CN105932250A - Preparation method and application of metal doped spinel structured and fast ionic conductor coated nickel-containing cathode material - Google Patents
Preparation method and application of metal doped spinel structured and fast ionic conductor coated nickel-containing cathode material Download PDFInfo
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention discloses a preparation method and application of a metal doped spinel structured and fast ionic conductor coated nickel-containing cathode material. The preparation method comprises the following steps of: dissolving and mixing organic titanium salt, a nickel-containing cathode material and doped metal salt so as to obtain dispersion liquid; transferring the dispersion liquid into a hydrothermal reaction kettle to perform hydrothermal reaction, such that a precursor is obtained; and roasting the precursor at high temperature so as to obtain the nickel-containing cathode material of a metal doped spinel structured and fast ionic conductor coated layer, which is dense, uniform and good in stability and ionic conductivity. The nickel-containing cathode material can be used for preparing a lithium ion battery having excellent cycle performance and rate capability; and the preparation method of the cathode material has the characteristics of being low in cost, simple to operate, environment-friendly and the like, and can be applied to industrial production.
Description
Technical field
The present invention relates to a kind of modification lithium-ion battery anode material, be specifically related to a kind of metal-doped spinel structure fast-ionic conductor and be coated with the preparation method of nickeliferous positive electrode and the application in preparing lithium ion battery thereof, belong to field of lithium ion battery.
Background technology
Nowadays, mobile electronic device, such as smart mobile phone, digital camera, notebook computer, and electric automobile and developing rapidly of hybrid vehicle promote advancing by leaps and bounds of lithium rechargeable battery technology.But, current anode material for lithium-ion batteries, such as cobalt acid lithium, spinel lithium manganate, LiFePO4, all there is the shortcoming that cycle life is low, it is impossible to enough meet the requirement of following pure electrical equipment.Therefore, study and develop and a kind of there is high cycle life and powerful positive electrode becomes the common objective of whole world research worker.
Coating modification is the material using a kind of physical and chemical performance excellent, forms the guard method of one layer of uniform clad at target material particle surface.Research worker utilizes fast-ionic conductor to be coated with positive electrode, and result shows, the positive electrode of fast-ionic conductor coating modification has preferable high rate performance and cycle performance.But, in traditional method for coating, the preparation process of fast-ionic conductor has the shortcoming that operation is complicated and cost is high, is difficulty with large-scale industrialization and produces.Therefore, finding a kind of simple to operate, low cost and eco-friendly preparation method are imperative.
Summary of the invention
The defect existed for prior art, it is an object of the invention to the preparation method being to provide a kind of nickeliferous positive electrode of modification with the good metal-doped spinel structure fast-ionic conductor clad of even compact, stability height and ionic conductivity, this preparation method has simple to operate, low cost, advantages of environment protection, beneficially large-scale application is in commercial production.
Present invention also offers the cladding nickeliferous positive electrode application in preparing lithium ion battery of a kind of described metal-doped spinel structure fast-ionic conductor, lithium ion battery high rate performance and cycle life can be effectively improved.
The invention provides a kind of metal-doped spinel structure fast-ionic conductor and be coated with the preparation method of nickeliferous positive electrode, the method is by the dissolving of organic titanium salt, nickeliferous positive electrode and doped metal salt, mixing, obtains dispersion liquid；Described dispersion liquid proceeds in hydrothermal reaction kettle, carries out hydro-thermal reaction, obtain presoma at a temperature of 80 DEG C～160 DEG C；Described presoma is placed in 500 DEG C～900 DEG C of temperature lower calcinations, to obtain final product.
Preferably scheme, the quality of organic titanium salt and doped metal salt is the 0.5%～10.0% of nickeliferous positive electrode quality to ensure the metal-doped spinel structure fast-ionic conductor quality generated.
Preferably scheme, the mass ratio of organic titanium salt and doped metal salt is with the mol ratio of titanium elements in metallic element in doped metal salt and organic titanium salt for (0.1～10): 100 meterings.
More preferably scheme, nickeliferous positive electrode is: have the LiNi of spinel structurexMn2-xO4(0.1 < x < 0.8), and/or there is the LiNi of layer structure1-x-yCoxMnyO2(0 < x < 0.5,0 < y < 0.5), and/or rich lithium manganese anode material xLi2MnO3·(1-x)LiMO2, (0.1 < x < 0.9, M=Ni, in Co, Mn at least one).
