CN105932251B - A kind of preparation method and applications of metal oxide coated lithium ion battery positive electrode - Google Patents

A kind of preparation method and applications of metal oxide coated lithium ion battery positive electrode Download PDF

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CN105932251B
CN105932251B CN201610389932.9A CN201610389932A CN105932251B CN 105932251 B CN105932251 B CN 105932251B CN 201610389932 A CN201610389932 A CN 201610389932A CN 105932251 B CN105932251 B CN 105932251B
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positive electrode
lithium ion
ion battery
metal oxide
oxide coated
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CN105932251A (en
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张治安
赖延清
徐�明
张凯
李劼
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Central South University
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Central South University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a kind of preparation method and application of metal oxide coated lithium ion battery positive electrode, after nano level metal powder and positive electrode ball milling mixing, in the resulting mixture plus water is reacted, and obtains the positive electrode of surface clad hydroxide colloid；The positive electrode of the surface clad hydroxide colloid, which is placed under high temperature, to be calcined, obtain the positive electrode that surface forms the good metal oxide clad of one layer of dense uniform, stability, obtained metal oxide coated lithium ion battery positive electrode can prepare good cycling stability, the lithium ion battery of cycle life layer；And the preparation method of metal oxide coated lithium ion battery positive electrode has the features such as cost is low, easy to operate, environmental-friendly, can be applied to industrialized production on a large scale.

Description

A kind of preparation method of metal oxide coated lithium ion battery positive electrode and its Using
Technical field
The present invention relates to a kind of preparation method of cell positive material, and in particular to a kind of metal oxide coated lithium ion The preparation method of cell positive material and its application in lithium ion battery, belong to technical field of lithium ion.
Background technology
Nowadays, mobile electronic device, such as smart mobile phone, digital camera, laptop, and electric automobile and mixed The rapid development for closing power vehicle promotes advancing by leaps and bounds for lithium rechargeable battery technology.But current lithium ion battery Positive electrode, such as cobalt acid lithium, spinel lithium manganate, LiFePO4, all has the shortcomings that cycle life is low, it is impossible to meets not Carry out the requirement of pure electric vehicle equipment.Therefore, study and develop a kind of positive electrode with the high circulation service life and become the whole world and grind Study carefully the common objective of personnel.
Coating modification is using a kind of excellent material of physical and chemical performance, and one layer is formed in target material particle surface The guard method of even clad.Since during the charge and discharge cycles of lithium ion battery, electrolyte has corruption to positive electrode Erosion acts on, and causes the Crystal Structure Distortion of positive electrode, and cycle life reduces.Therefore, coating modification is often applied to improve just The chemical property of pole material.Each quasi-metal oxides were widely used in the table of anode material for lithium-ion batteries in recent years Face coating modification.The cladding that the methods of some researchers utilize atom deposition method, magnetron sputtering method carries out metal oxide changes Property, but since operating process is complicated, the shortcomings of preparation process is cumbersome and cost is excessive, it is impossible to large-scale to be applied to industry Metaplasia is produced.
The content of the invention
In view of the defects existing in the prior art, there is dense uniform, steady the purpose of the invention is to provide a kind of The preparation method of the modification lithium-ion battery anode material of qualitative good metal oxide clad, preparation method operation letter Single, cost is low, environmental-friendly, is conducive to industrialized production.
Another object of the present invention is to be to provide the metal oxide coated lithium ion battery positive electrode Using the lithium ion battery having extended cycle life can be prepared as lithium ion anode material.
In order to realize above-mentioned technical purpose, the present invention provides a kind of metal oxide coated lithium ion battery positive electrode Preparation method, this method is by after nano level metal powder and positive electrode ball milling mixing, with water in 40 DEG C~80 DEG C temperature Under reacted, obtain the positive electrode of surface clad hydroxide colloid；The surface clad hydroxide glue The positive electrode of body is calcined at a temperature of being placed in 200 DEG C~900 DEG C, to obtain the final product.
Preferable scheme, nano level metal powder quality are the 0.5%~10.0% of positive electrode quality.
More preferably scheme, nano level metal powder particle diameter distribution are 50nm~500nm.
