CN107316991A - A kind of manufacture method of lithium nickel manganese cathode material for having spinel structure and application thereof - Google Patents

A kind of manufacture method of lithium nickel manganese cathode material for having spinel structure and application thereof Download PDF

Info

Publication number
CN107316991A
CN107316991A CN201710385994.7A CN201710385994A CN107316991A CN 107316991 A CN107316991 A CN 107316991A CN 201710385994 A CN201710385994 A CN 201710385994A CN 107316991 A CN107316991 A CN 107316991A
Authority
CN
China
Prior art keywords
lithium
cathode material
manganese
source
nickel
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.)
Pending
Application number
CN201710385994.7A
Other languages
Chinese (zh)
Inventor
王瑞瑜
杨纯诚
游承恩
李俊叡
吴宗翰
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.)
FORMOSA PLASTICS TRANSPORT Corp
Original Assignee
FORMOSA PLASTICS TRANSPORT Corp
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 FORMOSA PLASTICS TRANSPORT Corp filed Critical FORMOSA PLASTICS TRANSPORT Corp
Priority to CN201710385994.7A priority Critical patent/CN107316991A/en
Publication of CN107316991A publication Critical patent/CN107316991A/en
Pending legal-status Critical Current

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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—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

Abstract

A kind of preparation method for the lithium nickel manganese cathode material for having spinel structure, it is with solid phase method or spray drying process synthesis lithium phosphate ferrimanganic cathode material, lithium nickel manganese cathode material is modified especially in building-up process, this method can be effectively improved and improve the electrical conductivity of lithium phosphate ferrimanganic active material, also so that obtained lithium nickel manganese cathode material has extraordinary high power characteristic and good charge discharge cycles life-span, in the case where carrying out high-speed charge/discharge, with splendid stability and gram capacitance, it is adaptable to as the negative electrode of secondary lithium battery.