More preferably scheme, doped metal salt is at least one in the soluble metallic salt containing aluminum, cerium, chromium, vanadium, ferrum, stannum or zinc.
More preferably scheme, organic titanium salt is isopropyl titanate.
Preferably scheme, the hydro-thermal reaction time is 5.0h～36h.
Preferably scheme, calcination time is 2.0h～12h.
Preferably scheme, joins organic titanium salt alcohols solvent, stirring or ultrasonic disperse 0.1h～2.0h, is heated to 50 DEG C～80 DEG C, adds nickeliferous positive electrode, dispersed with stirring, add doped metal salt, dispersed with stirring 0.5h～5.0h, obtain dispersion liquid.
Present invention also offers the cladding nickeliferous positive electrode application in lithium ion battery of a kind of metal-doped spinel structure fast-ionic conductor, be applied to prepare lithium ion battery by the metal-doped spinel structure fast-ionic conductor nickeliferous positive electrode of cladding.
Preferably scheme, after being mixed with conductive agent and binding agent by the described metal-doped spinel structure fast-ionic conductor nickeliferous positive electrode of cladding, is coated in foil substrate by rubbing method, makes lithium ion cell positive.
Technical scheme it is critical only that by chemical method at LiTi2O4Fast-ionic conductor is doped with metallic element, makes LiTi simultaneously2O4Fast-ionic conductor clad is more uniform, fine and close, stable, can effectively protect positive electrode from the corrosion of electrolyte, and metal ion mixing further improves LiTi simultaneously2O4Ionic conductivity.Technical scheme makes full use of the feature of nickeliferous positive electrode remained on surface lithium salts impurity, only need to add organic titanium salt and doped metal salt, combine high-temperature calcination technique by hydro-thermal reaction and can prepare metal-doped spinel structure fast-ionic conductor clad on nickeliferous positive electrode surface, lithium salts and alkalescence chelating agent is added without secondary, with low cost, beneficially environmental protection.The metal-doped spinel structure nickeliferous positive electrode of fast-ionic conductor coating modification of preparation can improve high rate performance and the cycle life of lithium ion battery effectively.
The method preparing the metal-doped spinel structure nickeliferous positive electrode of fast-ionic conductor coating modification of the present invention includes step in detail below:
1) addition of isopropyl titanate is according to 0.5%～10.0% metering that metal-doped spinel structure fast-ionic conductor clad quality is nickeliferous positive electrode quality；Being sufficiently dispersed in dehydrated alcohol by mechanical mixing method or ultrasonic method by isopropyl titanate, stirring or ultrasonic time are 0.1h～2.0h, obtain isopropyl titanate dispersion liquid；
2) by step 1) in isopropyl titanate dispersion liquid, be placed in water-bath after being heated between 50 DEG C～80 DEG C, by the LiNi of nickeliferous spinel structurexMn2-xO4(0.1 < x < 0.8), and/or the LiNi of nickeliferous layer structure1-x-yCoxMnyO2(0 < x < 0.5,0 < y < 0.5),
And/or richness lithium manganese anode material xLi2MnO3·(1-x)LiMO2, (0.1 < x < at least one in 0.9, M=Ni, Co, Mn) adds to isopropyl titanate dispersion liquid, and dispersed with stirring；
3) 0.1%～10% metering being titanium atom mole with doped metallic elements mole, soluble-salt containing at least one doping metals in aluminum, cerium, chromium, vanadium, ferrum, stannum, zinc is dissolved in deionized water, and add to step 2) in isopropyl titanate dispersion liquid in, and to maintain temperature be 50 DEG C～80 DEG C, continuously stirred 0.5h～5.0h；
4) by step 3) in the mixed solution that obtains, proceed in hydrothermal reaction kettle, at a temperature of 80 DEG C～160 DEG C, be incubated 5h～36h, naturally cool to room temperature, after obtained precipitate washing and filtering, dry at 60 DEG C～80 DEG C and obtain presoma；
5) by step 4) in the presoma that obtains proceed in Muffle furnace, between 500 DEG C～900 DEG C, be incubated 5h～20h, naturally cool to room temperature, finally give metal-doped spinel structure fast-ionic conductor coated lithium ion battery positive electrode.