More preferably scheme, nano level metal powder is nanoscale rubidium powder, nano-grade lanthanum powder, nano-scale cerium powder, nanoscale At least one of yttrium powder, nanoscale magnesium powder, nanoscale aluminium powder.
Further preferred scheme, nano level metal powder carry out pre-activate processing by acid corrosion method.
Most preferred scheme, acid corrosion method be by concentration be the hydrochloric acid of 0.1mol/L~1.0mol/L, sulfuric acid, nitric acid into Row immersion treatment.
More preferably scheme, positive electrode are the LiM with spinel structure2O4, M=Ni and/or Mn；And/or there is layer The LiMO of shape structure2At least one of, M=Ni, Co, Mn, Al；And/or rich lithium manganese anode material xLi2MnO3·(1-x) LiMO2At least one of, M=Ni, Co, Mn.
Preferable scheme, ball milling realized by planetary ball mill or roller shaft type ball mill, drum's speed of rotation for 400~ 800p/min, Ball-milling Time are 1h~8h.Ball grinder is with agate, corundum, nylon or steel material, and abrading-ball is zirconia ball, steel ball Or agate ball.
Preferable scheme, reaction time are 0.5h~5.0h.
Preferable scheme, calcination time are 5h~20h.
Present invention also offers the application of the metal oxide coated lithium ion battery positive electrode, by the gold Belong to oxide coated lithium ion battery positive electrode application and prepare lithium ion battery.
The method for preparing metal oxide coated lithium ion battery positive electrode of the present invention includes step in detail below：
1) by rubidium (Rb) of the particle diameter between 50nm~500nm, lanthanum (La), cerium (Ce), yttrium (Y), magnesium (Mg), aluminium (Al) At least one metal dust and with spinel structure LiM2O4(M=Ni and/or Mn), and/or with layer structure LiMO2(at least one of M=Ni, Co, Mn, Al), and/or rich lithium manganese anode material xLi2MnO3·(1-x)LiMO2(M=Ni, At least one of Co, Mn), by planetary ball mill or roller shaft type ball mill ball milling mixing, drum's speed of rotation for 400~ 800p/min, incorporation time are 1h~8h, and the mass ratio of nanometre metal powder and positive electrode is 0.005:1.0~0.1:1.0 Ball-milling medium can be zirconia ball, steel ball or agate ball；
2) add water in the mixture obtained into step 1), in 40 DEG C~80 DEG C of water-bath, insulation 0.5h~ 5.0h, prepares the positive electrode after metal hydroxides cladding；
3) positive electrode after metal hydroxides is coated is by filtering, after washing, be put into vacuum drying oven 70~ Dry 8~14h at 120 DEG C, obtains the positive electrode material precursor after metal hydroxides cladding；
4) presoma is transferred in Muffle furnace, 5h~20h is kept the temperature between 200 DEG C~900 DEG C, naturally cools to room Temperature, finally obtains the positive electrode after metal oxide cladding.
Metal oxide coated lithium ion battery positive electrode prepared by the present invention is used to prepare lithium ion battery：By metal Oxide coated lithium ion battery positive electrode and conductive agent (conductive black) and binding agent (PVDF) and a small amount of NMP is ground fills Point be mixed to form uniform pastel, coated in foil substrate as test electrode, using lithium metal as electrode being made button Formula battery, its electrolyte are 1M LiPF6/EC:DMC(V:V=1:1).
Nano metal powder is carried out surface activation process by technical scheme using ball-milling method or acid corrosion method, Nano metal powder after activation process reacts generation metal hydroxides, the metal hydrogen-oxygen of generation with water under suitable condition Compound surface is electrically charged, can uniform adsorption on positive electrode surface, be further dehydrated at high temperature using metal hydroxides Generate metal oxide nano particles, the metal oxide nano particles in-situ deposition of generation is caused on positive electrode surface Close metal oxide clad uniform, stability is good.
Compared with the prior art, the advantageous effects that technical scheme is brought：
Metal oxide in metal oxide coated lithium ion battery positive electrode prepared by technical scheme Clad dense uniform, stability are good, can effectively prevent during the charge and discharge cycles of lithium ion battery, electrolyte is to cathode The corrosiveness of material, substantially prolongs the cycle life of lithium ion battery.