Description

A kind of manufacture method of lithium nickel manganese cathode material for having spinel structure and application thereof
Technical field
The present invention relates to a kind of lithium nickel manganese cathode material, particularly possesses the system of the lithium nickel manganese cathode material of spinel structure Make method and application thereof.
Background technology
In recent years, the performance of lithium rechargeable battery, as material and electrochemical techniques constantly develop, is significantly carried Rise, and it is a large amount of using on all kinds of 3C Products.
The component of the most critical of lithium rechargeable battery is positive electrode (or cathode material), its performance quality influence The overall performance of lithium rechargeable battery.Wherein, a kind of new 5V high voltages LiNiyMn2-yO4(0<y<1, abbreviation LNMO) it is cloudy The theoretical gram capacitance of pole material reaches 147mAh/g, possesses the characteristic of high-capacitance and high charge-discharge speed, it is adaptable to be made 4.7V to the lithium rechargeable battery of 5.0V high working voltages positive pole (or negative electrode).
But, when carrying out long-term charge/discharge test, LNMO cathode materials have a problem of gram capacitance fails.To solve This problem to LNMO cathode materials, it is necessary to be modified to improve its cycle charge discharge electrical property.
The content of the invention
In view of this, it is a primary object of the present invention to disclose a kind of lithium nickel manganese cathode material for having spinel structure, In building-up process, be using lithium source, nickel source, manganese source as raw material, using chelating as reducing agent, manufacture method be using solid phase method or Prepared by spray drying process, the preparation technology being modified to lithium nickel manganese cathode material is especially included in building-up process so that The lithium nickel manganese cathode material of preparation is obviously improved its cycle life in high temperature environments, 25 DEG C at room temperature carry out high-speed fill/ Electric discharge, with splendid stability and gram capacitance.
Another main purpose of the present invention is to disclose a kind of manufacturer for the lithium nickel manganese cathode material for having spinel structure Method, in the building-up process prepared using solid phase method or spray drying process, selection is used in following four kinds modified preparation technologies It is one or more so that the lithium nickel manganese cathode material of tool spinel structure is modified：
1) in ball milling preparation technology, using different sphere diameter sizes mill ball or zirconia ball fine grinding lithium nickel manganese raw material and The granular size of predecessor, adjustment lithium nickel manganese raw material and predecessor；The sphere diameter of the mill ball or zirconia ball, between 0.1mm ~0.3mm；
2) cladding carbon-coating modification is carried out to the surface of lithium nickel manganese cathode material, the lithium nickel manganese negative electrode material of bag carbon modification is made Material；For bag carbon be modified carbon source, selected from citric acid, sucrose, glucose, starch, furane resins, polyvinyl alcohol, polystyrene, One or more in polystyrene spheres or methyl methacrylate ball；The conductive carbon material being modified for bag carbon, leads selected from Super P Electrical carbon material, carbon ball conductive carbon material, carbon black conductive carbon materials, graphene conductive carbon materials, CNT carbon materials, electrographite, compound stone One or more in ink or carbonaceous mesophase spherules；
3) last layer modified layer is coated with to the surface of lithium nickel manganese cathode material, the lithium nickel manganese negative electrode for possessing core shell structure is made Material；The material of the modified layer, selected from lithium titanate, lithium phosphate aluminium titanium, lithium titanate lanthanum, ruthenic chloride, binary stratiform nickel ion doped, Cobalt acid lithium, layered LiMnO, LiFePO4, phosphoric acid vanadium lithium, ferric phosphate, 111 ternary materials, 424 ternary materials or 523 ternary materials One kind or their mixing in material；
4) it is cation-modified to lithium nickel manganese cathode material doping (doped), lift structure stability；The cation is selected from One or more cations in alkali metal, alkali earth metal, the 3rd race's element, transition metal and rare earth element； It is preferably selected from Ru4+、Mn2+、Mg2+、Al3+、Ti4+、Zr4+、Nb5+Or W+6Deng cation element.
The present invention another main purpose be to disclose a kind of lithium rechargeable battery, use tool spinel structure lithium nickel Manganese cathode material is positive pole, and battery electrolyte is selected from concentration 1M LiAsF6Add EC/MF (volume ratios 1:3, as follows) mixing Solvent, concentration 1M LiPF6Add EC/DEC (1:1) mixed solvent, concentration 1M LiPF6Add EC/DEC (3:7) mixed solvent, Concentration 1M LiPF6Add EC/EMC (2:1) mixed solvent, concentration 1M LiPF6Add EC/DMC (3:7) mixed solvent, concentration 1M LiPF6Add EC/DEC/DMC (1:1:1) mixed solvent, concentration 1M LiPF6Add EC/EMC/MA/toluene (toluene) (1: 1:1:1) mixed solvent, concentration 1M LiPF6Add EC/EMC/EP (30:30:40) mixed solvent, concentration 1M LiPF6Add EC/ EMC/DEC/EP(30:35:35) mixed solvent, concentration 1M LiPF6Add EC/DEC/IPA (30:35:35) mixed solvent, dense Spend 1M LiPF6Add EC/EMC/EA (30:30:40), concentration 1M LiPF6Add EC/DMC/MA (30:30:40) mixed solvent, Concentration 1M LiPF6Add EC/DMC/EA mixed solvents, concentration 1M LiPF6Add EC/DMC/MB mixed solvents, concentration 1M LiPF6Add PC/EC/MB mixed solvents, concentration 1M LiPF6Add PC/EC/EMC (1:1:3) mixed solvent；Wherein, MF refers to Methyl formate；MA refers to methyl acetate；EA refers to ethyl acetate；MP refers to methyl propionate；MB refers to methyl butyrate；EP refers to third Acetoacetic ester；PC refers to propene carbonate；EC refers to ethylene carbonate；DECRefer to diethyl carbonate；DMC refers to dimethyl carbonate； EMC refers to methyl ethyl ester；IPA refers to isopropyl acetate.
Brief description of the drawings
Fig. 1 is that 5V high voltages LiNi is made using oxide with solid phase method in the present invention0.5Mn1.5O4The preparation stream of positive electrode Cheng Tu.
Fig. 2 is that 5V high voltages LiNi is made with spray drying process in the present invention0.5Mn1.5O4The preparation flow figure of positive electrode.
Fig. 3 is the preparation flow figure of the spinelle-LNMO cathode electrode sheets of the present invention.
Fig. 4 is the structure chart of general 2032 button cell.
Fig. 5 is spinelle-LNMO (y=0.5) cathode materials of the invention prepared with electron microscope (SEM) observation analysis SEM configuration of surface detection figure of its configuration of surface under enlargement ratio 3K and 10K.
Fig. 6 is that spinelle-LNMO (y=0.5) cathode material prepared by the present invention passes through Surface coating 2wt%RuCl3Afterwards Figure is detected with SEM configuration of surface of its configuration of surface of electron microscope (SEM) observation analysis under enlargement ratio 3K and 10K.
Fig. 7 be the present invention using solid phase method (SS preparation methods) and different modified preparation technology be made different spinelles- X-ray diffraction (XRD) collection of illustrative plates of LNMO (y=0.5) cathode material samples (1)~(7).
Fig. 8 is charging and discharging curve figure of the button cell that is made of embodiment 1 under 0.1/0.1C charge/discharge rates.
Fig. 9 is charge and discharge of the button cell that is made of embodiment 1 under 0.2C/0.2C~0.2C/10C charge/discharge rates Electric curve map.
Figure 10 is charging and discharging curve figure of the button cell that is made of embodiment 2 under 0.1/0.1C charge/discharge rates.
Figure 11 is charge and discharge of the button cell that is made of embodiment 2 under 0.2C/0.2C~0.2C/10C charge/discharge rates Electric curve map.
Figure 12 is charging and discharging curve figure of the button cell that is made of embodiment 3 under 0.1/0.1C charge/discharge rates.
Figure 13 is charge and discharge of the button cell that is made of embodiment 3 under 0.2C/0.2C~0.2C/10C charge/discharge rates Electric curve map.
Figure 14 is charging and discharging curve figure of the button cell that is made of embodiment 4 under 0.1/0.1C charge/discharge rates.
Figure 15 is charge and discharge of the button cell that is made of embodiment 4 under 0.2C/0.2C~0.2C/10C charge/discharge rates Electric curve map.
Figure 16 is charging and discharging curve figure of the button cell that is made of embodiment 5 under 0.1/0.1C charge/discharge rates.
Figure 17 is charge and discharge of the button cell that is made of embodiment 5 under 0.2C/0.2C~0.2C/10C charge/discharge rates Electric curve map.
Figure 18 is charging and discharging curve figure of the button cell that is made of embodiment 6 under 0.1/0.1C charge/discharge rates.
Figure 19 is charge and discharge of the button cell that is made of embodiment 6 under 0.2C/0.2C~0.2C/10C charge/discharge rates Electric curve map.
Figure 20 is charging and discharging curve figure of the button cell that is made of embodiment 7 under 0.1/0.1C charge/discharge rates.
Figure 21 is charge and discharge of the button cell that is made of embodiment 7 under 0.2C/0.2C~0.2C/10C charge/discharge rates Electric curve map.
Figure 22 is charging and discharging curve figure of the button cell that is made of embodiment 8 under 0.1/0.1C charge/discharge rates.
Figure 23 is charge and discharge of the button cell that is made of embodiment 8 under 0.2C/0.2C~0.2C/10C charge/discharge rates Electric curve map.
Figure 24 is spinelle-LNMO cathode material of the embodiment 1 to embodiment 8, fill in 25 DEG C of room temperatures and 0.1C/0.1C/ Under discharge rate, the Electrical analysis through 30 (cycles) charge and discharge circulation life detections compares figure.
Figure 25 is spinelle-LNMO cathode material of the embodiment 1 to embodiment 8, in 25 DEG C of room temperatures and and 1C/1C discharge charges Under electric speed, the Electrical analysis through 100 (cycles) charge and discharge circulation life detections compares figure.
Figure 26 is the spinelle-LNMO cathode materials of embodiment 3, embodiment 4, embodiment 5 and embodiment 7, high at 55 DEG C Under temperature and 0.1C/0.1C charge/discharge rates, the Electrical analysis through 30 (cycles) charge and discharge circulation life detections compares figure.
Figure 27 is the spinelle-LNMO cathode materials of embodiment 3, embodiment 4, embodiment 5 and embodiment 7, high at 55 DEG C Under temperature and 1C/1C charge/discharge rates, the Electrical analysis through 100 (cycles) charge and discharge circulation life detections compares figure.
Reference
Covered on 10 button cells 20
The pad of 30 spring 40
The 50 circular barrier films of negative electrode 60
The lower cover of 70 lithium metal positive electrode 80
Embodiment
The present invention discloses a kind of Li, Ni, Mn oxide cathode material (or positive electrode) for having spinel structure, molecular formula For LiNiyMn2-yO4, and 0<y<1, hereinafter referred to as lithium nickel manganese cathode material or spinelle-LNMO cathode materials, it is adaptable to as The positive pole (or negative electrode) of lithium rechargeable battery.
Spinelle-LNMO the cathode materials of the present invention, preferred embodiment includes：
1) y=0.4 LiNi0.4Mn1.6O4Cathode material, wherein Li:Ni:Mn mol ratios are 1:0.4:1.6；
2) y=0.5 LiNi0.5Mn1.5O4Cathode material, wherein Li:Ni:Mn mol ratios are 1:0.5:1.5；
Or
3) y=0.6 LiNi0.6Mn1.4O4Cathode material, wherein Li:Ni:Mn mol ratios are 1:0.6:1.4.
Spinelle-LNMO the cathode materials of the present invention, most preferred embodiment is y=0.5 LiNi0.5Mn1.5O4Negative electrode material Material, hereinafter referred to as spinelle-LNMO (y=0.5) cathode material.
The lithium nickel manganese cathode material of the present invention, is the manufacture method using lithium source, nickel source, manganese source as raw material in building-up process It is to use solid phase method or spray drying process synthetic spinel-LNMO cathode materials, in building-up process, also selection uses following four Plant the one or more in modified preparation technology so that Spinel-LNMO cathode materials are modified：
1) in ball milling preparation technology, the mill ball or zirconia ball (ZrO of different sphere diameter sizes are used2Ball, hereafter Abbreviation zirconium ball) fine grinding or Ultrafine Grinding raw material and predecessor, by passing through different fine grindings or the grinding of Ultrafine Grinding degree and crushing, adjustment Raw material and predecessor are ground and be crushed into the granular size after powder；
The powder particle size of raw material and predecessor, size is more tiny or trickle, obtained spinelle-LNMO negative electrode materials Material has more preferably high power characteristic and good charge discharge cycles life-span；
2) cladding carbon-coating is carried out to the surfaces of spinelle-LNMO cathode materials to be modified, be made the spinelle of bag carbon modification- LNMO/C cathode materials；
3) last layer modified layer is coated with to the surface of spinelle-LNMO cathode materials, is made and possesses core shell structure (core- Shell structure) spinelle-LNMO cathode materials；
4) it is cation-modified to spinelle-LNMO cathode materials doping (doped), to lift its structural stability and circulation Life-span.
The lithium nickel manganese cathode material of the present invention, by one or more preparation technologies in described four kinds modified preparation technologies It is modified, it can be effectively improved and improve the electrical conductivity of the active material of lithium nickel manganese cathode material so that obtained spinelle- LNMO cathode materials have extraordinary high power characteristic and good charge discharge cycles life-span, are carrying out high-speed charge/discharge Under, with splendid stability and gram capacitance.Especially, obtained LiNi0.5Mn1.5O4(y=0.5) cathode material, Under voltage 3.5V~5.0V, gram capacitance about 145mAh/g under 0.1C rate discharges reaches theory gram capacitance 147mAh/ The 98.6% of g, gram capacitance sequentially about 135mAh/g, 125mAh/g, 111mAh/g, are fitted under 1C, 5C, 10C rate discharge Positive pole for secondary lithium battery to be made：