The metal-doped modified spinelle structure nickeliferous positive electrode of fast-ionic conductor coating modification that the present invention prepares is for the method preparing lithium ion cell positive: metal-doped spinel structure fast-ionic conductor is coated with nickeliferous positive electrode and conductive agent (conductive black) and binding agent (PVDF) and NMP is ground on a small quantity is thoroughly mixed to form uniform pastel, it is coated in foil substrate as test electrode, making button cell using lithium metal as to electrode, its electrolyte is 1M LiPF6/ EC:DMC (V:V=1:1).
Hinge structure, the Advantageous Effects that technical scheme is brought:
1, technical scheme makes full use of nickeliferous positive electrode surface residual lithium salts, with organic titanium salt as base stock, doped metal salt simultaneously, combine high-temperature calcination technique by hydro-thermal reaction, the most successfully synthesize a kind of metal-doped spinel structure nickeliferous positive electrode of fast-ionic conductor coating modification.The method operating process is simple, reproducible, it is not necessary to secondary adds lithium salts, with low cost, and avoids using alkalescence chelating agent, environmentally friendly, beneficially large-scale industrial production.
2, the metal-doped spinel structure fast-ionic conductor that prepared by technical scheme is coated with nickeliferous positive electrode, fast-ionic conductor clad is carried out doped with metal elements modified, further increased ionic conductivity and the electron conduction of fast-ionic conductor clad.
3, combined by " bridged bond " of lithium ion between metal-doped spinel structure fast-ionic conductor clad and the nickeliferous positive electrode in the metal-doped spinel structure nickeliferous positive electrode of fast-ionic conductor coating modification of the present invention, there is extraordinary stability.Lithium salts mainly due to nickeliferous positive electrode surface residual is being formed during metal-doped spinel structure fast-ionic conductor clad, and there is chemical bond between nickeliferous positive electrode and metal-doped spinel structure fast-ionic conductor simultaneously.
4, the metal-doped spinel structure fast-ionic conductor clad dense uniform in the metal-doped spinel structure nickeliferous positive electrode of fast-ionic conductor coating modification of the present invention, good stability, can effectively prevent positive active material and electrolyte solution contacts and loss by dissolution, substantially prolongs the cycle life of battery.
5, the metal-doped spinel structure nickeliferous positive electrode of fast-ionic conductor coating modification of the present invention is used for lithium ion battery, shows excellent cycle performance and preferable high rate performance.
Accompanying drawing explanation
[Fig. 1] is the LiNi in embodiment 1 before coating modification0.8Co0.1Mn0.1O2Positive electrode scanning electron microscope (SEM) photograph (SEM).
[Fig. 2] is the LiNi in embodiment 1 after the coating modification of spinelle fast-ionic conductor0.8Co0.1Mn0.1O2Positive electrode scanning electron microscope (SEM) photograph (SEM).
[Fig. 3] is the LiNi without coating modification0.8Co0.1Mn0.1O2The LiAl that positive electrode and embodiment 1 prepare0.1Ti1.9O4LiNi after coating modification0.8Co0.1Mn0.1O2100 cycle performance curve charts of positive electrode.
Detailed description of the invention
Following example are intended to be described in further details present invention, and the protection domain of the claims in the present invention is not limited by the example.
Embodiment 1
(1) according to LiAl0.1Ti1.9O4Fast-ionic conductor is 0.5% quantitative isopropyl titanate to utilize mechanical mixing method or ultrasonic method disperse 0.5h in dehydrated alcohol fully relative to the cladding mass percent of positive electrode.
(2) by the isopropyl titanate dispersion liquid in step (1) at 80 DEG C of heating in water bath, by the LiNi of layer structure0.8Co0.1Mn0.1O2Positive electrode adds to isopropyl titanate dispersion liquid, and dispersed with stirring 0.5h.
(3) according to 1.4% aluminiferous metals salt being dissolved in deionized water of atomic percentage conc of fast-ionic conductor shared by doped metallic elements, and in the isopropyl titanate dispersion liquid added to step (2), and continuously stirred 1.0h.