The method for preparing metal oxide coated lithium ion battery positive electrode of the present invention, takes full advantage of nanometer grade gold Belonging to powder and water reaction generation metal hydroxides colloidal sol and metal hydroxides has preferable adsorptivity, and metal hydroxide Thing colloidal sol pyrolytic generates the principle of metal oxide.The good metal of dense uniform, stability is formed on positive electrode surface Oxide skin(coating), can effectively prevent positive active material and electrolyte solution contacts and loss by dissolution, substantially prolongs following for battery The ring service life；The ion and electronic conductivity of electrode are substantially increased at the same time, improve the chemical property of lithium ion battery.
The metal oxide coated lithium ion battery positive electrode of the present invention synthesizes persursor material combination by low temperature Prepared by the method for high temperature sintering, have cost of material low, the characteristics of being simple to operate and friendly to environment, overcome traditional metal oxygen In compound coating modification method, since cost of material is high, the shortcomings of operating process is complicated and technique is cumbersome.
The method for preparing metal oxide coated lithium ion battery positive electrode of the present invention passes through ball-milling method or acid corrosion Method, makes metal surface activation, substantially increases metal and the efficiency of water reaction, makes process simplification, mild condition.
The metal oxide coated lithium ion battery positive electrode of the present invention prepares cathode, applied to lithium ion battery, table Reveal excellent cycle performance, substantially prolongs cycle life.
Brief description of the drawings
【Fig. 1】For the LiNi before coating modification in embodiment 10.8Co0.15Al0.05O2Positive electrode scanning electron microscope (SEM) photograph (SEM).
【Fig. 2】For Al in embodiment 12O3LiNi after coating modification0.8Co0.15Al0.05O2Positive electrode scanning electron microscope (SEM) photograph (SEM)。
【Fig. 3】For without the LiNi of coating modification0.8Co0.15Al0.05O2Al made from positive electrode and embodiment 12O3Bag Cover modified LiNi0.8Co0.15Al0.05O2100 cycle performance curve maps of positive electrode.
Embodiment
Following embodiments are intended to be described in further details present invention, and the protection domain of the claims in the present invention It is not limited by the example.
Embodiment 1
(1) superfine aluminium power that particle diameter is 50nm is weighed into aluminium respectively according to the mass percent that opposite positive electrode is 1% Powder and LiNi0.8Co0.15Al0.05O2Positive electrode, is added to capacity as 250mL and fills in the agate jar of zirconia ball, Then rotating speed is adjusted to 400p/min grindings 2h.
(2) mixture after grinding is added in the three-necked flask that capacity is 250mL and adds 100mL deionized waters, The stirring reaction 1h at 50 DEG C.
(3) precipitation 3 times that step (2) obtains is washed with deionized, is then washed 3 times with absolute ethyl alcohol, then filtered, Filter cake is kept the temperature in 80 DEG C of convection oven 12 it is small when, obtain the LiNi of aluminium hydroxide cladding0.8Co0.15Al0.05O2Cathode material The presoma of material.
(4) presoma that step (3) obtains is fitted into crucible, when 450 DEG C of insulations 5 are small, obtains Al2O3Coating modification LiNi afterwards0.8Co0.15Al0.05O2Positive electrode.
(5) Al obtained above of 0.48g is weighed2O3LiNi after coating modification0.8Co0.15Al0.05O2Positive electrode, adds Enter 0.05g conductive blacks adds a small amount of NMP is ground to be thoroughly mixed to form as conductive agent, 0.05g PVDF as binding agent Even pastel, coated in test electrode is used as in foil substrate, is made button cell, it is electrolysed using lithium metal as to electrode Liquid is 1M LiPF6/EC:DMC(V:V=1:1) it is 1C, to test charge-discharge magnification.
Using Al manufactured in the present embodiment2O3LiNi after coating modification0.8Co0.15Al0.05O2Positive electrode, its material table Chemical property seek peace as shown in Figures 1 to 3：
It can be seen that the LiNi without coating modification in Fig. 10.8Co0.15Al0.05O2Positive electrode by size for 300~ The spherical structure of the primary particle composition of 800nm, surface are smooth.
It can be seen that in Fig. 2 by Al2O3LiNi after coating modification0.8Co0.15Al0.05O2Positive electrode particle surface has The sheet clad being evenly distributed.