The lithium nickel manganese cathode material or spinelle-LNMO cathode materials of the present invention, using solid phase method, (prepared by hereinafter referred SS Method) prepare the step of, including：
1) selection lithium source, nickel source and manganese source are raw material；Wherein, lithium source:Nickel source:The mol ratio of manganese source is 1:y:2-y, and 0< y<1；Preferably y=0.4,0.5 or 0.6, most preferably y=0.5；
2) be based on step 1) raw material weight, select the chelating of certain usage amount；
3) lithium source, nickel source, four kinds of raw materials of manganese source and chelating are directly done into solid phase mixing formation spinelle-LNMO negative electrode materials Expect predecessor；
4) one or more in following modified preparation technology are carried out to spinelle-LNMO cathode materials predecessor；Including：
A) mill ball or zirconium ball from sphere diameter size between 0.1~0.3mm carry out fine grinding or Ultrafine Grinding spinelle-LNMO Cathode material predecessor；
B) or depending on the circumstances or the needs of the situation, the carbon source and/or conductive carbon material for selecting certain usage amount are selected else, to spinelle-LNMO negative electrodes The surface of material precursor carries out cladding carbon-coating and is modified；
C) last layer modified layer is coated with to the surface of spinelle-LNMO cathode material predecessors；
D) adulterate one or more of selected cations to spinelle-LNMO cathode materials predecessor；
5) the cathode material predecessor by modified preparation technology is inserted into the calcining of high temperature (tubulose) stove, tool spinelle is made The lithium nickel manganese cathode material or spinelle-LNMO cathode materials of structure.
The lithium nickel manganese cathode material or spinelle-LNMO cathode materials of the present invention, using another spray drying process (hereafter Abbreviation SP preparation methods) prepare the step of, including：
1) selection lithium source, nickel source and manganese source are raw material；Wherein, lithium source:Nickel source:The mol ratio of manganese source is 1:y:2-y, and 0< y<1；Preferably y=0.4,0.5 or 0.6, most preferably y=0.5；
2) be based on step 1) raw material weight, select the chelating of certain usage amount；
3) lithium source, nickel source, four kinds of raw materials of manganese source and chelating are directly done into solid phase mixing formation spinelle-LNMO negative electrode materials Expect predecessor；
4) take step 3) spinelle-LNMO cathode materials predecessor directly do liquid phase with carbon source and mix；
5) the sphere structure spinelle-LNMO/C cathode material predecessors that spray drying forms cladding carbon source are bestowed；
6) insert high temperature furnace and carry out calcining heat treatment, sphere structure spinelle-LNMO/C cathode materials are made.
The definition of the lithium source, refers to the source of lithium metal, can for (lithium) metal hydroxides, (lithium) metal chloride or (lithium) metallic salt, be preferably selected from lithium hydroxide, lithium nitrate, lithium acetate, lithium chloride, lithium hydrogen phosphate, lithium phosphate, lithium carbonate or One or more of mixing in lithium bicarbonate.
The definition of the nickel source, refers to the source of nickel metal, can for (nickel) metal hydroxides, (nickel) metal chloride or (nickel) metallic salt, the one kind being preferably selected from nickel sulfate, nickel oxalate, nickel acetate, nickel nitrate, nickel chloride or nickel hydroxide or Their mixing.
The definition of the manganese source, refers to the source of manganese Metal, can be (manganese) metal oxide or (manganese) metallic salt, preferably For selected from manganese oxalate, manganese carbonate, manganese citrate, manganese sulfate, manganese acetate, manganese nitrate, manganese phosphate, electrolytic manganese dioxide or manganese oxide (including α-MnO2、β-MnO2、γ-MnO2、Mn2O3Or Mn3O4) in one kind or their mixing.
The lithium nickel manganese cathode material of the present invention, in solid phase method (SS preparation methods) or spray drying process (SP preparation methods) , it is necessary to using chelating as reducing agent, can be used in organic acid chelating or high score subclass chelating in preparation technology A kind of or their mixing.Wherein, the organic acid chelating be selected from citric acid (citric acid, hereinafter referred CA), oneself Diacid (adipic acid), ascorbic acid (Vitamin C) (ascorbic acid), ethylenediamine tetra-acetic acid (EDTA), stearic acid (stearic acid, hereinafter referred SA), oxalic acid (oxalic acid) or one kind in laurate (lauric acid) or it Mixing, it is preferable to use stearic acid (SA) or/and citric acid (CA)；The high score subclass chelating is selected from polyvinyl pyrrole In pyridine (polyvinylpyrrolidone, PVP), polyvinyl alcohol (polyvinyl alcohol, PVA) or furans (furan) A kind of or their mixing.
The definition of the carbon source, refers to the source of carbon, can be organic compound, natural polymer or synthesis high score Sub- compound, is preferably selected from citric acid (CA), sucrose (Sucrose, hereinafter referred to as Suc), glucose (Glucose), starch (Starch), furans (Furan) resin, polyvinyl alcohol (PVA), polystyrene (PS), polystyrene spheres (PS balls) or methyl-prop One kind or their mixing in alkene methyl esters ball (PMMA balls) high polymer material.
The carbon source can be any size shape, including 1D, 2D or 3D nano material, and preferred embodiment is using tool 3D Spherical, size 100~1,000nm high polymer material as carbon source, for example, the particle diameter of the PS balls or PMMA balls, preferably Between 200~400nm.The usage amount of the carbon source, based on spinelle-LNMO/C gross weights, be between 0.1~80wt%, it is excellent Elect 20~30wt% as.
For concise description, " carbon source " is mentioned with hereinafter all, also the source including conductive carbon material.The conductive carbon material can To be led using selected from Super P conductive carbon materials (hereinafter referred to as SP conductive carbon materials), carbon ball conductive carbon material (hereinafter referred to as CS), carbon black Electrical carbon material (hereinafter referred to as CB), graphene conductive carbon materials, CNT carbon materials (hereinafter referred to as CNTs carbon materials), electrographite, conjunction Into the one of which of graphite or carbonaceous mesophase spherules (MCMB)；The conductive carbon material of various combination can also be used, for example, using SP The combination of combination or SP conductive carbon material and CNTs carbon materials of the conductive carbon material with CS conductive carbon materials or use graphite and CNTs carbon The combination of material；The conductive carbon material of identical or different form can also be used.Wherein, the particle diameter of the CS conductive carbon materials, between 200 ~500nm.
Spinelle-LNMO the cathode materials of the present invention, in solid phase method (SS preparation methods) or spray drying process (SP preparation sides Method) preparation technology in, using chelating as reducing agent, chelating can also be used cloudy to spinelle-LNMO as carbon source Pole material bestows surface bag carbon modification, so that the spinelle-LNMO/C cathode materials of surface bag carbon are made.Wherein, it is described The usage amount of chelating, based on spinelle-LNMO/C gross weights, between 1.0~80wt%, preferably 20~40wt%.
Spinelle-LNMO the cathode materials of the present invention, in modified preparation technology, except using chelating and/or carbon source Surface bag carbon modification is bestowed to spinelle-LNMO cathode materials outer, can also select to be coated with (surface using another surface Coating) method of modifying, by well known coating technique, is modified to the surface coating last layer of spinelle-LNMO cathode materials Layer, it is, the spinelle-LNMO cathode materials of the present invention, after surface coating last layer is modified material, as nucleocapsid knot Structure (core-shell structure), concrete structure be using spinelle-LNMO cathode materials as nuclear structure, and, with pass through Cross coating and be coated on the modified layer on nuclear structure surface as shell structure.The coating amount of the modified layer, based on being used as nuclear structure Spinelle-LNMO/C gross weight, between 0.1~20wt%；Preferably between 0.5~10wt%.
Spinelle-LNMO the cathode materials for possessing core shell structure, hereinafter represented as spinelle-LNMO/Xwt%Y materials Material, wherein, spinelle-LNMO refers to possess the nuclear structure in core shell structure, and Y materials refer to the modified layer material as shell structure Material, Xwt% refers to coating amount of the Y materials with respect to nuclear structure.The Y materials (or constituting the material of modified layer) are selected from lithium titanate (Li4Ti5O12, abbreviation LTO), lithium phosphate aluminium titanium (Li1.4Al0.4Ti1.6P3O12, abbreviation LATP), lithium titanate lanthanum (Li0.75La0.42TiO3, abbreviation LLTO), ruthenic chloride (RuCl3), binary stratiform nickel ion doped (LiNi0.5Mn0.5O2), cobalt acid lithium (LiCoO2, abbreviation LCO), layered LiMnO (Li2MnO3), LiFePO4 (LiFePO4, abbreviation LFP), phosphoric acid vanadium lithium (Li3V2 (PO4)3, abbreviation LVP), ferric phosphate (FePO4)、LiNi1/3Co1/3Mn1/3O2(referred to as 111 ternary materials), LiNi0.4Co0.2Mn0.4O2(referred to as 424 ternary materials) or LiNi0.5Co0.2Mn0.3O2One kind in (referred to as 523 ternary materials) or It is mixed above.
Spinelle-LNMO/Xwt%Y the materials of the present invention, because possessing core shell structure, are made for lithium ion secondary electricity During the positive pole in pond, the LNMO active materials of spinelle-LNMO cathode materials are coated on outer modified layer and isolate and prevent LNMO Active material is directly contacted with lithium battery electrolytes, so as to prevent or reduce the decomposition of lithium battery electrolytes.
The present invention spinelle-LNMO cathode materials, through overdoping (doped) it is cation-modified after, can be lifted spinelle- The structural stability of LNMO cathode materials, so as to improve its electronic conductivity and improve its high power charge-discharge battery performance and follow The ring life-span.Wherein, the spinelle-LNMO (0<y<1) the cation blended amount of cathode material, excellent between 0.01~20mol% Elect as between 0.5~10mol%.
Spinelle-LNMO the cathode materials being modified by foreign cation, hereinafter represented as spinelle-LNMO/ Xmol%Zn+Cation, wherein, Zn+Cation refers to be applied to spinelle-LNMO negative electrodes when being modified preparation technology Material is doped modified cation, and Xmol% refers to Zn+Blended amount (mol%) of the cation relative to LNMO raw materials.It is described Zn+Cation in alkali metal, alkali earth metal, the 3rd race's element, transition metal and rare earth element wherein One or more cations；It is preferably selected from Ru4+、Mn2+、Mg2+、Al3+、Ti4+、Zr4+、Nb5+Or W+6Deng cation element.
Spinelle-LNMO the cathode materials of the present invention, whether using solid phase method (SS preparation methods) or spray drying process (SP preparation methods) is made, and inserts spinelle-LNMO predecessors before high-temperature tubular stove calcined in preparation technology, can Selectivity carries out pre-burning heat treatment, in 400~550 DEG C of nitrogen (N of temperature2) or argon gas (Ar) atmosphere in, carry out heat treatment 1~ 20 hours, preferred embodiment was the nitrogen (N in 475~525 DEG C of temperature2) or argon gas (Ar) atmosphere in, carry out heat treatment 5~7 Hour, the moisture content and small molecule of spinelle-LNMO predecessors are removed, and improve the crystallinity of spinelle-LNMO predecessors Afterwards, then insert high temperature furnace carry out calcining heat treatment.
Spinelle-LNMO the cathode materials of the present invention, whether using solid phase method (SS preparation methods) or spray drying process (SP preparation methods) is made, and carries out the condition of calcining heat treatment in high temperature furnace, is in the environment of air or is being passed through purity oxygen (pure O2) in the environment of, with 2~10 DEG C/min heating rate, the first stage is carried out at 800~1000 DEG C of calcining heat Calcining heat treatment, and be persistently heat-treated 5~25 hours, preferably persistently it is heat-treated 8-12 hours；After first stage calcining terminates, 500~700 DEG C are cooled to, and second stage calcining heat treatment is carried out in the environment of air, constant temperature heat treatment 5~25 is kept Hour, preferably keep constant temperature to be heat-treated 8-12 hours；Afterwards, treat that high-temperature tubular stove is down to room temperature, i.e., a kind of obtained spinelle- LNMO cathode materials.
Spinelle-LNMO/C the cathode materials of the present invention, whether using solid phase method (SS preparation methods) or spray drying When method (SP preparation methods) is made, carbon source content (or residual carbon amounts) of the spinelle-LNMO/C cathode materials after calcining, Between the 0.10~20wt% of percentage by weight for accounting for spinelle-LNMO/C cathode materials, carbon amounts is preferably remained between 2~10wt% Between, optimal residual carbon amounts is between 5~10wt%.
In order to illustrate the spinelle-LNMO cathode materials that the present invention is prepared using SS preparation methods (solid phase method), y is lifted =0.5 LiNi0.5Mn1.5O4Illustrate exemplified by cathode material, its material composition includes：Take lithium, nickel and manganese Metal salt or its oxygen Compound is raw material, and uses stearic acid (SA) and citric acid (CA) to be reducing agent or carbon source, or further adds conductive carbon material For carbon source.
