed in coprecipitation reaction process is 500rpm, the liquid feeding speed of each raw material is 5mol/L, and the flow velocity by regulating and controlling precipitation reagent in course of reaction regulates the pH value of reaction system to be 11.
In the step 2.1 of embodiment 3, add the 0.5 ~ 2mol/L ammoniacal liquor accounting for reaction vessel volume 10% ~ 20% and all can implement as end liquid in there-necked flask, the liquid feeding speed of each raw material is that 2 ~ 5mol/L all can implement; The pH value of reaction system is 10 ~ 11.5 all can to implement.
2.2, the mixed solution obtained by coprecipitation reaction in step 2.1 stirs with 500rpm rotating speed constant speed in the water-bath of 60 DEG C, carries out ripening 12h(ripening 12 ~ 24h, all can implement).Then filter, wash be placed on 80 DEG C vacuum drying oven in dry 12h(vacuumize 12 ~ 24h at 80 ~ 110 DEG C, all can implement), namely obtain core material presoma.
2.3, mixed solution B step 1.2 prepared continues to join in core material presoma, under the water-bath system of 60 DEG C, carry out coated coprecipitation reaction, and it is 10 that the flow velocity by regulating and controlling precipitation reagent in reaction system carrys out regulation system pH value.The suspension solution obtained after coprecipitation reaction completes keeps constant agitation, carries out ripening 12h, filters, fully washs, at the vacuumize 24h of 80 DEG C, prepare gradient-structure persursor material after cooling.
(3) lithium-rich anode material that NCA is coated is prepared:
3.1, gradient-structure persursor material step 2.3 prepared heat-treats 24h at 200 DEG C, is then in molar ratio with lithium source to mix at 1: 1.22.
In the step 3.1 of embodiment 3, gradient-structure persursor material prepared by step 2.3, after Overheating Treatment, is 1: 1.1 ~ 1.3 to mix with the lithium source of LiOH and all can implement in molar ratio.
3.2, by sample mixed in step 3.1 with the heating rate of 0.5 DEG C/min, be warming up to 500 DEG C and carry out presintering process 10h.
In the step 3.2 of embodiment 3, heating rate is that 0.5 ~ 5 DEG C/min all can implement, and pre-sintering temperature is 450 ~ 600 DEG C, and the presintering time is 10 ~ 20h, all can implement.
3.3, the sample after completing presintering process in step 3.2 is warming up to 780 DEG C with the heating rate of 1 DEG C/min under oxygen atmosphere and carries out high temperature sintering process 15h, prepare the lithium-rich anode material that NCA is coated.
In the step 3.3 of embodiment 3, the heating rate of high temperature sintering process is 1 ~ 5 DEG C/min, and the temperature of high temperature sintering process is 750 ~ 950 DEG C; The time of high temperature sintering is that 10 ~ 24h all can implement.
The high-capacity lithium-rich cathode material of embodiment 3 is characterized:
Fig. 8 is the XRD spectra of the coated lithium-rich anode material of NCA prepared by the embodiment of the present invention 3.X-ray diffraction (XRD) analysis shows that the main crystal formation of product is α-NaFeO 2laminar configuration, space group is 20 ~ 25 in R-3m, XRD collection of illustrative plates othere is superlattice peak, absolutely prove that stratiform crystalline phase still remains unchanged with rich lithium after coated process.
The comparison diagram of Fig. 9 not coated lithium-rich anode material 0.1C circulation volume that to be the coated lithium-rich anode material of NCA prepared of the embodiment of the present invention 3 prepare with comparative example 1 and the mean voltage that discharges.Electro-chemical test shows, under 0.1C multiplying power, carry out charge-discharge test, and discharge capacity is 238.7mAhg-1 first, still keeps 186.9mAhg after 50 circulations -1capacity, although decay to a certain degree appears in discharge capacity, stability of its electric discharge mean voltage significantly improves.
embodiment 4
A kind of lithium-rich anode material of the present invention, its general formula is expressed as:
XLi 2mnO 3yLiNi x1mn y1co (1-x1-y1)o 2zLiNi x2mn y2co z2al x3o 2, wherein x=27/100, y=63/100, z=1/10, x1=1/3, y1=1/3, x2=4/5, y2=0, z2=3/20, x3=0.05.
This lithium-rich anode material comprises rich lithium solid solution (core A) and has the material (shell B) of lithium ion conduction ability, and the material with lithium ion conduction ability is coated on rich lithium solid solution surface and forms nucleocapsid structure; The material with lithium ion conduction ability is stratiform ternary material.