Show to use Al in Fig. 32O3LiNi after coating modification0.8Co0.15Al0.05O2Electrode made of positive electrode, in room Under temperature under 1C multiplying powers during constant-current discharge, specific capacity may remain in 190mAh/g after circulating 100 times；Show good circulation Performance.
Embodiment 2
(1) superfine magnesium powder that particle diameter is 100nm is weighed respectively according to the mass percent that opposite positive electrode is 0.5% Magnesium powder and 0.3Li2MnO3·0.7LiNi0.333Co0.333Mn0.333O2Positive electrode, is added to capacity as 250mL and fills steel ball Corundum ball grinder in, then adjust rotating speed to 500p/min grind 4h.
(2) mixture after grinding is added in the three-necked flask that capacity is 250mL and adds 100mL deionized waters, The stirring reaction 2h at 40 DEG C.
(3) precipitation 3 times that step (2) obtains is washed with deionized, is then washed 3 times with absolute ethyl alcohol, then filtered, Filter cake is kept the temperature in 80 DEG C of convection oven 12 it is small when, obtain the 0.3Li of magnesium hydroxide cladding2MnO3· 0.7LiNi0.333Co0.333Mn0.333O2The presoma of positive electrode.
(4) presoma that step (3) obtains is fitted into crucible, when 400 DEG C of insulations 3 are small, after obtaining MgO coating modifications 0.3Li2MnO3·0.7LiNi0.333Co0.333Mn0.333O2Positive electrode.
(5) 0.3Li after the MgO coating modifications obtained above of 0.48g is weighed2MnO3· 0.7LiNi0.333Co0.333Mn0.333O2Positive electrode, adds 0.05g conductive blacks as conductive agent, 0.05g PVDF are as viscous Agent is tied, adds a small amount of NMP is ground to be thoroughly mixed to form uniform pastel, electrode is tested coated in being used as in foil substrate, with For lithium metal as button cell is made to electrode, its electrolyte is 1M LiPF6/EC:DMC(V:V=1:1) discharge and recharge times, is tested Rate is 1C.
Using the 0.3Li after MgO coating modifications manufactured in the present embodiment2MnO3·0.7LiNi0.333Co0.333Mn0.333O2Just Pole material is assembled into button cell for electrode and with metal lithium sheet, at room temperature during 1C constant-current discharges, specific capacity after circulating 100 times 267mAh/g is may remain in, shows good cycle performance.
Embodiment 3
(1) mass percent that the ultra-fine cerium powder that particle diameter is 200nm is 2.0% according to opposite positive electrode is weighed respectively Cerium powder and 0.5Li2MnO3·0.5LiNi0.5Co0.2Mn0.3O2Positive electrode, is added to capacity as 250mL and fills agate ball In nylon ball grinder, rotating speed is then adjusted to 600p/min grindings 6h.
(2) mixture after grinding is added in the three-necked flask that capacity is 250mL and adds 100mL deionized waters, The stirring reaction 3h at 60 DEG C.
(3) precipitation 3 times that step (2) obtains is washed with deionized, is then washed 3 times with absolute ethyl alcohol, then filtered, Filter cake is kept the temperature in 80 DEG C of convection oven 12 it is small when, obtain the 0.5Li of cerium hydroxide cladding2MnO3· 0.5LiNi0.5Co0.2Mn0.3O2The presoma of positive electrode.
(4) presoma that step (3) obtains is fitted into crucible, when 600 DEG C of insulations 8 are small, obtains CeO2Coating modification 0.5Li afterwards2MnO3·0.5LiNi0.5Co0.2Mn0.3O2Positive electrode.
(5) CeO obtained above of 0.48g is weighed20.5Li after coating modification2MnO3· 0.5LiNi0.5Co0.2Mn0.3O2Positive electrode, adds 0.05g conductive blacks as conductive agent, 0.05g PVDF as binding agent, Add a small amount of NMP is ground to be thoroughly mixed to form uniform pastel, coated in test electrode is used as in foil substrate, with lithium metal Button cell is made as to electrode, its electrolyte is 1M LiPF6/EC:DMC(V:V=1:1), test charge-discharge magnification is 1C。
Using CeO manufactured in the present embodiment20.5Li after coating modification2MnO3·0.5LiNi0.5Co0.2Mn0.3O2Cathode Material is assembled into button cell for electrode and with metal lithium sheet, at room temperature during 1C constant-current discharges, circulation 100 times after specific capacity still 274mAh/g is positively retained at, shows good cycle performance.