(4) mixture obtained in step (3) is added to reactor, air dry oven is incubated at 80 DEG C 24h, naturally cools to room temperature, obtain presoma by drying at 60 DEG C after obtained precipitate washing and filtering.
(5) presoma obtained in step (4) is proceeded in Muffle furnace, be incubated 5h at 700 DEG C, naturally cool to room temperature, finally give LiAl0.1Ti1.9O4The LiNi of spinel structure fast-ionic conductor coating modification0.8Co0.1Mn0.1O2Positive electrode.
(6) the above-mentioned prepared LiAl of 0.48g is weighed0.1Ti1.9O4The LiNi of spinel structure fast-ionic conductor coating modification0.8Co0.1Mn0.1O2Positive electrode, addition 0.05g conductive black is as conductive agent, and 0.05g PVDF is as binding agent, add that a small amount of NMP is ground is thoroughly mixed to form uniform pastel, being coated in foil substrate as test electrode, make button cell using lithium metal as to electrode, its electrolyte is 1M LiPF6/ EC:DMC (V:V=1:1), test charge-discharge magnification is 1C.
Use LiAl prepared by the present embodiment0.1Ti1.9O4Coating modification LiNi0.8Co0.1Mn0.1O2Positive electrode, its material characterization and chemical property as shown in Figures 1 to 3:
Fig. 1 can be seen that the LiNi without coating modification0.8Co0.1Mn0.1O2The spherical structure that positive electrode is made up of the primary particle of a size of 200～500nm, smooth surface.
Fig. 2 can be seen that through LiAl0.1Ti1.9O4LiNi after coating modification0.8Co0.1Mn0.1O2Positive electrode particle surface has the lamellar clad being evenly distributed.
Fig. 3 shows use LiAl0.1Ti1.9O4LiNi after coating modification0.8Co0.1Mn0.1O2The electrode that positive electrode is made, at room temperature under 1C multiplying power during constant-current discharge, after circulating 100 times, specific capacity may remain in 188mAh/g；Show good cycle performance.
Embodiment 2
(1) according to LiCe0.05Ti1.95O4Fast-ionic conductor is 1.5% quantitative isopropyl titanate to utilize mechanical mixing method or ultrasonic method disperse 0.2h in dehydrated alcohol fully relative to the cladding mass percent of positive electrode.
(2) by the isopropyl titanate dispersion liquid in step (1) at 50 DEG C of heating in water bath, by the LiNi of layer structure0.85Co0.05Mn0.1O2Positive electrode adds to isopropyl titanate dispersion liquid, and dispersed with stirring 0.8h.
(3) according to 0.7% the containing ce metal salt and be dissolved in deionized water of atomic percentage conc of fast-ionic conductor shared by doped metallic elements, and in the isopropyl titanate dispersion liquid added to step (2), and continuously stirred 1.5h.
(4) mixture obtained in step (3) is added to reactor, air dry oven is incubated at 120 DEG C 48h, naturally cools to room temperature, obtain presoma by drying at 60 DEG C after obtained precipitate washing and filtering.
(5) presoma obtained in step (4) is proceeded in Muffle furnace, be incubated 8h at 800 DEG C, naturally cool to room temperature, finally give LiCe0.05Ti1.95O4The LiNi of spinel structure fast-ionic conductor coating modification0.85Co0.05Mn0.1O2Positive electrode.
(6) the above-mentioned prepared LiCe of 0.48g is weighed0.05Ti1.95O4The LiNi of spinel structure fast-ionic conductor coating modification0.85Co0.05Mn0.1O2Positive electrode, addition 0.05g conductive black is as conductive agent, and 0.05g PVDF is as binding agent, add that a small amount of NMP is ground is thoroughly mixed to form uniform pastel, being coated in foil substrate as test electrode, make button cell using lithium metal as to electrode, its electrolyte is 1M LiPF6/ EC:DMC (V:V=1:1), test charging and discharging currents density is 1C.
Use LiCe prepared by the present embodiment0.05Ti1.95O4LiNi after coating modification0.85Co0.05Mn0.1O2Positive electrode is prepared electrode and is assembled into button cell with metal lithium sheet, and at room temperature during 1C constant-current discharge, after circulating 100 times, specific capacity may remain in 189mAh/g, shows good cycle performance.