As shown in figure 1, with " solid phase method (SS preparation methods) preparation " spinelle-LNMO (y=0.5) cathode material, Including following step：
1) lithium (Li) is taken:Nickel (Ni):The mol ratio of manganese (Mn) is 1:0.5:1.5 lithium, nickel and manganese Metal salt is raw material (hereinafter referred LNMO raw materials)；
Concrete example is to measure 5.035g lithium hydroxides (LiOH), 1.854g hydroxides nickel (OH)2And 5.216g titanium dioxides Manganese (MnO2) it is raw material, wherein, lithium (Li):Nickel (Ni):The mol ratio of manganese (Mn) is 1:0.5:1.5；
2) LNMO raw material gross weights are based on, takes 1~80wt% chelatings as reducing agent, preferably takes 20~40wt% to sting Mixture is used as reducing agent；
Concrete example is takes stearic acid (SA) and citric acid (CA) to be reducing agent, according to weight ratio, by SA:CA:LNMO raw materials= 20~50%:5~10%:75~80% ratio, adds stearic acid (SA) and citric acid (CA)；
3) by LNMO raw materials and chelating be dissolved in together in water it is rearmounted enter ball grinder in；
4) mill ball in ball grinder, using sphere diameter between 0.1~0.3mm zirconium ball, control zirconium ball is with treating before ball milling The volume ratio (abbreviation ball compares admittedly) of thing material is driven between 8~10:1, preferably 10:1；
5) after ball grinder addition acetone or water are expired to eight points, insert and fine grinding and scattered LNMO raw materials are carried out in ball mill； Drum's speed of rotation is set under 400rpm, uniform grinding about 9 hours；
6) predecessor after grinding is washed out with acetone, isolates acetone solvent or water using vacuum convolution thickener, obtain To dry brown ceramic powder；
7) brown ceramic powder of preceding step is put into agate pot, the mill ball in agate pot, uses sphere diameter 4mm agate balls (SiO2Ball), control ball is solid than being 1.5~2:1, preferably 2:1；
8) agate pot of preceding step is inserted into progress Ultrafine Grinding brown ceramic powder in ball mill, be set in drum's speed of rotation Under 300rpm, uniform grinding about 1 hour is taken out and passes through extra-fine grinding and scattered LNMO predecessor fine powders；
9) LNMO predecessor fine powders are put into aluminum oxide (Al2O3) in boat, then high temperature furnace calcining heat treatment is inserted, institute is made State spinelle-LNMO (y=0.5) cathode material.
The solid phase method (SS preparation methods) of above-mentioned spinelle-LNMO (y=0.5) cathode material, in step 9) carry out high temperature During stove calcining heat treatment, the calcination condition of high temperature furnace is to be calcined in atmosphere, with 2 DEG C/min heating rate, in temperature At 400 DEG C, constant temperature pre-burning heat treatment about 2 hours is carried out；Again with 5 DEG C/min heating rate, in calcining heat 950 DEG C~1000 At DEG C, the progress first stage heats processing about 5 hours；Afterwards, it is cooled at 650 DEG C~700 DEG C of calcining heat, constant temperature about 10 is small When；Calcining is treated after terminating, and is down to room temperature, that is, y=0.5 LiNi is made0.5Mn1.5O4Cathode material.
The solid phase method (SS preparation methods) of above-mentioned spinelle-LNMO (y=0.5) cathode material, in step 8) take out and pass through After extra-fine grinding and scattered LNMO predecessor fine powders, alternative bestows spray drying granulation again to LNMO predecessor fine powders After (spray dry) technology, the LNMO predecessor powder to obtain spheroid form, step 9 is entered back into) carry out high temperature furnace calcining heat Processing, so that y=0.5 spherical LiNi is made0.5Mn1.5O4Cathode material.
As shown in Fig. 2 preparing spinelle-LNMO (y=0.5) the negative electrode material with " spray drying process (SP preparation methods) " Material, including following step：
1) with the step 1 of above-mentioned " SS preparation methods ") to step 6) dry LNMO brown ceramic powders are made；
2) 10g LNMO brown ceramic powders and 0.5g citric acids (CA), 0.5g polyvinyl alcohol (PVA) and 1g polystyrene spheres are taken (PS balls) does liquid phase mixing；
3) carry out mist projection granulating (spray dry) and sphere structure LNMO/C predecessor fine powders are made；60 DEG C of baking ovens are inserted to do After dry 2 hours, then insert 120 DEG C of vacuum drying ovens and dry 8 hours；
4) by step 3) dried LNMO/C predecessors fine powder is put into aluminum oxide (Al2O3) in boat, then insert high temperature furnace and forge Processing is heated, spinelle-LNMO (y=0.5) cathode material is made.
The spray drying process (SP preparation methods) of above-mentioned spinelle-LNMO (y=0.5) cathode material, in step 4) carry out During high temperature furnace calcining heat treatment, the calcination condition of high temperature furnace is to be calcined in atmosphere, with 2 DEG C/min heating rate, At 500 DEG C of temperature, first stage pre-burning heat treatment about 2.5 hours is carried out；Again with 5 DEG C/min heating rate, in calcining heat At 950 DEG C~1000 DEG C, the progress first stage heats processing about 5 hours；Afterwards, it is cooled to 650 DEG C~700 DEG C of calcining heat Under, constant temperature about 10 hours；Calcining is treated after terminating, and is down to room temperature, that is, y=0.5 LiNi is made0.5Mn1.5O4/ C cathode materials.
As shown in figure 3, spinelle-LNMO the cathode materials of the present invention, it is adaptable to cathode electrode sheet is made, during making, takes The present invention uses spinelle-LNMO cathode materials, polyvinylidene fluoride (PVDF, the poly that " SS preparation methods " is made (vinylidene difluoride)) sticker/N- N-methyl 2-pyrrolidone Ns [i.e. 7wt%PVDF in NMP], N- N-methyl 2-pyrrolidone Ns Solvent (NMP organic solvents, Bry gram (Panreac) company product) and Super P conductive carbon materials are raw material；According to spinelle- LNMO/C:PVDF/NMP:Super P=80wt%:10wt%:10wt% ratio is blended, and measures 3.0g's respectively LiNi0.5Mn1.5O4Cathode material, 5.375g PVDF/NMP (about 7wt%), 3.768g NMP and 0.375g SP conductive carbons After material；PVDF/NMP and NMP are first stirred after 10min, SP conductive carbon materials are slowly added into 9.143g PVDF/NMP and are used in combination Mixer is stirred, it is to be mixed it is uniform after, then by LiNi0.5Mn1.5O4Cathode material is slowly added among slurry and persistently stirred, and treats After stirring completely, by the slurry prepared with scraper for coating on treated aluminium foil (Al foil), and negative electricity is made Pole, and the negative electrode made is put into baking oven, after being dried 2~3 hours under temperature 60 C, then at 120 DEG C of drying of temperature 10 hours, to remove the organic solvent of residual；Negative electrode after drying is rolled into leveling processing using roller press.Finally, use 13mm guillotines cut circular negative electrode.Solid-to-liquid ratio control in cathode electrode sheet manufacturing process is 1:3, the work of cathode electrode sheet Property material average weight is about between 4~6mg.
As shown in figure 4, the structure of general 2032 button cell 10, including lid 20 on one, a spring 30, a pad 40, One circular negative electrode 50, a barrier film 60, a lithium metal positive electrode 70 and a lower cover 80.Spinelle-LNMO the negative electrodes of the present invention Material, it is adaptable to cathode electrode sheet is made, can be used as the circular negative electrode 50 of 2032 button cells 10.
The electrolyte of lithium rechargeable battery (hereinafter referred lithium battery), is by electrolyte lithium salt (such as lithium hexafluoro phosphate (LiFL6) or hexafluoroarsenate lithium (LiAsF6)) plus organic solvent, (such as ethylene carbonate (EC) or diethyl carbonate (DEC) are adjusted With into.When lithium battery selects the spinelle-LNMO cathode materials of the present invention as cathode electrode sheet, lithium battery can arrange in pairs or groups Using the lithium battery electrolytes of different formulations, to lift its electric discharge gram capacitance in high temperature and low temperature.So-called applicable lithium electricity The composition of pond electrolyte, can be selected from concentration 1M LiAsF6Add EC/MF (volume ratios 1:3) mixed solvent, concentration 1M LiPF6 Add EC/DEC (volume ratios 1:1) mixed solvent, concentration 1M LiPF6Add EC/DEC (volume ratios 3:7) mixed solvent, concentration 1M LiPF6Add EC/EMC (volume ratios 2:1) mixed solvent, concentration 1M LiPF6Add EC/DMC (volume ratios 3:7) mix molten Agent, concentration 1M LiPF6Add EC/DEC/DMC (volume ratios 1:1:1) mixed solvent, concentration 1M LiPF6Add EC/EMC/MA/ Toluene (toluene) (volume ratio 1:1:1:1) mixed solvent, concentration 1M LiPF6Add EC/EMC/EP (volume ratios 30:30: 40) mixed solvent, concentration 1M LiPF6Add EC/EMC/DEC/EP (volume ratios 30:35:35) mixed solvent, concentration 1M LiPF6 Add EC/DEC/IPA (volume ratios 30:35:35) mixed solvent, concentration 1M LiPF6Add EC/EMC/EA (volume ratios 30:30: 40), concentration 1M LiPF6Add EC/DMC/MA (volume ratios 30:30:40) mixed solvent, concentration 1M LiPF6Add EC/DMC/ EA mixed solvents, concentration 1M LiPF6Add EC/DMC/MB mixed solvents, concentration 1M LiPF6Addition PC/EC/MB mixed solvents, Concentration 1M LiPF6Add PC/EC/EMC (volume ratios 1:1:3) mixed solvent.Wherein, MF refers to methyl formate；MA refers to acetic acid Methyl esters；EA refers to ethyl acetate；MP refers to methyl propionate；MB refers to methyl butyrate；EP refers to ethyl propionate；PC refers to carbonic acid third Alkene ester；EC refers to ethylene carbonate；DEC refers to diethyl carbonate；DMC refers to dimethyl carbonate；EMC refers to methyl ethyl Ester；IPA refers to isopropyl acetate.
Spinelle-LNMO (y=0.5) cathode material prepared by the present invention, with electron microscope (Hitachi 2600S SEM) its configuration of surface of observation analysis, obtains SEM surface analysis structure charts as shown in Figure 5.
Spinelle-LNMO (y=0.5) cathode material prepared by the present invention passes through Surface coating 2wt%RuCl3Afterwards, with electricity Its configuration of surface of sub- microscope (Hitachi 2600S SEM) observation analysis, obtains SEM surface analysis structures as shown in Figure 6 Figure.
From observation analysis Fig. 5 and Fig. 6 SEM surface analysis structure charts, obtain drawing a conclusion：
1) spinelle-LNMO (y=0.5) cathode material prepared by the present invention, point is can be seen that from the SEM figures shown in Fig. 5 There are some agglomerations on the surface of spar-LNMO (y=0.5) cathode material；
2) spinelle-LNMO (y=0.5) cathode material prepared by the present invention passes through Surface coating 2wt%RuCl3Afterwards, from The RuCl of many nanoscale small particles is can be seen that in SEM figures shown in Fig. 63Cathode material is equably attached to, it is, institute State nanometer-RuO of the surface of spinelle-LNMO (y=0.5) cathode material by one layer of spinelle (spinel) structure of cladding2 After oxide, because RuO2It is highly conductive sub- oxide material, nanoscale RuCl can be promoted3Effectively it is attached to LiNi0.5Mn1.5O4The surface of active material and surrounding, when carrying out high charge-discharge, are conducive to electronics to be easier turnover, Jin Erti Rise electronic conductivity, reduction interface impedance and Li+Ion diffusion rates and the long-term charge and discharge cycles stability of improvement.
More specifically, the spinelle-LNMO cathode materials that prepared by the present invention, applied to the negative electrode that button cell is made During electrode slice, there is splendid stability and gram capacitance really when carrying out high charge-discharge, the overall stabilization of battery can be increased Property and gram capacitance.
Using prefabricated spinelle-LNMO (y=0.5) cathode material of solid phase method (SS preparation methods), and according to following table one The modified preparation technologies of difference, prefabricated spinelle-LNMO (y=0.5) cathode material that modification degree is differed further is made Sample (1)~(7)：
Table one
Spinelle-LNMO (y=0.5) cathode material samples (1)~(7) of table one are taken, it is levigate respectively with stainless steel mortar Afterwards, insert in stainless steel microscope carrier and flatten, then be respectively put into X-ray diffractometer (XRD, computer hardware：D2PHASER, BRUKER, DE) Middle analyzing crystal structure.Operating condition is as follows：D2PHASER voltage is set to 40KV, and electric current is 20mA, scanning range be 2 θ= Between 10 °~70 °, sweep speed is 0.02 °/spacing and 0.5sec/ spacing, obtains X-ray diffraction (XRD) collection of illustrative plates shown in Fig. 7.
X-ray diffraction (XRD) collection of illustrative plates of Fig. 7 sample (1)~(7) is observed, through comparing：
1) X-ray diffraction (XRD) collection of illustrative plates of cathode material sample (1) and sample (2) is the same, has no other miscellaneous or not pure phases Produce, this explanation：In ball milling preparation technology, LNMO raw materials are ground using the mill ball or zirconium ball of different sphere diameter sizes, for The crystalline phase of obtained spinelle-LNMO (y=0.5) cathode material, is unaffected；
2) cathode material sample (3), sample (4), sample (5) and sample (6) are the spinelle-LNMO (y of tool core shell structure =0.5) cathode material, its surface is respectively coated 1wt%LTO, 1wt%LATP or 2wt%RuCl3, it is modified with no coating The cathode material sample (1) and sample (2) of layer are compared, and X-ray diffraction (XRD) collection of illustrative plates of cathode material sample (1)~(6) is the same, Have no other miscellaneous or not pure phase generations, this explanation：In modified preparation technology, it is made by coating modified layer and possesses core shell structure Spinelle-LNMO (y=0.5) cathode material, it is cloudy for the obtained spinelle-LNMO (y=0.5) for possessing core shell structure The crystalline phase of pole material, is unaffected；