Embodiment 4
(1) mass percent that the ultra-fine rubidium powder that particle diameter is 300nm is 4.0% according to opposite positive electrode is weighed respectively Rubidium powder and 0.7Li2MnO3·0.3LiNi0.6Co0.2Mn0.2O2Positive electrode, is added to capacity as 250mL and fills the agate of steel ball In Nao ball grinders, rotating speed is then adjusted to 800p/min grindings 8h.
(2) mixture after grinding is added in the three-necked flask that capacity is 250mL and adds 100mL deionized waters, The stirring reaction 5h at 80 DEG C.
(3) precipitation 3 times that step (2) obtains is washed with deionized, is then washed 3 times with absolute ethyl alcohol, then filtered, Filter cake is kept the temperature in 80 DEG C of convection oven 12 it is small when, obtain the 0.7Li of rubidium hydroxide cladding2MnO3· 0.3LiNi0.6Co0.2Mn0.2O2The presoma of positive electrode.
(4) presoma that step (3) obtains is fitted into crucible, when 600 DEG C of insulations 12 are small, obtains RbO2Coating modification 0.7Li afterwards2MnO3·0.3LiNi0.6Co0.2Mn0.2O2Positive electrode.
(5) RbO obtained above of 0.48g is weighed20.7Li after coating modification2MnO3· 0.3LiNi0.6Co0.2Mn0.2O2Positive electrode, adds 0.05g conductive blacks as conductive agent, 0.05g PVDF as binding agent, Add a small amount of NMP is ground to be thoroughly mixed to form uniform pastel, coated in test electrode is used as in foil substrate, with lithium metal Button cell is made as to electrode, its electrolyte is 1M LiPF6/EC:DMC(V:V=1:1), test charge-discharge magnification is 1C。
Using RbO manufactured in the present embodiment20.7Li after coating modification2MnO3·0.3LiNi0.6Co0.2Mn0.2O2Cathode Material is assembled into button cell for electrode and with metal lithium sheet, at room temperature during 1C constant-current discharges, circulation 100 times after specific capacity still 282mAh/g is positively retained at, shows good cycle performance.
Embodiment 5
(1) mass percent that the ultra-fine yttrium powder that particle diameter is 500nm is 6.0% according to opposite positive electrode is weighed respectively Yttrium powder and LiNi0.5Mn1.5O4Positive electrode, is added to capacity as 250mL's and fills in the nylon ball grinder of agate ball, then Rotating speed is adjusted to 600p/min grindings 5h.
(2) mixture after grinding is added in the three-necked flask that capacity is 250mL and adds 100mL deionized waters, The stirring reaction 5h at 70 DEG C.
(3) precipitation 3 times that step (2) obtains is washed with deionized, is then washed 3 times with absolute ethyl alcohol, then filtered, Filter cake is kept the temperature in 80 DEG C of convection oven 12 it is small when, obtain the LiNi of yttrium hydroxide cladding0.5Mn1.5O4Before positive electrode Drive body.
(4) presoma that step (3) obtains is fitted into crucible, when 800 DEG C of insulations 16 are small, obtains Y2O3Coating modification LiNi afterwards0.5Mn1.5O4Positive electrode.
(5) Y obtained above of 0.48g is weighed2O3LiNi after coating modification0.5Mn1.5O4Positive electrode, adds 0.05g Conductive black adds a small amount of NMP is ground to be thoroughly mixed to form uniform paste as conductive agent, 0.05g PVDF as binding agent Thing, coated in test electrode is used as in foil substrate, is made button cell, its electrolyte is 1M using lithium metal as to electrode LiPF6/EC:DMC(V:V=1:1) it is 1C, to test charge-discharge magnification.
Using Y manufactured in the present embodiment2O3LiNi after coating modification0.5Mn1.5O4Positive electrode is for electrode and and lithium metal Piece is assembled into button cell, and at room temperature during 1C constant-current discharges, specific capacity may remain in 142mAh/g after circulating 100 times, put Piezoelectric voltage is maintained at 4.5V, shows good cycle performance.