Embodiment 3
(1) according to LiV0.15Ti1.85O4Fast-ionic conductor is 2.0% quantitative isopropyl titanate to utilize mechanical mixing method or ultrasonic method disperse 1.5h in dehydrated alcohol fully relative to the cladding mass percent of positive electrode.
(2) by the isopropyl titanate dispersion liquid in step (1) at 50 DEG C of heating in water bath, by the LiNi of layer structure0.5Co0.2Mn0.3O2Positive electrode adds to isopropyl titanate dispersion liquid, and dispersed with stirring 4.0h.
(3) according to 2.0% the containing vanadium metal salt and be dissolved in deionized water of atomic percentage conc of fast-ionic conductor shared by doped metallic elements, and in the isopropyl titanate dispersion liquid added to step (2), and continuously stirred 1.0h.
(4) mixture obtained in step (3) is added to reactor, air dry oven is incubated at 140 DEG C 36h, naturally cools to room temperature, obtain presoma by drying at 60 DEG C after obtained precipitate washing and filtering.
(5) presoma obtained in step (4) is proceeded in Muffle furnace, be incubated 12h at 900 DEG C, naturally cool to room temperature, finally give LiV0.15Ti1.85O4The LiNi of spinel structure fast-ionic conductor coating modification0.5Co0.2Mn0.3O2Positive electrode.
(6) the above-mentioned prepared LiV of 0.48g is weighed0.15Ti1.85O4The LiNi of spinel structure fast-ionic conductor coating modification0.5Co0.2Mn0.3O2Positive electrode, addition 0.05g conductive black is as conductive agent, and 0.05g PVDF is as binding agent, add that a small amount of NMP is ground is thoroughly mixed to form uniform pastel, being coated in foil substrate as test electrode, make button cell using lithium metal as to electrode, its electrolyte is 1M LiPF6/ EC:DMC (V:V=1:1), test charging and discharging currents density is 1C.
Use LiV prepared by the present embodiment0.15Ti1.85O4LiNi after coating modification0.5Co0.2Mn0.3O2Positive electrode is prepared electrode and is assembled into button cell with metal lithium sheet, and at room temperature during 1C constant-current discharge, after circulating 100 times, specific capacity may remain in 185mAh/g, shows good cycle performance.
Embodiment 4
(1) according to LiFe0.2Ti1.8O4Fast-ionic conductor is 10% quantitative isopropyl titanate to utilize mechanical mixing method or ultrasonic method disperse 1.5h in dehydrated alcohol fully relative to the cladding mass percent of positive electrode.
(2) by the isopropyl titanate dispersion liquid in step (1) at 60 DEG C of heating in water bath, by the 0.3Li of layer structure2MnO3·0.7LiNi0.6Co0.2Mn0.2O2Positive electrode adds to isopropyl titanate dispersion liquid, and dispersed with stirring 2.5h.
(3) according to 2.8% ferrous metal salt being dissolved in deionized water of atomic percentage conc of fast-ionic conductor shared by doped metallic elements, and in the isopropyl titanate dispersion liquid added to step (2), and continuously stirred 3.0h.
(4) mixture obtained in step (3) is added to reactor, air dry oven is incubated at 160 DEG C 30h, naturally cools to room temperature, obtain presoma by drying at 60 DEG C after obtained precipitate washing and filtering.
(5) presoma obtained in step (4) is proceeded in Muffle furnace, be incubated 8h at 550 DEG C, naturally cool to room temperature, finally give LiFe0.2Ti1.8O4The 0.3Li of spinel structure fast-ionic conductor coating modification2MnO3·0.7LiNi0.6Co0.2Mn0.2O2Positive electrode.
(6) the above-mentioned prepared LiFe of 0.48g is weighed0.2Ti1.8O4The 0.3Li of spinel structure fast-ionic conductor coating modification2MnO3·0.7LiNi0.6Co0.2Mn0.2O2Positive electrode, addition 0.05g conductive black is as conductive agent, and 0.05g PVDF is as binding agent, add that a small amount of NMP is ground is thoroughly mixed to form uniform pastel, being coated in foil substrate as test electrode, make button cell using lithium metal as to electrode, its electrolyte is 1M LiPF6/ EC:DMC (V:V=1:1), test charging and discharging currents density is 1C.