3) cathode material sample (7) is doping 1mol%Ru4+Spinelle-LNMO (y=0.5) cathode material of ion, with There is no the cathode material sample (1) of foreign cation and sample (2) to compare, the X-ray of cathode material sample (1), (2) and (7) around Penetrate (XRD) collection of illustrative plates the same, have no other miscellaneous or not pure phase generations, this explanation：In modified preparation technology, by foreign cation Spinelle-LNMO (y=0.5) cathode material of foreign cation is made, for obtained foreign cation spinelle- The crystalline phase of LNMO (y=0.5) cathode material, is unaffected.
【Embodiment】
Spinelle-LNMO the cathode materials that embodiments below is made, are further made for secondary lithium battery (example Such as, button cell) circular negative electrode after, carry out charge/discharge analysis.
The condition determination of charge/discharge analysis：
Measure hardware：Use (model Model BAT-750B) analysis by charged and discharged instrument of good excellent company system.
Measurement mode：It will be placed in without short-circuit button cell on charge/discharge analyzer, setting and adjusting parameter, if Voltage range is determined between 2.0V to 5.0V, is carried out the different charge/discharge rates in the case where determining electric current according to different setting electric current values and is examined Survey.
Qualifications：After each discharge and recharge terminates, lounge is further continued for carrying out next cycle detection every after about 3 minutes.
Detected by continuously charge/discharge for several times, utilize computer recording and acquirement voltage and the discharge curve of time change And capacitance data, through com-parison and analysis, that is, obtain actual discharge amount of the test battery under different discharge rates.
Embodiment 1：
Spinelle-LNMO (y=0.5) cathode material is prepared using solid phase method (SS preparation methods), and in modified preparation Sphere diameter 0.3mm zirconium ball grinding LNMO raw materials are used in technique.By obtained LiNi0.5Mn1.5O4Cathode material is made for button The circular negative electrode of button-type battery, and the electrolyte of button cell uses general electrolyte (blank electrolyte), its Composition is 1M LiPF6Add EC/DEC (volume ratios 1:1) mixed solvent.
Under 25 DEG C of normal temperature, by voltage range setting between 3.5V to 5.0V, 0.1C/ is tested using Discharge analysis instrument Discharge capacity under 0.1C, 0.2C/0.2C~0.2C/10C charge/discharge rates.Test result is as shown in table two and table three, discharge and recharge Curve difference is as can be seen from figures 8 and 9.
Gram capacitance of the table two under 0.1C/0.1C charge/discharge rates
Gram capacitance of the table three under the different charge/discharge rates of 0.2C/0.2C~0.2C/10C
According to gram capacitance value of table two and table three, the button cell of the present embodiment, using in modified preparation technology In with 0.3mm zirconiums ball grind LiNi0.5Mn1.5O4Circular negative electrode is made in cathode material；In 0.1C/0.1C charge/discharge rates Under, the electric discharge gram capacitance of its first time cycle detection (cycle 1) can be of about 117.98mAh/g, in third time cycle detection Gram capacitance still reaches 114.19mAh/g after the electric discharge of (cycle 3), and coulombic efficiency is up to 82.66%.
Under 0.2C/0.2C, 0.2C/0.5C, 0.2C/1C, 0.2C/3C, 0.2C/5C and 0.2C/10C charge/discharge rate, Gram capacitance of its second of cycle detection (cycle 2) be respectively 119.79mAh/g, 119.98mAh/g, 118.44mAh/g, 113.04mAh/g, 107.45mAh/g and 92.01mAh/g, average coulombic efficiency can be confirmed according to this up to 95.25~98.40% The button cell of the present embodiment possesses splendid high-speed charging and discharging capabilities and good electrical performance.
Embodiment 2：
LiNi is made in the preparation method of be the same as Example 10.5Mn1.5O4Cathode material, but be changed to make in modified preparation technology LNMO raw materials are ground with sphere diameter 0.1mm zirconium ball.By obtained LiNi0.5Mn1.5O4Cathode material is made for button cell Circular negative electrode, and button cell electrolyte use general electrolyte (blank same as Example 1 electrolyte)。
Under 25 DEG C of normal temperature, by voltage range setting between 3.5V to 5.0V, 0.1C/ is tested using Discharge analysis instrument Discharge capacity under 0.1C, 0.2C/0.2C~0.2C/10C charge/discharge rates.Test result is as shown in table four and table five, discharge and recharge Curve difference is as shown in Figures 10 and 11.
Gram capacitance of the table four under 0.1C/0.1C charge/discharge rates
Gram capacitance of the table five under the different charge/discharge rates of 0.2C/0.2C~0.2C/10C
According to gram capacitance value of table four and table five, the button cell of the present embodiment, using in modified preparation technology In with 0.1mm zirconiums ball grind LiNi0.5Mn1.5O4Circular negative electrode is made in cathode material；In 0.1C/0.1C charge/discharge rates Under, the electric discharge gram capacitance of its first time cycle detection (cycle 1) can be of about 121.44mAh/g, in third time cycle detection Gram capacitance still reaches 123.65mAh/g after the electric discharge of (cycle 3), and coulombic efficiency is up to 94.69%.
Under 0.2C/0.2C, 0.2C/0.5C, 0.2C/1C, 0.2C/3C, 0.2C/5C and 0.2C/10C charge/discharge rate, Gram capacitance of its second of cycle detection (cycle 2) be respectively 123.88mAh/g, 129.74mAh/g, 130.23mAh/g, 127.37mAh/g, 124.50mAh/g and 110.04mAh/g, average coulombic efficiency can be demonstrate,proved according to this up to 96.04~104.25% The button cell of real the present embodiment possesses splendid high-speed charging and discharging capabilities and good electrical performance.
Compared with embodiment 1 in modified preparation technology using 0.3mm zirconiums ball grinding raw material, the button type electricity of embodiment 2 Pond, gram capacitance under 0.1C/0.1C and 0.2C/0.2C~0.2C/10C charge/discharge rates, better than the button of embodiment 1 Type battery.This explanation：Raw material is ground using sphere diameter smaller zirconium ball in modified preparation technology, the smaller point of particle diameter can be made brilliant Stone-LNMO cathode materials (or active material), so that circular negative electrode is made, are more conducive to being lifted the lithium ion of button cell (Li+) spread and electrically transmission.
Embodiment 3：
Spinelle-LNMO (the y=0.5)/1wt% metatitanic acids for possessing core shell structure are prepared using solid phase method (SS preparation methods) Lithium (LTO), and grind LNMO raw materials using sphere diameter 0.3mm zirconium ball in modified preparation technology.Will be obtained LiNi0.5Mn1.5O4The circular negative electrode for button cell, and the electricity of button cell is made in/1wt%LTO cathode materials Solve liquid and use general electrolyte (blank electrolyte), its composition is 1M LiPF6Add EC/DEC (volume ratios 1:1) mix Bonding solvent.
Under 25 DEG C of normal temperature, by voltage range setting between 3.5V to 5.0V, 0.1C/ is tested using Discharge analysis instrument Discharge capacity under 0.1C, 0.2C/0.2C~0.2C/10C charge/discharge rates.Test result is as shown in table six and table seven, discharge and recharge Curve difference is as shown in FIG. 12 and 13.
Gram capacitance of the table six under 0.1C/0.1C charge/discharge rates
Gram capacitance of the table seven under the different charge/discharge rates of 0.2C/0.2C~0.2C/10C
According to gram capacitance value of table six and table seven, the button cell of the present embodiment, using in modified preparation technology In with 0.3mm zirconiums ball grind LiNi0.5Mn1.5O4Circular negative electrode is made in/1wt%LTO cathode materials；Fill in 0.1C/0.1C/ Under discharge rate, the electric discharge gram capacitance of its first time cycle detection (cycle 1) can be of about 123.59mAh/g, in third time Gram capacitance still reaches 123.19mAh/g after the electric discharge of cycle detection (cycle 3), and coulombic efficiency is up to 95.33%.
Under 0.2C/0.2C, 0.2C/0.5C, 0.2C/1C, 0.2C/3C, 0.2C/5C and 0.2C/10C charge/discharge rate, Gram capacitance of its second of cycle detection (cycle 2) be respectively 121.53mAh/g, 123.84mAh/g, 122.11mAh/g, 116.32mAh/g, 110.73mAh/g or 93.44mAh/g, average coulombic efficiency can be confirmed according to this up to 96.33~98.44% The button cell of the present embodiment possesses splendid high-speed charging and discharging capabilities and good electrical performance.
Embodiment 4：
The preparation method of be the same as Example 3, is made the LiNi for possessing core shell structure0.5Mn1.5O4/ 1wt% lithium phosphate aluminium titaniums (LATP) cathode material, then the circular negative electrode for button cell is made, and the electrolyte of button cell is used and reality Apply the general electrolyte of the identical of example 3 (blank electrolyte).
Under 25 DEG C of normal temperature, by voltage range setting between 3.5V to 5.0V, 0.1C/ is tested using Discharge analysis instrument Discharge capacity under 0.1C, 0.2C/0.2C~0.2C/10C charge/discharge rates.Test result is as shown in table eight and table nine, discharge and recharge Curve is respectively as shown in Figure 14 and Figure 15.
Gram capacitance of the table eight under 0.1C/0.1C charge/discharge rates
Gram capacitance of the table nine under the different charge/discharge rates of 0.2C/0.2C~0.2C/10C
According to gram capacitance value of table eight and table nine, the button cell of the present embodiment, using in modified preparation technology In with 0.3mm zirconiums ball grind LiNi0.5Mn1.5O4Circular negative electrode is made in/1wt%LATP cathode materials；In 0.1C/0.1C Under charge/discharge rate, the electric discharge gram capacitance of its first time cycle detection (cycle 1) can be of about 110.85mAh/g, the 3rd Gram capacitance still reaches 116.19mAh/g after the electric discharge of secondary cycle detection (cycle 3), and coulombic efficiency is up to 96.53%.
Under 0.2C/0.2C, 0.2C/0.5C, 0.2C/1C, 0.2C/3C, 0.2C/5C and 0.2C/10C charge/discharge rate, Gram capacitance of its second of cycle detection (cycle 2) be respectively 116.16mAh/g, 113.85mAh/g, 111.74mAh/g, 103.11mAh/g, 93.22mAh/g, 67.13mAh/g, average coulombic efficiency can confirm this according to this up to 64.34~99.25% The button cell of embodiment possesses splendid high-speed charging and discharging capabilities and good electrical performance.
Embodiment 5：
The preparation method of be the same as Example 3, but LiNi is made0.5Mn1.5O4/ 2wt%RuCl3Cathode material, and will be obtained LiNi0.5Mn1.5O4/ 2wt%RuCl3The circular negative electrode for button cell is made in cathode material；The electricity of button cell Solution liquid is changed to using the electrolyte A for being adapted to the 55 DEG C of applications of 5V high voltages and high temperature, and its composition is 1M LiPF6Except addition EC/DEC (volume ratio 1:2) outside solvent, 1wt% high voltage additives are additionally added.Under 25 DEG C of normal temperature, by voltage range setting between 3.5V To 5.0V, the discharge capacity tested using Discharge analysis instrument under 0.1C/0.1C, 0.2C/0.2C~0.2C/10C charge/discharge rates. Test result is as shown in table ten and table 11, and charging and discharging curve difference is as shown in FIG. 16 and 17.
Gram capacitance of the table ten under 0.1C/0.1C charge/discharge rates
Gram capacitance of the table 11 under the different charge/discharge rates of 0.2C/0.2C~0.2C/10C
According to gram capacitance value of table ten and table 11, the button cell of the present embodiment prepares work using modified The LiNi ground in skill with 0.3mm zirconiums ball0.5Mn1.5O4/ 2wt%RuCl3Circular negative electrode is made in cathode material, and uses electrolysis Liquid A is lithium battery electrolytes；Under 0.1C/0.1C charge/discharge rates, the electric discharge gram of its first time cycle detection (cycle 1) Capacitance can be of about 145.39mAh/g, and gram capacitance still reaches after third time cycle detection (cycle 3) electric discharge 135.57mAh/g, coulombic efficiency is up to 90.43%.
Under 0.2C/0.2C, 0.2C/0.5C, 0.2C/1C, 0.2C/3C, 0.2C/5C and 0.2C/10C charge/discharge rate, Gram capacitance of its second of cycle detection (cycle 2) be respectively 134.53mAh/g, 136.26mAh/g, 135.52mAh/g, 132.43mAh/g, 125.87mAh/g and 111.39mAh/g, average coulombic efficiency can be demonstrate,proved according to this up to 95.10~99.26% The button cell of real the present embodiment possesses splendid high-speed charging and discharging capabilities and good electrical performance.
1) button cell of embodiment 5, the electric discharge gram capacitance under 0.1C/0.1C charge/discharge rates reaches 145.39mAh/g, reaches the 98.90% of theory gram capacitance 147mAh/g；
2) the button cell selection with embodiment 1 is electric for battery using general electrolyte (blank electrolyte) Liquid phase is solved compared with the button cell of embodiment 5, under 0.1C/0.1C and 0.2C/0.2C~0.2C/10C charge/discharge rates Gram capacitance, better than the button cell of embodiment 1.This explanation：The LiNi being made with the same terms0.5Mn1.5O4Cathode material The circular negative electrode for button cell is made, suitable battery electrolyte is selected by careful, additionally it is possible to lift button cell Lithium ion (Li+) diffusion and electrically transmission.
Embodiment 6：
From RuO2As Ru4+Dopant (dopant), prepares foreign cation with solid phase method (SS preparation methods) and is modified Spinelle-LNMO (y=0.5)/1mol%Ru4+, and ground in modified preparation technology using sphere diameter 0.1mm zirconium ball LNMO raw materials.By obtained LiNi0.5Mn1.5O4/ 1mol%Ru4+The circular negative electricity for button cell is made in cathode material Pole, and the electrolyte of button cell uses general electrolyte (blank electrolyte).
Under 25 DEG C of normal temperature, by voltage range setting between 3.5V to 5.0V, 0.1C/ is tested using Discharge analysis instrument Discharge capacity under 0.1C, 0.2C/0.2C~0.2C/10C charge/discharge rates.Test result is filled as shown in table 12 and table 13 Discharge curve is respectively as shown in Figure 18 and Figure 19.
Gram capacitance of the table 12 under 0.1C/0.1C charge/discharge rates
Gram capacitance of the table 13 under the different charge/discharge rates of 0.2C/0.2C~0.2C/10C