Embodiment 6
(1) mass percent that the ultra-fine lanthanum powder that particle diameter is 300nm is 10.0% according to opposite positive electrode is claimed respectively Take lanthanum powder and LiNi0.6Co0.2Mn0.2O2Positive electrode, is added to capacity as 250mL and fills in the steel ball grinder of agate ball, Then rotating speed is adjusted to 500p/min grindings 4h.
(2) mixture after grinding is added in the three-necked flask that capacity is 250mL and adds 100mL deionized waters, The stirring reaction 5h at 50 DEG C.
(3) precipitation 3 times that step (2) obtains is washed with deionized, is then washed 3 times with absolute ethyl alcohol, then filtered, Filter cake is kept the temperature in 80 DEG C of convection oven 12 it is small when, obtain the LiNi of lanthanum hydroxide cladding0.6Co0.2Mn0.2O2Positive electrode Presoma.
(4) presoma that step (3) obtains is fitted into crucible, when 550 DEG C of insulations 8 are small, obtains La2O3Coating modification LiNi afterwards0.6Co0.2Mn0.2O2Positive electrode.
(5) La obtained above of 0.48g is weighed2O3LiNi after coating modification0.6Co0.2Mn0.2O2Positive electrode, adds 0.05g conductive blacks add a small amount of NMP is ground to be thoroughly mixed to form uniformly as conductive agent, 0.05g PVDF as binding agent Pastel, coated in foil substrate as test electrode, button cell is made using lithium metal as to electrode, its electrolyte For 1M LiPF6/EC:DMC(V:V=1:1) it is 1C, to test charge-discharge magnification.
Using La manufactured in the present embodiment2O3LiNi after coating modification0.6Co0.2Mn0.2O2Positive electrode for electrode and with Metal lithium sheet is assembled into button cell, and at room temperature during 1C constant-current discharges, specific capacity may remain in after circulating 100 times 185mAh/g, shows good cycle performance
Embodiment 7
(1) superfine aluminium power that particle diameter is 300nm is added to capacity is 250mL and to fill concentration be 0.1mol/L hydrochloric acid Immersion activation process is carried out in three-necked flask.
(2) aluminium in step (1) after overactivation is weighed respectively according to the mass percent that opposite positive electrode is 2.0% Powder and LiNi0.333Co0.333Mn0.333O2Positive electrode be added to capacity be 250mL three-necked flask in and add 100mL go from Sub- water, the stirring reaction 5h at 60 DEG C.
(3) precipitation 3 times that step (2) obtains is washed with deionized, is then washed 3 times with absolute ethyl alcohol, then filtered, Filter cake is kept the temperature in 80 DEG C of convection oven 12 it is small when, obtain the LiNi of aluminium hydroxide cladding0.333Co0.333Mn0.333O2Cathode The presoma of material.
(4) presoma that step (3) obtains is fitted into crucible, when 500 DEG C of insulations 8 are small, obtains Al2O3Coating modification LiNi afterwards0.333Co0.333Mn0.333O2Positive electrode.
(5) Al obtained above of 0.48g is weighed2O3LiNi after coating modification0.333Co0.333Mn0.333O2Positive electrode, Add 0.05g conductive blacks adds a small amount of NMP is ground to be thoroughly mixed to form as conductive agent, 0.05g PVDF as binding agent Uniform pastel, coated in test electrode is used as in foil substrate, button cell is made using lithium metal as to electrode, its electricity Solution liquid is 1M LiPF6/EC:DMC(V:V=1:1) it is 1C, to test charge-discharge magnification.
Using Al manufactured in the present embodiment2O3LiNi after coating modification0.333Co0.333Mn0.333O2Positive electrode is for electrode And button cell is assembled into metal lithium sheet, at room temperature during 1C constant-current discharges, specific capacity may remain in after circulating 100 times 172mAh/g, shows good cycle performance.
Embodiment 8
(1) superfine magnesium powder that particle diameter is 400nm is added to capacity is 250mL and to fill concentration be 0.5mol/L sulfuric acid Immersion activation process is carried out in three-necked flask.