Use LiFe prepared by the present embodiment0.2Ti1.8O40.3Li after coating modification2MnO3·0.7LiNi0.6Co0.2Mn0.2O2Positive electrode is prepared electrode and is assembled into button cell with metal lithium sheet, and at room temperature during 1C constant-current discharge, after circulating 100 times, specific capacity may remain in 256mAh/g, shows good cycle performance.
Embodiment 5
(1) according to LiSn0.25Ti1.75O4Fast-ionic conductor is 2.0% quantitative isopropyl titanate to utilize mechanical mixing method or ultrasonic method disperse 1.0h in dehydrated alcohol fully relative to the cladding mass percent of positive electrode.
(2) by the isopropyl titanate dispersion liquid in step (1) at 80 DEG C of heating in water bath, by the LiNi of layer structure0.5Mn1.5O4Positive electrode adds to isopropyl titanate dispersion liquid, and dispersed with stirring 1.0h.
(3) according to 3.5% stanniferous slaine being dissolved in deionized water of atomic percentage conc of fast-ionic conductor shared by doped metallic elements, and in the isopropyl titanate dispersion liquid added to step (2), and continuously stirred 2.0h.
(4) mixture obtained in step (3) is added to reactor, air dry oven is incubated at 110 DEG C 36h, naturally cools to room temperature, obtain presoma by drying at 60 DEG C after obtained precipitate washing and filtering.
(5) presoma obtained in step (4) is proceeded in Muffle furnace, be incubated 8h at 850 DEG C, naturally cool to room temperature, finally give LiSn0.25Ti1.75O4The LiNi of spinel structure fast-ionic conductor coating modification0.5Mn1.5O4Positive electrode.
(6) the above-mentioned prepared LiSn of 0.48g is weighed0.25Ti1.75O4The LiNi of spinel structure fast-ionic conductor coating modification0.5Mn1.5O4Positive electrode, addition 0.05g conductive black is as conductive agent, and 0.05g PVDF is as binding agent, add that a small amount of NMP is ground is thoroughly mixed to form uniform pastel, being coated in foil substrate as test electrode, make button cell using lithium metal as to electrode, its electrolyte is 1M LiPF6/ EC:DMC (V:V=1:1), test charging and discharging currents density is 1C.
Use LiSn prepared by the present embodiment0.25Ti1.75O4LiNi after coating modification0.5Mn1.5O4Positive electrode is prepared electrode and is assembled into button cell with metal lithium sheet, and at room temperature during 1C constant-current discharge, after circulating 100 times, specific capacity may remain in 145mAh/g, and discharge voltage, at 4.5V, shows good cycle performance.
Comparative example 1
(1) according to LiTi2O4Fast-ionic conductor is 2.0% quantitative isopropyl titanate to utilize mechanical mixing method or ultrasonic method disperse 1.0h in dehydrated alcohol fully relative to the cladding mass percent of positive electrode.
(2) by the isopropyl titanate dispersion liquid in step (1) at 80 DEG C of heating in water bath, by the LiNi of layer structure0.8Co0.1Mn0.1O2Positive electrode adds to isopropyl titanate dispersion liquid, and dispersed with stirring 1.0h.
(3) mixture obtained in step (2) is added to reactor, air dry oven is incubated at 110 DEG C 36h, naturally cools to room temperature, obtain presoma by drying at 60 DEG C after obtained precipitate washing and filtering.
(4) presoma obtained in step (4) is proceeded in Muffle furnace, be incubated 8h at 850 DEG C, naturally cool to room temperature, finally give LiTi2O4The LiNi of spinel structure fast-ionic conductor coating modification0.8Co0.1Mn0.1O2Positive electrode.
(5) the above-mentioned prepared LiTi of 0.48g is weighed2O4The LiNi of spinel structure fast-ionic conductor coating modification0.8Co0.1Mn0.1O2Positive electrode, addition 0.05g conductive black is as conductive agent, and 0.05g PVDF is as binding agent, add that a small amount of NMP is ground is thoroughly mixed to form uniform pastel, being coated in foil substrate as test electrode, make button cell using lithium metal as to electrode, its electrolyte is 1M LiPF6/ EC:DMC (V:V=1:1), test charging and discharging currents density is 1C.