According to gram capacitance value of table 12 and table 13, the button cell of the present embodiment, using in modified preparation The LiNi ground in technique with 0.1mm zirconiums ball0.5Mn1.5O4/ 1mol%Ru4+Circular negative electrode is made in cathode material；In 0.1C/ Under 0.1C charge/discharge rates, the electric discharge gram capacitance of its first time cycle detection (cycle 1) can of about 108.80mAh/g, Gram capacitance still reaches 110.42mAh/g after the electric discharge of 5th cycle detection (cycle 5), and coulombic efficiency is up to 92.53%.
Under 0.2C/0.2C, 0.2C/0.5C, 0.2C/1C, 0.2C/3C, 0.2C/5C and 0.2C/10C charge/discharge rate, Gram capacitance of its second of cycle detection (cycle 2) be respectively 111.86mAh/g, 111.08mAh/g, 106.44mAh/g, 92.53mAh/g, 86.08mAh/g and 72.16mAh/g, average coulombic efficiency can confirm this according to this up to 94.35~97.18% The button cell of embodiment possesses splendid high-speed charging and discharging capabilities and good electrical performance.
Compared with embodiment 2 in modified preparation technology using 0.1mm zirconiums ball grinding raw material, the button type electricity of embodiment 6 Pond, gram capacitance under 0.1C/0.1C and 0.2C/0.2C~0.2C/10C charge/discharge rates, though there is decline phenomenon and be inferior to The button cell of embodiment 2, but stability is greatly improved.This explanation：Spinelle-LNMO (y=0.5) cathode material It is modified in modified preparation technology using foreign cation, so that circular negative electrode is made, is conducive to improving button cell Stability.
Embodiment 7：
Spinelle-LNMO (the y=0.5)/2wt% chlorinations for possessing core shell structure are prepared using solid phase method (SS preparation methods) Ruthenium (RuCl3), and respectively using sphere diameter 0.1mm zirconium ball grinding LNMO raw materials in modified preparation technology.Will be obtained LiNi0.5Mn1.5O4/ 2wt%RuCl3The circular negative electrode for button cell, and the electricity of button cell is made in cathode material Solve liquid and use general electrolyte (blank electrolyte).
Under 25 DEG C of normal temperature, by voltage range setting between 3.5V to 5.0V, 0.1C/ is tested using Discharge analysis instrument Discharge capacity under 0.1C, 0.2C/0.2C~0.2C/10C charge/discharge rates.Test result is filled as shown in table 14 and table 15 Discharge curve is respectively as shown in Figure 20 and Figure 21.
Gram capacitance of the table 14 under 0.1C/0.1C charge/discharge rates
Gram capacitance of the table 15 under the different charge/discharge rates of 0.2C/0.2C~0.2C/10C
According to gram capacitance value of table 14 and table 15, the button cell of the present embodiment, using in modified preparation The LiNi ground in technique with 0.1mm zirconiums ball0.5Mn1.5O4/ 2wt%RuCl3Circular negative electrode is made in cathode material；In 0.1C/ Under 0.1C charge/discharge rates, the electric discharge gram capacitance of its first time cycle detection (cycle 1) can of about 132.27mAh/g, Gram capacitance still reaches 133.31mAh/g after the electric discharge of third time cycle detection (cycle 3), and coulombic efficiency is up to 93.45%.
Under 0.2C/0.2C, 0.2C/0.5C, 0.2C/1C, 0.2C/3C, 0.2C/5C and 0.2C/10C charge/discharge rate, Gram capacitance of its second of cycle detection (cycle 2) be respectively 132.23mAh/g, 136.02mAh/g, 134.64mAh/g, 127.41mAh/g, 122.93mAh/g, 112.95mAh/g, average coulombic efficiency can be confirmed according to this up to 91.21~98.50% The button cell of the present embodiment possesses splendid high-speed charging and discharging capabilities and good electrical performance.
Embodiment 8：
Button cell, but LiNi is made in the preparation method of be the same as Example 70.5Mn1.5O4/ 2wt%RuCl3Cathode material exists The zirconium ball grinding LNMO raw materials using sphere diameter 0.3mm are changed in modified preparation technology.
Under 25 DEG C of normal temperature, by voltage range setting between 3.5V to 5.0V, 0.1C/ is tested using Discharge analysis instrument Discharge capacity under 0.1C, 0.2C/0.2C~0.2C/10C charge/discharge rates.Test result is filled as shown in table 16 and table 17 Discharge curve difference is as shown in FIG. 22 and 23.
Gram capacitance of the table 16 under 0.1C/0.1C charge/discharge rates
Gram capacitance of the table 17 under the different charge/discharge rates of 0.2C/0.2C~0.2C/10C
According to gram capacitance value of table 16 and table 17, the button cell of the present embodiment, using in modified preparation The LiNi ground in technique with 0.3mm zirconiums ball0.5Mn1.5O4/ 2wt%RuCl3Circular negative electrode is made in cathode material；In 0.1C/ Under 0.1C charge/discharge rates, the electric discharge gram capacitance of its first time cycle detection (cycle 1) can of about 118.65mAh/g, Gram capacitance still reaches 122.71mAh/g after the electric discharge of third time cycle detection (cycle 3), and coulombic efficiency is up to 93.06%.
Under 0.2C/0.2C, 0.2C/0.5C, 0.2C/1C, 0.2C/3C, 0.2C/5C and 0.2C/10C charge/discharge rate, Gram capacitance of its second of cycle detection (cycle 2) be respectively 125.95mAh/g, 131.64mAh/g, 132.12mAh/g, 128.56mAh/g, 126.66mAh/g and 117.17mAh/g, average coulombic efficiency can be demonstrate,proved according to this up to 90.77~98.02% The button cell of real the present embodiment possesses splendid high-speed charging and discharging capabilities and good electrical performance.
Compared with embodiment 7 in modified preparation technology using 0.1mm zirconiums ball grinding raw material, the button type electricity of embodiment 7 Pond, gram capacitance under 0.1C/0.1C and 0.2C/0.2C~0.2C/10C charge/discharge rates, better than the button of embodiment 8 Type battery.This explanation：Raw material is ground using sphere diameter smaller zirconium ball in modified preparation technology, particle diameter can be made smaller LiNi0.5Mn1.5O4/ 2wt%RuCl3Cathode material (or active material), so that circular negative electrode is made, is more conducive to lifting button Lithium ion (the Li of button-type battery+) spread and electrically transmission.
Embodiment 9：
Button cell made from Example 1 to embodiment 8 is sample, and under 25 DEG C of normal temperature, voltage range is set Between 3.5V to 5.0V, 30 cycle life detections are carried out under 0.1C/0.1C charge/discharge rates using Discharge analysis instrument, are surveyed Test result is as shown in table 18 to table 25, and electrical result collects as shown in figure 24.
Table 18 is at 25 DEG C, and the button cell of embodiment 1 under 0.1C/0.1C charge/discharge rates follow for 30 times Ring life tests
Note：Fading rate=(1 electric discharge gram capacitance of the 30th electric discharge gram capacitance-the)/the 1st electric discharge gram capacitance
Table 19 is at 25 DEG C, and the button cell of embodiment 2 under 0.1C/0.1C charge/discharge rates follow for 30 times Ring life tests
Table 20 is at 25 DEG C, and the button cell of embodiment 3 under 0.1C/0.1C charge/discharge rates follow for 30 times Ring life tests
Table 21 is at 25 DEG C, and the button cell of embodiment 4 is carried out 30 times under 0.1C/0.1C charge/discharge rates Cycle life is detected
Table 22 is at 25 DEG C, and the button cell of embodiment 8 is carried out 30 times under 0.1C/0.1C charge/discharge rates Cycle life is detected
Table 23 is at 25 DEG C, and the button cell of embodiment 7 is carried out 30 times under 0.1C/0.1C charge/discharge rates Cycle life is detected
Table 24 is at 25 DEG C, and the button cell of embodiment 6 is carried out 30 times under 0.1C/0.1C charge/discharge rates Cycle life is detected
Table 25 is at 25 DEG C, and the button cell of embodiment 5 is carried out 30 times under 0.1C/0.1C charge/discharge rates Cycle life is detected
Compared according to fading rate (Fading rate) of the table 18 into table 25, with the embodiment 7 of table 23 Button cell carries out long-term 30 times charge and discharge circulation life detection under 25 DEG C of room temperatures and 0.1C/0.1C charge/discharge rates Electrical performance is optimal, and fading rate only has -0.196%；Secondly, with the electrical of the button cell of the embodiment 5 of table 25 Show as sub-optimal, fading rate only has -1.10%.This explanation, button cell uses spinelle-LNMO (y=0.5) of the invention By Surface coating 2wt%RuCl3The use of electrolyte A is battery electrolyte for positive pole, the use for having extension button cell Life-span effect.
Embodiment 10：
Button cell made from Example 1 to embodiment 8 is sample, and under 25 DEG C of normal temperature, voltage range is set Between 3.5V to 5.0V, 100 cycle life detections, test knot are carried out under 1C/1C charge/discharge rates using Discharge analysis instrument Fruit is as shown in table 26 to table 33, and electrical result collects as shown in figure 25.
Table 26 is at 25 DEG C, and the button cell of embodiment 1 under 1C/1C charge/discharge rates follow for 100 times Ring life tests
Note：Fading rate=(1 electric discharge gram capacitance of the 100th electric discharge gram capacitance-the)/the 1st electric discharge gram capacitance
Table 27 is at 25 DEG C, and the button cell of embodiment 2 under 1C/1C charge/discharge rates follow for 100 times Ring life tests
Table 28 is at 25 DEG C, and the button cell of embodiment 3 under 1C/1C charge/discharge rates follow for 100 times Ring life tests
Table 29 is at 25 DEG C, and the button cell of embodiment 4 under 1C/1C charge/discharge rates follow for 100 times Ring life tests
Table 30 is at 25 DEG C, and the button cell of embodiment 8 carries out 100 circulations under 1C/1C charge/discharge rates Life tests
Table 31 is at 25 DEG C, and the button cell of embodiment 7 under 1C/1C charge/discharge rates follow for 100 times Ring life tests
Table 32 is at 25 DEG C, and the button cell of embodiment 6 under 1C/1C charge/discharge rates follow for 100 times Ring life tests
Table 33 is at 25 DEG C, and the button cell of embodiment 5 under 1C/1C charge/discharge rates follow for 100 times Ring life tests
Compared according to fading rate (Fading rate) of the table 26 into table 33, with the embodiment 5 of table 33 Button cell the electricity of long-term 100 times charge and discharge circulation life detection is carried out under 25 DEG C of room temperatures and 1C/1C charge/discharge rates Sex expression is optimal, and fading rate only has -1.76%；Secondly, with the electrical performance of the button cell of the embodiment 6 of table 32 To be sub-optimal, fading rate only has -2.93%.This explanation, button cell is using the spinelle-LNMO (y=0.5) of the present invention for just Pole, is battery electrolyte, the effect also increased the service life with promotion with the use of electrolyte A.
Embodiment 11：
Example 3, embodiment 4, embodiment 5 and button cell made from embodiment 7 are sample, in 55 DEG C of high temperature Under, by voltage range setting between 3.5V to 5.0V, 30 are carried out under 0.1C/0.1C charge/discharge rates using Discharge analysis instrument Secondary cycle life detection, test result is as shown in table 34 to table 37, and electrical result collects as shown in figure 26.
Table 34 is at 55 DEG C, and the button cell of embodiment 3 is carried out 30 times under 0.1C/0.1C charge/discharge rates Cycle life is detected
Note：Fading rate=(1 electric discharge gram capacitance of the 30th electric discharge gram capacitance-the)/the 1st electric discharge gram capacitance
Table 35 is at 55 DEG C, and the button cell of embodiment 4 is carried out 30 times under 0.1C/0.1C charge/discharge rates Cycle life is detected
Table 36 is at 55 DEG C, and the button cell of embodiment 5 is carried out 30 times under 0.1C/0.1C charge/discharge rates Cycle life is detected
Table 37 is at 55 DEG C, and the button cell of embodiment 7 is carried out 30 times under 0.1C/0.1C charge/discharge rates Cycle life is detected
Compared according to fading rate (Fading rate) of the table 34 into table 37, with the embodiment 7 of table 37 Button cell the detection of long-term 30 times charge and discharge circulation life is carried out under 55 DEG C of high temperature and 0.1C/0.1C charge/discharge rates Electrical performance be optimal, fading rate only has -0.202%；Secondly, with the electricity of the button cell of the embodiment 4 of table 35 Sex expression is sub-optimal, and fading rate is -9.57%.This explanation, button cell uses spinelle-LNMO (y=0.5) of the invention By Surface coating 2wt%RuCl3For positive pole, not only it is adapted under 55 DEG C of high temperature using outer, also with splendid service life.
Embodiment 12：
Example 3, embodiment 4, embodiment 5 and button cell made from embodiment 7 are sample, in 55 DEG C of high temperature Under, by voltage range setting between 3.5V to 5.0V, under 1C/1C charge/discharge rates follow for 100 times using Discharge analysis instrument Ring life tests, test result such as table 38 shows that electrical result collects as shown in figure 27 to table No. 41 Institute.
Table 38 is at 55 DEG C, and the button cell of embodiment 3 under 1C/1C charge/discharge rates follow for 100 times Ring life tests
Note：Fading rate=(1 electric discharge gram capacitance of the 100th electric discharge gram capacitance-the)/the 1st electric discharge gram capacitance
Table 39 is at 55 DEG C, and the button cell of embodiment 4 under 1C/1C charge/discharge rates follow for 100 times Ring life tests
Table 40 is at 55 DEG C, and the button cell of embodiment 5 carries out 100 circulations under 1C/1C charge/discharge rates Life tests
Table 41 is at 55 DEG C, and the button cell of embodiment 7 under 1C/1C charge/discharge rates follow for 100 times Ring life tests
Compared according to fading rate (Fading rate) of the table 38 into table 41, with the embodiment 4 of table 39 Button cell the electricity of long-term 100 times charge and discharge circulation life detection is carried out under 55 DEG C of room temperatures and 1C/1C charge/discharge rates Sex expression is optimal, and fading rate only has -1.31%；Secondly, with the electrical performance of the button cell of the embodiment 7 of table 41 To be sub-optimal, fading rate is -12.83%.This explanation, button cell is passed through using the spinelle-LNMO (y=0.5) of the present invention Surface coating 1wt%LATP is positive pole, is not only adapted under 55 DEG C of high temperature using outer, also with the effect increased the service life.