In the lithium-rich anode material of the present embodiment, rich lithium solid solution is the second particle piled up by primary particle, and the particle diameter of primary particle is about 0.1 μm ~ 0.3 μm, piles up composition second particle particle diameter in coprecipitation process within the scope of 4 μm ~ 6 μm.Its chemical formula is Li 7/6mn 1/2ni 1/6co 1/6o 2.Stratiform ternary material (i.e. Shell Materials) is LiNi 0.8co 0.15al 0.05o 2(NCA), thickness is at 0.002 μm ~ 0.01 μm.
A preparation method for lithium-rich anode material in above-mentioned the present embodiment, comprises the following steps:
(1) preparation raw material solution:
1.1, be 1/6: 1/6: 1/2 by the mol ratio of Ni: Co: Mn, get nickelous sulfate, cobaltous sulfate, manganese sulfate be made into mixed solution A, in this mixed solution A, the concentration of metal cation is 1mol/L.
1.2, be 80: 15: 5 by the mol ratio of Ni: Co: Al, get NiSO 46H 2o, CoSO 46H 2o, MnSO 4h 2o, Al (NO 3) 39H 2o is made into mixed solution B, and in this mixed solution B, the concentration of metal cation is 0.025mol/L.
(2) core material is prepared:
2.1, first add in there-necked flask account for reaction vessel volume 20% 0.5mol/L ammoniacal liquor as end liquid, then the mixed solution A of preparation in step 1.1 and the NaOH solution (precipitation reagent) of 1mol/L, the ammonia spirit (complexing agent) of 0.5mol/L are added in reaction system (there-necked flask) by peristaltic pump, under the water-bath of 60 DEG C, carry out coprecipitation reaction obtain mixed solution, controlling rotating speed in coprecipitation reaction process is 500rpm, the liquid feeding speed of each raw material is 5mol/L, and the flow velocity by regulating and controlling precipitation reagent in course of reaction regulates the pH value of reaction system to be 11.
2.2, the mixed solution obtained by coprecipitation reaction in step 2.1 stirs with 500rpm rotating speed constant speed in the water-bath of 60 DEG C, ripening 12h.Then filter, wash and be placed on vacuumize 12h at 80 DEG C and namely obtain the core material presoma (now forming the primary particle of core material) that particle diameter is 4 μm ~ 6 μm.
2.3, by the core material presoma that obtains after drying in step 2.2 at 200 DEG C of heat treatment 10h, then adopt the mode of wet grinding blended with lithium hydroxide according to the ratio that mol ratio is 1: 1.225, be placed in Muffle furnace under atmosphere in atmosphere after to be dried and be warming up to 500 DEG C of presintering process 10h with the programming rate of 5 DEG C/min, carry out being placed in Muffle furnace subsequently and be warming up to 900 DEG C of high temperature sintering 10h with the programming rate of 5 DEG C/min, obtain the core material (now forming the second particle of core material) that particle diameter is 4 ~ 6 μm.
(3) Shell Materials is coated on core material:
3.1, the core material obtained in step 2.3 is placed in reaction unit, keep Keep agitation, then the ammoniacal liquor (complexing agent) of mixed solution B and 0.5mol/L step 1.2 prepared by peristaltic pump and the NaOH solution (precipitation reagent) of 0.05mol/L are together added in reaction unit, coated coprecipitation reaction is carried out under the water-bath system of 60 DEG C, reaction system is kept to be in the stirring of 700rpm constant speed, the liquid feeding speed of each raw material is 0.001L/min, carries out adjustment make system pH maintain about 11 by the flow velocity regulating and controlling precipitation reagent.
3.2, the suspension solution obtained after being completed by coprecipitation reaction coated in step 3.1 keeps constant speed 700rpm to stir in the water-bath system of 60 DEG C, carries out ripening 24h, obtains the core material being coated with Shell Materials presoma.
(4) lithium-rich anode material is prepared:
4.1, the core material being coated with Shell Materials presoma step 3.2 obtained under 80 DEG C of conditions after vacuumize 12h, with LiOH by 1: 1 stoichiometric proportion carry out flooding mixed lithium, obtain mixture.
4.2, the mixture drying that step 4.1 prepared is placed in tube furnace, pass into oxygen and carry out presintering process, be warming up to 500 DEG C of presintering process 10h with the programming rate of 0.5 DEG C/min.