Use LiTi prepared by the present embodiment2O4LiNi after coating modification0.8Co0.1Mn0.1O2Positive electrode is prepared electrode and is assembled into button cell with metal lithium sheet, and at room temperature during 1C constant-current discharge, after circulating 100 times, specific capacity is maintained at 160mAh/g, shows relatively low discharge capacity compared with the Surface coating effect after doped with metal elements.
Claims (10)
1. metal-doped spinel structure fast-ionic conductor is coated with a preparation method for nickeliferous positive electrode, its feature
It is: organic titanium salt, nickeliferous positive electrode and doped metal salt are dissolved, mixes, obtain dispersion liquid；Described
Dispersion liquid proceeds in hydrothermal reaction kettle, carries out hydro-thermal reaction, obtain presoma at a temperature of 80 DEG C～160 DEG C；
Described presoma is placed in 500 DEG C～900 DEG C of temperature lower calcinations, to obtain final product.
Metal-doped spinel structure fast-ionic conductor coating modification the most according to claim 1 nickeliferous positive pole material
The preparation method of material, it is characterised in that: the quality of organic titanium salt and doped metal salt is to ensure that the metal generated is mixed
Miscellaneous spinel structure fast-ionic conductor quality is the 0.5%～10.0% of nickeliferous positive electrode quality.
Metal-doped spinel structure fast-ionic conductor the most according to claim 2 is coated with nickeliferous positive electrode
Preparation method, it is characterised in that: the mass ratio of organic titanium salt and doped metal salt is with metal unit in doped metal salt
Element is (0.1～10) with the mol ratio of titanium elements in organic titanium salt: 100 meterings.
Metal-doped spinel structure fast-ionic conductor coating modification the most according to claim 2 nickeliferous positive pole material
The preparation method of material, it is characterised in that: described nickeliferous positive electrode is:
There is the LiNi of spinel structurexMn2-xO4, 0.1 < x < 0.8；
And/or there is the LiNi of layer structure1-x-yCoxMnyO2, 0 < x < 0.5,0 < y < 0.5；
And/or richness lithium manganese anode material xLi2MnO3·(1-x)LiMO2, 0.1 < x < 0.9, M=Ni, in Co, Mn extremely
Few one.
5. nickeliferous just according to the metal-doped spinel structure fast-ionic conductor cladding described in any one of claims 1 to 3
The preparation method of pole material, it is characterised in that: described doped metal salt be containing aluminum, cerium, chromium, vanadium, ferrum,
At least one in the soluble metallic salt of stannum or zinc.
Metal-doped spinel structure fast-ionic conductor the most according to claim 1 is coated with nickeliferous positive electrode
Preparation method, it is characterised in that: the described hydro-thermal reaction time is 5.0h～36h.
Metal-doped spinel structure fast-ionic conductor the most according to claim 1 is coated with nickeliferous positive electrode
Preparation method, it is characterised in that: described calcination time is 2.0h～12h.
8. it is coated with according to the metal-doped spinel structure fast-ionic conductor described in Claims 1 to 4,6,7 any one
The preparation method of nickeliferous positive electrode, it is characterised in that: organic titanium salt is joined alcohols solvent, stirs or super
After sound dispersion 0.1h～2.0h, it is heated to 50 DEG C～80 DEG C, adds nickeliferous positive electrode, be sufficiently stirred for
Dispersion, adds doped metal salt, dispersed with stirring 0.5h～5.0h, obtains dispersion liquid.
9. the metal-doped spinel structure that preparation method described in Claims 1 to 4,6,7 any one prepares soon from
The cladding nickeliferous positive electrode application in lithium ion battery of sub-conductor, it is characterised in that: be applied to prepare lithium from
Sub-battery.
Metal-doped spinel structure fast-ionic conductor the most according to claim 9 is coated with nickeliferous positive electrode and exists
Application in lithium ion battery, it is characterised in that: by described metal-doped modified spinelle structure fast-ionic conductor
It is coated with after nickeliferous positive electrode mixes with conductive agent and binding agent, is coated in foil substrate by rubbing method, system
Become based lithium-ion battery positive plate.
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| WO2019041057A1 (en) | 2017-09-01 | 2019-03-07 | Universidad De Antofagasta | Manganese spinel doped with magnesium, cathode material comprising same, method for preparing same and lithium ion battery comprising same |
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