Claims (10)

1. a kind of manufacture method for the lithium nickel manganese cathode material for having spinel structure, it comprises the following steps：
1) selection lithium source, nickel source and manganese source are raw material；Wherein, lithium source:Nickel source:The mol ratio of manganese source is 1:y:2-y, and 0<y<1；
2) be based on step 1) raw material gross weight, selection usage amount between 1~80wt% chelating；Wherein, the chelating Selected from citric acid (CA), adipic acid, ascorbic acid, ethylenediamine tetra-acetic acid (EDTA), stearic acid (SA), oxalic acid, laurate, poly- second Alkene Pyrrolizidine (PVP), polyvinyl alcohol (PVA) or one kind in furans or their mixing；
3) lithium source of selection, nickel source, four kinds of raw materials of manganese source and chelating are directly done into solid phase mixing formation lithium nickel manganese cathode material Predecessor；
4) one or more in following modified preparation technology are carried out to lithium nickel manganese cathode material predecessor；
A) mill ball or zirconium ball from sphere diameter size between 0.1~0.3mm carry out fine grinding or Ultrafine Grinding lithium nickel manganese cathode material Predecessor；
B) be based on step 1) raw material gross weight, selection usage amount between 1~80wt% carbon source and/or conductive carbon material, to lithium The surface of nickel manganese cathode material predecessor carries out cladding carbon-coating and is modified；
C) last layer modified layer is coated with to the surface of lithium nickel manganese cathode material predecessor；The coating amount of the modified layer, based on step Rapid raw material gross weight 1), between 0.1~20wt%；
D) adulterate one or more of selected cations to lithium nickel manganese cathode material predecessor；The blended amount of the cation, is situated between In 0.01~20mol%；
5) step 4 will be passed through) the lithium nickel manganese cathode material predecessor of modified preparation technology inserts high temperature furnace, in atmosphere or it is passed through In the environment of purity oxygen, first stage calcining heat treatment is carried out at 800~1000 DEG C of calcining heat, through lasting heat treatment 5~ After 25 hours, it is cooled at 500~700 DEG C, second stage calcining heat treatment is carried out in atmosphere, 5~25 are heat-treated through constant temperature After hour, treat that high temperature furnace is down to room temperature, that is, it is LiNi that molecular formula, which is made,yMn2-yO4And 0<y<The lithium nickel manganese of 1 tool spinel structure Cathode material.
2. manufacture method as claimed in claim 1, wherein, the material of the modified layer, selected from lithium titanate, lithium phosphate aluminium titanium, Lithium titanate lanthanum, ruthenic chloride, binary stratiform nickel ion doped, cobalt acid lithium, layered LiMnO, LiFePO4, phosphoric acid vanadium lithium, ferric phosphate, 111 ternary materials, 424 ternary materials or one kind in 523 ternary materials or their mixing.
3. manufacture method as claimed in claim 1, wherein, for what is be doped to the lithium nickel manganese cathode material predecessor Cation, wherein one in alkali metal, alkali earth metal, the 3rd race's element, transition metal and rare earth element Plant or a variety of cations.
4. manufacture method as claimed in claim 1, wherein, for what is be doped to the lithium nickel manganese cathode material predecessor Cation, selected from Ru4+、Mn2+、Mg2+、Al3+、Ti4+、Zr4+、Nb5+Or W+6Cation.
5. a kind of manufacture method for the lithium nickel manganese cathode material for having spinel structure, it comprises the following steps：
1) selection lithium source, nickel source and manganese source are raw material；Wherein, lithium source:Nickel source:The mol ratio of manganese source is 1:y:2-y, and 0<y<1；
2) be based on step 1) raw material gross weight, selection usage amount between 1~80wt% chelating；Wherein, the chelating Selected from citric acid (CA), adipic acid, ascorbic acid, ethylenediamine tetra-acetic acid (EDTA), stearic acid (SA), oxalic acid, laurate, poly- second Alkene Pyrrolizidine (PVP), polyvinyl alcohol (PVA) or one kind in furans or their mixing；
3) lithium source of selection, nickel source, four kinds of raw materials of manganese source and chelating are directly done into solid phase mixing formation lithium nickel manganese cathode material Predecessor；
4) take step 3) lithium nickel manganese cathode material predecessor directly do liquid phase with carbon source and/or conductive carbon material and mix；
5) the sphere structure lithium nickel manganese cathode material predecessor that spray drying forms cladding carbon source is bestowed；
6) by step 5) lithium nickel manganese cathode material predecessor insert high temperature furnace, in atmosphere or be passed through in the environment of purity oxygen, First stage calcining heat treatment is carried out at 800~1000 DEG C of calcining heat, after lasting heat treatment 5~25 hours, is cooled to At 500~700 DEG C, second stage calcining heat treatment is carried out in atmosphere, after being heat-treated 5~25 hours through constant temperature, high temperature furnace is treated Room temperature is down to, that is, it is LiNi that molecular formula, which is made,yMn2-yO4And 0<y<The lithium nickel manganese cathode material of 1 tool sphere structure.
6. the manufacture method as described in claim 1 or 5, wherein, carrying out step 5) before lasting calcining heat treatment, to inserting The lithium nickel manganese predecessor of high temperature furnace first carries out pre-burning heat treatment, in nitrogen (N2) or argon gas (Ar) atmosphere in, temperature 400~ It is heat-treated 1~20 hour at 550 DEG C, the moisture content and small molecule of predecessor is removed.
7. the manufacture method as described in claim 1 or 5, wherein, the lithium source is selected from lithium hydroxide, lithium nitrate, lithium acetate, chlorine Change lithium, lithium hydrogen phosphate, lithium phosphate, lithium carbonate or one kind in lithium bicarbonate or their mixing；The nickel source be selected from nickel sulfate, One kind or their mixing in nickel oxalate, nickel acetate, nickel nitrate, nickel chloride or nickel hydroxide；The manganese source be selected from manganese oxalate, One kind in manganese carbonate, manganese citrate, manganese sulfate, manganese acetate, manganese nitrate, manganese phosphate, electrolytic manganese dioxide or manganese oxide or it Mixing.
8. the manufacture method as described in claim 1 or 5, wherein, the carbon source, selected from citric acid, sucrose, glucose, starch, Furane resins, polyvinyl alcohol, polystyrene, the one or more of which of polystyrene spheres or methyl methacrylate ball；It is described to lead Electrical carbon material, selected from Super P conductive carbon materials, carbon ball conductive carbon material, carbon black conductive carbon materials, graphene conductive carbon materials, CNT One or more in carbon materials, electrographite, synthetic graphite or carbonaceous mesophase spherules.
9. the manufacture method as described in claim 1 or 5, wherein, obtained lithium nickel manganese cathode material, molecular formula is LiNiyMn2-yO4, and y=0.4,0.5 or 0.6.
10. a kind of cathode electrode of lithium rechargeable battery, lithium nickel manganese cathode material made from usage right requirement 9 is made.
CN201710385994.7A 2017-05-26 2017-05-26 A kind of manufacture method of lithium nickel manganese cathode material for having spinel structure and application thereof Pending CN107316991A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710385994.7A CN107316991A (en) 2017-05-26 2017-05-26 A kind of manufacture method of lithium nickel manganese cathode material for having spinel structure and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710385994.7A CN107316991A (en) 2017-05-26 2017-05-26 A kind of manufacture method of lithium nickel manganese cathode material for having spinel structure and application thereof