4.3, by after the sample grinding after step 4.2 presintering process, be warming up to 800 DEG C of high temperature sintering process 15h with the programming rate of 0.5 DEG C/min, in oxygen atmosphere, carry out high temperature sintering process, namely obtain the lithium-rich anode material sample that NCA is coated.
The high-capacity lithium-rich cathode material of embodiment 4 is characterized:
Figure 10 is the XRD spectra of the coated lithium-rich anode material of NCA prepared by the embodiment of the present invention 4.X-ray diffraction (XRD) analysis shows that the main crystal formation of product is α-NaFeO 2laminar configuration, space group is R-3m, it can also be seen that obvious spinel structure characteristic diffraction peak from diffraction pattern, absolutely proves the crystal structure defining spinelle and layer structure and coexist, simultaneously in XRD collection of illustrative plates 20 ~ 25 othere is superlattice peak, absolutely prove that stratiform crystalline phase still remains unchanged with rich lithium after coated process.
Figure 11 not coated lithium-rich anode material 0.1C circulation volume that to be the coated lithium-rich anode material of NCA prepared of the embodiment of the present invention 4 prepare with comparative example 1 with discharge in the comparison diagram of pressing.Electro-chemical test shows, under 0.1C multiplying power, carry out charge-discharge test, and discharge capacity is 288mAhg first -1, 0.5C multiplying power discharging capacity can reach 193.5mAhg -1, discharge voltage plateau drops to 3.59 by 3.78 through 50 circulations, and the anode material discharging voltage platform not carrying out coated process drops to 3.15V by 3.51V.
comparative example 1
A preparation method for lithium-rich anode material material, comprises the following steps:
(1) Co deposited synthesis lithium-rich anode material Li is adopted 7/6mn 1/2ni 1/6co 1/6o 2, first according to the sulfate liquor of corresponding stoichiometric proportion preparation Ni: Co: Mn=1/6: 1/6: 1/2, concentration is 1mol/L, and the ammonia spirit of preparation 0.5mol/L is as cushioning liquid, and the NaOH of preparation 1mol/L is as precipitation reagent.
(2) the three kinds of solution adopting peristaltic pump step (1) to be prepared pump in the reaction unit of constant agitation speed simultaneously, regulate the flow control pH of NaOH solution about 11, coprecipitation reaction is carried out under the water bath condition of 60 DEG C, carry out after having reacted filtering and washing, in the vacuum drying oven of 110 DEG C, namely isothermal holding 12h obtains presoma positive electrode subsequently.
(3) the presoma positive electrode prepared of step (2) and LiOH fully blended according to the ratio of 1: 1.2,500 DEG C of presintering process are carried out in air atmosphere through 2h, in Muffle furnace, be warming up to 900 DEG C of insulation 10h through 10h after milled processed, obtain not coated lithium-rich anode material.The second particle that the lithium-rich anode material obtained in comparative example 1 is piled up by the primary particle of 200 ~ 300nm is formed.
Figure 12 is the XRD spectra of the not coated lithium-rich anode material of preparation in comparative example 1.X-ray diffraction (XRD) analysis shows that the main crystal formation of product is α-NaFeO 2laminar configuration, space group is R-3m, has superlattice peak at 20 ~ 25 °, is typical solid solution structure XRD spectra.
The not coated charge-discharge performance of lithium-rich anode material under corresponding conditions of preparation in comparative example 1, is shown in Fig. 7, Fig. 9 and Figure 11.
The above is only preferred embodiment of the present invention, not does any pro forma restriction to the present invention.Although the present invention discloses as above with preferred embodiment, but and be not used to limit the present invention.Any those of ordinary skill in the art, when not departing from Spirit Essence of the present invention and technical scheme, the Method and Technology content of above-mentioned announcement all can be utilized to make many possible variations and modification to technical solution of the present invention, or be revised as the Equivalent embodiments of equivalent variations.Therefore, every content not departing from technical solution of the present invention, according to technical spirit of the present invention to any simple modification made for any of the above embodiments, equivalent replacement, equivalence change and modification, all still belongs in the scope of technical solution of the present invention protection.

Claims (10)

1. a lithium-rich anode material, is characterized in that, described lithium-rich anode material comprises rich lithium solid solution and has the material of lithium ion conduction ability, described in there is lithium ion conduction ability material be coated on described rich lithium solid solution surface and form nucleocapsid structure; The described material with lithium ion conduction ability is stratiform ternary material or spinel structure material.
2. lithium-rich anode material according to claim 1, is characterized in that, the chemical formula of described lithium-rich anode material is: xLi 2mnO 3yLiNi x1mn y1co (1-x1-y1)o 2zLiNi x2mn y2co z2al x3o 2wherein 0<x<1/2,0<y<7/10,0<z<3/10,1/3≤x1≤1/2,1/3≤y1≤1/2,0≤x2≤4/5,0≤y2≤3/2,0≤z2≤1/6,0≤x3≤1/10.
3. lithium-rich anode material according to claim 2, is characterized in that, layered ternary material is LiNi 0.8co 0.15al 0.05o 2; Described spinel structure material is LiNi 0.5mn 1.5o 4.
4. a preparation method for lithium-rich anode material as claimed any one in claims 1 to 3, is characterized in that, comprises the following steps:
S1, nickel salt, cobalt salt, manganese salt are made into mixed solution A, then described mixed solution A and precipitation reagent, complexing agent are carried out coprecipitation reaction, through ripening, prepare core material presoma;
S2, the described core material presoma prepared by step S1 mix with lithium source, then carry out high temperature sintering 10 ~ 24h with 700 ~ 900 DEG C and obtain core material;
S3, one or more in nickel salt, cobalt salt, aluminium salt, manganese salt are made into mixed solution B, then described mixed solution B and precipitation reagent, complexing agent are together joined in described core material prepared by step S2 and carry out coated coprecipitation reaction, through ripening, prepare the core material being coated with Shell Materials presoma;
S4, prepared by step S3 described in be coated with Shell Materials presoma core material mix with lithium source, then carry out high temperature sintering 10 ~ 24h with 700 ~ 900 DEG C, complete the preparation of described lithium-rich anode material.
5. a preparation method for lithium-rich anode material as claimed any one in claims 1 to 3, is characterized in that, comprises the following steps:
S1, nickel salt, cobalt salt, manganese salt are made into mixed solution A, then described mixed solution A and precipitation reagent, complexing agent are carried out coprecipitation reaction, through ripening, prepare core material presoma;
S2, one or more in nickel salt, cobalt salt, aluminium salt, manganese salt are made into mixed solution B, described mixed solution B is joined in described core material presoma prepared by step S1 and carry out coated coprecipitation reaction, through ripening, prepare gradient-structure persursor material;
S3, the described gradient-structure persursor material prepared by step S2 mix with lithium source, then carry out high temperature sintering 10 ~ 24h with 750 ~ 950 DEG C, complete the preparation of described lithium-rich anode material.
6. the preparation method according to claim 4 or 5, is characterized in that, described nickel salt comprise in nickel nitrate, nickelous sulfate, nickel chloride one or more; Described cobalt salt comprise in cobalt nitrate, cobaltous sulfate, cobalt chloride one or more; Described manganese salt comprise in manganese nitrate, manganese sulfate, manganese chloride one or more; Described aluminium salt comprise in aluminum nitrate, aluminum sulfate, aluminium chloride one or more; Described lithium source comprise in lithium hydroxide, lithium carbonate, lithium nitrate one or more; Hydroxide and/or the concentration of described precipitation reagent to be concentration be 0.05 ~ 5mol/L are the carbonate of 1 ~ 2mol/L; The ammoniacal liquor of described complexing agent to be concentration be 0.02 ~ 2mol/L.
7. preparation method according to claim 6, is characterized in that, described hydroxide is one or both in NaOH, potassium hydroxide; Described carbonate is one or more in sodium carbonate, potash, carbonic hydroammonium.
8. the preparation method according to claim 4 or 5, is characterized in that, in described mixed solution A, the concentration of metal cation is 0.5mol/L ~ 2mol/L; In described mixed solution B, the concentration of metal cation is 0.01mol/L ~ 0.05mol/L.
9. the lithium-rich anode material that prepared by the lithium-rich anode material according to any one of claims 1 to 3 or the preparation method according to any one of claim 4 ~ 8 is preparing the application in lithium ion cell positive.
10. according to the application described in claim 9, it is characterized in that, the preparation method of described lithium ion cell positive comprises the following steps: by described lithium-rich anode material, conductive agent, binding agent according to mass ratio be 70 ~ 97: 2 ~ 10: 2 ~ 10 mixing, be mixed with slurry, then by even for described slurry blade coating on aluminium foil, compressing.
CN201510370957.XA 2015-06-30 2015-06-30 Lithium-rich anode material and its preparation method and application Active CN105161679B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510370957.XA CN105161679B (en) 2015-06-30 2015-06-30 Lithium-rich anode material and its preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510370957.XA CN105161679B (en) 2015-06-30 2015-06-30 Lithium-rich anode material and its preparation method and application