Publications (1)

Publication Number Publication Date
CN107316991A true CN107316991A (en) 2017-11-03

Family

ID=60181467

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710385994.7A Pending CN107316991A (en) 2017-05-26 2017-05-26 A kind of manufacture method of lithium nickel manganese cathode material for having spinel structure and application thereof

Country Status (1)

Country Link
CN (1) CN107316991A (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109678216A (en) * 2018-12-12 2019-04-26 无锡晶石新型能源股份有限公司 A kind of preparation method of nickel ion doped material
CN109713283A (en) * 2018-12-29 2019-05-03 江苏特丰新材料科技有限公司 The lithium titanate composite material and preparation method thereof of phosphorus aluminium cladding
CN110380054A (en) * 2019-08-02 2019-10-25 北方奥钛纳米技术有限公司 A kind of titanium niobium oxide electrode material and preparation method thereof, lithium ion button shape cell
CN110662315A (en) * 2019-08-28 2020-01-07 大同新成新材料股份有限公司 Processing method of carbon fiber heating pad
CN111370682A (en) * 2020-03-26 2020-07-03 四川青源新材料有限公司 Lithium ion battery anode material precursor, anode material and preparation method
CN112736227A (en) * 2020-12-29 2021-04-30 天津国安盟固利新材料科技股份有限公司 Composite cathode and secondary battery using the same
CN113517437A (en) * 2021-07-14 2021-10-19 中国石油大学(北京) Cation modified spinel type lithium nickel manganese oxide and preparation method and application thereof
CN114430037A (en) * 2022-04-06 2022-05-03 比亚迪股份有限公司 Cathode material and application thereof
CN114566646A (en) * 2022-01-28 2022-05-31 上海兰钧新能源科技有限公司 Nickel-doped lithium manganese iron phosphate positive electrode material and preparation method and application thereof
US11539046B2 (en) 2019-12-27 2022-12-27 Industrial Technology Research Institute Ion-conducting material, core-shell structure containing the same, electrode prepared with the core-shell structure and metal-ion battery employing the electrode
WO2023283168A1 (en) * 2021-07-06 2023-01-12 33 Tech, Inc. Lithium-rich nickel manganese oxide battery cathode materials and methods

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102683709A (en) * 2012-05-22 2012-09-19 吉首大学 Surface coverage method for high-voltage nickel manganese acid lithium anode material
CN102931395A (en) * 2012-11-27 2013-02-13 中国科学院新疆理化技术研究所 Method for preparing nickel lithium manganate serving as cathode material of lithium ion battery
CN103094552A (en) * 2012-10-12 2013-05-08 合肥国轩高科动力能源股份公司 Surface coating method of 5V lithium ion battery positive pole material LiNi0.5-xMn1.5MxO4
CN104766970A (en) * 2015-04-28 2015-07-08 湖南瑞翔新材料股份有限公司 Synthetic method for lithium nickel manganese oxygen covered with lithium titanate
CN106684346A (en) * 2016-12-13 2017-05-17 苏州宇量电池有限公司 Carbon coating method suitable for preparing electrode material by spray drying method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102683709A (en) * 2012-05-22 2012-09-19 吉首大学 Surface coverage method for high-voltage nickel manganese acid lithium anode material
CN103094552A (en) * 2012-10-12 2013-05-08 合肥国轩高科动力能源股份公司 Surface coating method of 5V lithium ion battery positive pole material LiNi0.5-xMn1.5MxO4
CN102931395A (en) * 2012-11-27 2013-02-13 中国科学院新疆理化技术研究所 Method for preparing nickel lithium manganate serving as cathode material of lithium ion battery
CN104766970A (en) * 2015-04-28 2015-07-08 湖南瑞翔新材料股份有限公司 Synthetic method for lithium nickel manganese oxygen covered with lithium titanate
CN106684346A (en) * 2016-12-13 2017-05-17 苏州宇量电池有限公司 Carbon coating method suitable for preparing electrode material by spray drying method

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109678216A (en) * 2018-12-12 2019-04-26 无锡晶石新型能源股份有限公司 A kind of preparation method of nickel ion doped material
CN109713283A (en) * 2018-12-29 2019-05-03 江苏特丰新材料科技有限公司 The lithium titanate composite material and preparation method thereof of phosphorus aluminium cladding
CN110380054A (en) * 2019-08-02 2019-10-25 北方奥钛纳米技术有限公司 A kind of titanium niobium oxide electrode material and preparation method thereof, lithium ion button shape cell
CN110662315A (en) * 2019-08-28 2020-01-07 大同新成新材料股份有限公司 Processing method of carbon fiber heating pad
US11539046B2 (en) 2019-12-27 2022-12-27 Industrial Technology Research Institute Ion-conducting material, core-shell structure containing the same, electrode prepared with the core-shell structure and metal-ion battery employing the electrode
CN111370682A (en) * 2020-03-26 2020-07-03 四川青源新材料有限公司 Lithium ion battery anode material precursor, anode material and preparation method
CN112736227A (en) * 2020-12-29 2021-04-30 天津国安盟固利新材料科技股份有限公司 Composite cathode and secondary battery using the same
WO2023283168A1 (en) * 2021-07-06 2023-01-12 33 Tech, Inc. Lithium-rich nickel manganese oxide battery cathode materials and methods
CN113517437A (en) * 2021-07-14 2021-10-19 中国石油大学(北京) Cation modified spinel type lithium nickel manganese oxide and preparation method and application thereof
CN114566646A (en) * 2022-01-28 2022-05-31 上海兰钧新能源科技有限公司 Nickel-doped lithium manganese iron phosphate positive electrode material and preparation method and application thereof
CN114566646B (en) * 2022-01-28 2024-01-16 上海兰钧新能源科技有限公司 Nickel-doped lithium iron manganese phosphate positive electrode material and preparation method and application thereof
CN114430037A (en) * 2022-04-06 2022-05-03 比亚迪股份有限公司 Cathode material and application thereof

Similar Documents

Publication Publication Date Title
CN107316991A (en) A kind of manufacture method of lithium nickel manganese cathode material for having spinel structure and application thereof
CN111554919B (en) Positive electrode active material, preparation method thereof and sodium ion battery
CN109461928A (en) A kind of high-energy density polynary positive pole material and preparation method thereof
CN108140820A (en) Cathode active material for lithium secondary battery and preparation method thereof
CN107845781B (en) Negative electrode active material for lithium ion secondary battery, method for producing same, and lithium ion secondary battery
CN109461927A (en) A kind of compound nickel-cobalt-manganese multi positive electrode of high magnification and preparation method thereof
CN107863514A (en) 622 type nickel-cobalt-manganternary ternary anode materials and preparation method thereof are covered in double-contracting
JP2002279985A (en) Positive electrode active material for non-aqueous lithium secondary battery and the non-aqueous lithium secondary battery using the active material
KR20070103023A (en) Method for producing lithium containing complex oxide for positive electrode of lithium secondary battery
KR20140101915A (en) Manufacturing method of cathode complex material for lithium batteries and manufacturing method of electrode of lithium batteries using the cathode complex material, and charge and discharge method of the the lithium batteries
TWI513084B (en) Process for producing lfmp/c composite material and use the same
CN108432001A (en) Manufacturing method, positive active material, anode and the lithium rechargeable battery of positive active material
CN104681808A (en) Method for preparing strontium salt doped lithium nickel manganese oxide cathode material of lithium ion battery
CN115207340A (en) Sodium ion battery layered oxide positive electrode material and preparation method and application thereof
TWI651272B (en) Process for producing lr-lnmo composite materials and use the same
CN113845152A (en) Lithium nickel manganese oxide positive electrode material, preparation method thereof and lithium ion battery
CN108511749A (en) Copper doped lithium nickelate positive electrode and preparation method thereof and lithium ion battery
JP4628704B2 (en) Positive electrode material for lithium secondary battery and method for producing the same
JP2012166966A (en) B type titanium oxide and method of manufacturing the same, and lithium ion battery using the same
Lin et al. Preparation and electrochemical properties of Li [Ni1/3Co1/3Mn1− x/3Zrx/3] O2 cathode materials for Li-ion batteries
CN108511697A (en) Cupro-nickel acid lithium anode material and preparation method thereof and lithium ion battery
CN1581561A (en) Lithium ion secondary cell and method for preparing anode thereof
CN110190277A (en) A kind of anode material for lithium-ion batteries LiMnO2@C and preparation method thereof
CN111233052A (en) Nickel cobalt lithium manganate ternary positive electrode material, preparation method thereof, positive electrode and battery
CN105977475A (en) Cathodematerial for high-capacity lithium ion battery as well as preparation method and application of cathode material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20171103