Publications (2)

Publication Number Publication Date
CN105161679A true CN105161679A (en) 2015-12-16
CN105161679B CN105161679B (en) 2018-01-16

Family

ID=54802487

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510370957.XA Active CN105161679B (en) 2015-06-30 2015-06-30 Lithium-rich anode material and its preparation method and application

Country Status (1)

Country Link
CN (1) CN105161679B (en)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106207138A (en) * 2016-09-20 2016-12-07 中国科学院化学研究所 A kind of method for preparing anode material of lithium-ion battery and application thereof
CN106532038A (en) * 2017-01-18 2017-03-22 宁波金和锂电材料有限公司 Lithium nickel and cobalt aluminate anode material and preparation method and lithium ion battery thereof
CN107785551A (en) * 2017-10-20 2018-03-09 北京工业大学 The lithium-rich oxide material and preparation method of a kind of phase structure ratio gradient
CN107834041A (en) * 2017-10-11 2018-03-23 苏州宇量电池有限公司 The preparation method of core shell structure high-performance lithium-rich manganese-based anode material
CN108550791A (en) * 2018-04-20 2018-09-18 中国科学院化学研究所 A kind of layered cathode material and its preparation method and application of spinelle cladding
CN108767254A (en) * 2018-05-24 2018-11-06 湘潭大学 A kind of surface texture and chemical composition synchronization modulation method of stratiform lithium-rich anode material
CN109461891A (en) * 2017-11-02 2019-03-12 北京当升材料科技股份有限公司 A kind of high voltage lithium cobalt oxide anode and preparation method thereof
CN109704415A (en) * 2018-12-26 2019-05-03 惠州亿纬锂能股份有限公司 A kind of lithium-rich manganese-based presoma, and preparation method thereof and lithium-rich manganese-based anode material
CN110010887A (en) * 2019-04-11 2019-07-12 南开大学 A kind of high voltage high-energy long circulation life lithium cobaltate cathode material and preparation method thereof
CN110336020A (en) * 2019-07-22 2019-10-15 广东邦普循环科技有限公司 A kind of high voltage compound lithium cobaltate cathode material and its preparation method and application
CN110518219A (en) * 2019-09-04 2019-11-29 中南大学 The nickelic gradient nickel cobalt manganese aluminium quaternary positive electrode of core-shell structure and preparation method
US20200067083A1 (en) * 2018-08-22 2020-02-27 Ecopro Bm Co., Ltd. Positive electrode active material and lithium secondary battery comprising the same
CN111162249A (en) * 2018-11-07 2020-05-15 天津国安盟固利新材料科技股份有限公司 Positive electrode material for improving first discharge capacity and preparation method thereof
US20200280065A1 (en) * 2017-12-11 2020-09-03 Lg Chem, Ltd. Positive Electrode Active Material for Lithium Secondary Battery, Method of Preparing the Same, and Positive Electrode for Lithium Secondary Battery and Lithium Secondary Battery which Include the Positive Electrode Active Material
CN112838195A (en) * 2019-11-22 2021-05-25 中国科学院大连化学物理研究所 Surface-coated lithium ion battery positive electrode material and preparation method and application thereof
WO2021136490A1 (en) * 2019-12-31 2021-07-08 北京当升材料科技股份有限公司 Lithium-rich manganese-based material, preparation method therefor and application thereof
CN114566626A (en) * 2022-03-02 2022-05-31 北京卫蓝新能源科技有限公司 Multilayer composite phase structure cathode material and preparation method and application thereof
WO2024021287A1 (en) * 2022-07-29 2024-02-01 中伟新材料股份有限公司 Positive electrode material precursor, preparation method therefor, positive electrode material, and lithium ion battery

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103367733A (en) * 2013-07-09 2013-10-23 奇瑞汽车股份有限公司 Lithium ion battery cathode material and preparation method thereof and lithium ion battery
CN103515606A (en) * 2012-06-21 2014-01-15 中国科学院宁波材料技术与工程研究所 High energy density lithium ion battery oxide positive electrode material and preparation method thereof
CN104157831A (en) * 2014-08-19 2014-11-19 哈尔滨工业大学 Spinel nickel manganese acid lithium and layered lithium-rich manganese-based composite cathode material with core-shell structure and preparation method thereof
CN104409685A (en) * 2014-11-28 2015-03-11 东莞市迈科科技有限公司 Lithium ion cell cathode material with core shell structure and preparation method thereof
WO2015067316A1 (en) * 2013-11-08 2015-05-14 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Method of manufacturing an electrode material, electrode material and vehicle comprising a battery including such an electrode material
CN104681784A (en) * 2015-02-10 2015-06-03 华中科技大学 Lithium vanadate anode material, anode, battery and anode material preparation method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103515606A (en) * 2012-06-21 2014-01-15 中国科学院宁波材料技术与工程研究所 High energy density lithium ion battery oxide positive electrode material and preparation method thereof
CN103367733A (en) * 2013-07-09 2013-10-23 奇瑞汽车股份有限公司 Lithium ion battery cathode material and preparation method thereof and lithium ion battery
WO2015067316A1 (en) * 2013-11-08 2015-05-14 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Method of manufacturing an electrode material, electrode material and vehicle comprising a battery including such an electrode material
CN104157831A (en) * 2014-08-19 2014-11-19 哈尔滨工业大学 Spinel nickel manganese acid lithium and layered lithium-rich manganese-based composite cathode material with core-shell structure and preparation method thereof
CN104409685A (en) * 2014-11-28 2015-03-11 东莞市迈科科技有限公司 Lithium ion cell cathode material with core shell structure and preparation method thereof
CN104681784A (en) * 2015-02-10 2015-06-03 华中科技大学 Lithium vanadate anode material, anode, battery and anode material preparation method

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106207138A (en) * 2016-09-20 2016-12-07 中国科学院化学研究所 A kind of method for preparing anode material of lithium-ion battery and application thereof
CN106532038A (en) * 2017-01-18 2017-03-22 宁波金和锂电材料有限公司 Lithium nickel and cobalt aluminate anode material and preparation method and lithium ion battery thereof
CN107834041A (en) * 2017-10-11 2018-03-23 苏州宇量电池有限公司 The preparation method of core shell structure high-performance lithium-rich manganese-based anode material
CN107785551A (en) * 2017-10-20 2018-03-09 北京工业大学 The lithium-rich oxide material and preparation method of a kind of phase structure ratio gradient
CN107785551B (en) * 2017-10-20 2020-11-27 北京工业大学 Lithium-rich layered oxide material with gradient phase structure proportion and preparation method thereof
CN109461891A (en) * 2017-11-02 2019-03-12 北京当升材料科技股份有限公司 A kind of high voltage lithium cobalt oxide anode and preparation method thereof
US20200280065A1 (en) * 2017-12-11 2020-09-03 Lg Chem, Ltd. Positive Electrode Active Material for Lithium Secondary Battery, Method of Preparing the Same, and Positive Electrode for Lithium Secondary Battery and Lithium Secondary Battery which Include the Positive Electrode Active Material
CN108550791A (en) * 2018-04-20 2018-09-18 中国科学院化学研究所 A kind of layered cathode material and its preparation method and application of spinelle cladding
CN108767254B (en) * 2018-05-24 2020-12-15 湘潭大学 Surface structure and chemical composition synchronous regulation and control method of layered lithium-rich cathode material
CN108767254A (en) * 2018-05-24 2018-11-06 湘潭大学 A kind of surface texture and chemical composition synchronization modulation method of stratiform lithium-rich anode material
US20200067083A1 (en) * 2018-08-22 2020-02-27 Ecopro Bm Co., Ltd. Positive electrode active material and lithium secondary battery comprising the same
CN111162249A (en) * 2018-11-07 2020-05-15 天津国安盟固利新材料科技股份有限公司 Positive electrode material for improving first discharge capacity and preparation method thereof
CN109704415A (en) * 2018-12-26 2019-05-03 惠州亿纬锂能股份有限公司 A kind of lithium-rich manganese-based presoma, and preparation method thereof and lithium-rich manganese-based anode material
CN110010887A (en) * 2019-04-11 2019-07-12 南开大学 A kind of high voltage high-energy long circulation life lithium cobaltate cathode material and preparation method thereof
CN110010887B (en) * 2019-04-11 2022-03-11 南开大学 High-voltage high-energy long-cycle-life lithium cobalt oxide cathode material and preparation method thereof
CN110336020A (en) * 2019-07-22 2019-10-15 广东邦普循环科技有限公司 A kind of high voltage compound lithium cobaltate cathode material and its preparation method and application
CN110518219A (en) * 2019-09-04 2019-11-29 中南大学 The nickelic gradient nickel cobalt manganese aluminium quaternary positive electrode of core-shell structure and preparation method
CN110518219B (en) * 2019-09-04 2023-08-01 中南大学 Core-shell structured high nickel gradient nickel-cobalt-manganese-aluminum quaternary positive electrode material and preparation method thereof
CN112838195A (en) * 2019-11-22 2021-05-25 中国科学院大连化学物理研究所 Surface-coated lithium ion battery positive electrode material and preparation method and application thereof
CN112838195B (en) * 2019-11-22 2022-09-13 中国科学院大连化学物理研究所 Surface-coated lithium ion battery positive electrode material and preparation method and application thereof
WO2021136490A1 (en) * 2019-12-31 2021-07-08 北京当升材料科技股份有限公司 Lithium-rich manganese-based material, preparation method therefor and application thereof
CN114566626A (en) * 2022-03-02 2022-05-31 北京卫蓝新能源科技有限公司 Multilayer composite phase structure cathode material and preparation method and application thereof
WO2024021287A1 (en) * 2022-07-29 2024-02-01 中伟新材料股份有限公司 Positive electrode material precursor, preparation method therefor, positive electrode material, and lithium ion battery

Also Published As

Publication number Publication date
CN105161679B (en) 2018-01-16

Similar Documents

Publication Publication Date Title
CN105161679B (en) Lithium-rich anode material and its preparation method and application
CN108878818B (en) Core-shell structure nickel-cobalt-manganternary ternary anode material presoma and preparation method thereof
CN104934595B (en) Prepare the nickel cobalt aluminium precursor material being distributed with aluminium element gradient and the method for positive electrode
CN106711434B (en) One type sea urchin shape positive electrode of lithium-rich containing sodium and preparation method thereof
CN102983326B (en) Spherical lithium-nickel-cobalt composite oxide positive electrode material preparation method
CN102386391B (en) Method for preparing ternary complex anode material (LiNixCoyMn1-x-yO2)
CN109560276A (en) A kind of monocrystalline tertiary cathode material and preparation method thereof and lithium ion battery with concentration gradient distribution primary particle oriented growth
CN104362295B (en) A kind of lithium ion battery nickel-base anode material and preparation method thereof
CN107968202A (en) A kind of positive electrode of nickel cobalt manganese core shell structure containing aluminium and preparation method thereof
CN104409716A (en) Nickel lithium ion battery positive material with concentration gradient, and preparation method thereof
CN109088067B (en) Preparation method of low-cobalt-doped spinel-layered-structure lithium nickel manganese oxide two-phase composite positive electrode material
CN103715424A (en) Core-shell structured cathode material and preparation method thereof
CN104466158A (en) Lithium-rich positive electrode material and preparation method thereof
CN102683645A (en) Preparation method of layered lithium-rich manganese base oxide of positive material of lithium ion battery
CN103068770A (en) Alumina dry -coated cathode material precursors
CN110323432A (en) A kind of miscellaneous modification lithium-ion battery anode material of cation-anion co-doping and preparation method thereof
CN106602015A (en) Preparation method for fluorine-doped nickel-cobalt-manganese system ternary positive electrode material and prepared material
CN102013481A (en) Method for synthesizing spherical gradient lithium-rich anode material
CN108767216A (en) Anode material for lithium-ion batteries and its synthetic method with the full concentration gradient of variable slope
CN103715418A (en) Preparation method for spherical cobaltosic oxide
CN107482213A (en) A kind of nickel aluminium codope mangano-manganic oxide and preparation method thereof
WO2007000075A1 (en) Method for preparing spherical nickelous hydroxide which is dopped and multiple metal oxides, and lithium ion secondary battery
CN106602004A (en) High-safety power lithium ion secondary battery composite positive material and preparation method thereof
CN107634196A (en) Adulterate the preparation method of the nickel-cobalt-manganese ternary material of zinc
CN108448109A (en) A kind of stratiform lithium-rich manganese-based anode material and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
CB02 Change of applicant information

Address after: 410073 Hunan province Changsha Deya Road No. 109

Applicant after: National Defence Science &. Technology Univ., PLA

Address before: Zheng Jie in Hunan province 410073 Changsha City Yan w pool No. 109

Applicant before: National Defence Science &. Technology Univ., PLA

COR Change of bibliographic data
GR01 Patent grant
GR01 Patent grant