(2) magnesium in step (1) after overactivation is weighed respectively according to the mass percent that opposite positive electrode is 3.0% Powder and LiNi0.85Co0.05Mn0.1O2Positive electrode is added in the three-necked flask that capacity is 250mL and adds 100mL deionizations Water, the stirring reaction 5h at 60 DEG C.
(3) precipitation 3 times that step (2) obtains is washed with deionized, is then washed 3 times with absolute ethyl alcohol, then filtered, Filter cake is kept the temperature in 80 DEG C of convection oven 12 it is small when, obtain the LiNi of magnesium hydroxide cladding0.85Co0.05Mn0.1O2Cathode material The presoma of material.
(4) presoma that step (3) obtains is fitted into crucible, when 500 DEG C of insulations 8 are small, after obtaining MgO coating modifications LiNi0.85Co0.05Mn0.1O2Positive electrode.
(5) LiNi after the MgO coating modifications obtained above of 0.48g is weighed0.85Co0.05Mn0.1O2Positive electrode, adds 0.05g conductive blacks add a small amount of NMP is ground to be thoroughly mixed to form uniformly as conductive agent, 0.05g PVDF as binding agent Pastel, coated in foil substrate as test electrode, button cell is made using lithium metal as to electrode, its electrolyte For 1M LiPF6/EC:DMC(V:V=1:1) it is 1C, to test charge-discharge magnification.
Using the LiNi after MgO coating modifications manufactured in the present embodiment0.85Co0.05Mn0.1O2Positive electrode for electrode and with Metal lithium sheet is assembled into button cell, and at room temperature during 1C constant-current discharges, specific capacity may remain in after circulating 100 times 186mAh/g, shows good cycle performance.

Claims (7)

  1. A kind of 1. preparation method of metal oxide coated lithium ion battery positive electrode, it is characterised in that：By nano level metal Powder with water at a temperature of 40 DEG C~80 DEG C with after positive electrode ball milling mixing, being reacted, obtaining surface clad hydrogen-oxygen The positive electrode of compound colloid；The positive electrode of the surface clad hydroxide colloid is placed in 200 DEG C~900 DEG C temperature Under calcined, to obtain the final product；The nanometre metal powder carries out pre-activate processing by acid corrosion method；The nano level metal Powder is nanoscale rubidium powder, nano-grade lanthanum powder, nano-scale cerium powder, nanoscale yttrium powder, nanoscale magnesium powder, in nanoscale aluminium powder extremely Few one kind.
  2. 2. the preparation method of metal oxide coated lithium ion battery positive electrode according to claim 1, its feature exist In：Nano level metal powder quality is the 0.5%~10.0% of positive electrode quality.
  3. 3. the preparation method of metal oxide coated lithium ion battery positive electrode according to claim 2, its feature exist In：The nano level metal powder particle diameter distribution is 50nm~500nm.
  4. 4. the preparation method of metal oxide coated lithium ion battery positive electrode according to claim 1, its feature exist In：The acid corrosion method is that the hydrochloric acid, sulfuric acid, nitric acid for being 0.1mol/L~1.0mol/L by concentration carry out immersion treatment.
  5. 5. the preparation method of metal oxide coated lithium ion battery positive electrode according to claim 1 or 2, its feature It is：The positive electrode is：LiM with spinel structure2O4, M=Ni and/or Mn；And/or with layer structure LiMO2At least one of, M=Ni, Co, Mn, Al；
    And/or rich lithium manganese anode material xLi2MnO3·(1-x)LiMO2, 0.1<x<0.9, M=Ni, at least one of Co, Mn.
  6. 6. the preparation method of metal oxide coated lithium ion battery positive electrode according to claim 1, its feature exist In：The ball milling realized by planetary ball mill or roller shaft type ball mill, and drum's speed of rotation is 400~800p/min, ball Consume time as 1h~8h.
  7. 7. according to Claims 1 to 4, the preparation side of 6 any one of them metal oxide coated lithium ion battery positive electrodes Method, it is characterised in that：Reaction time is 0.5h~5.0h；Calcination time is 5h~20h.
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CN108232150A (en) * 2017-12-29 2018-06-29 贵州振华义龙新材料有限公司 Anode material for lithium-ion batteries and its preparation method and application
CN108390065A (en) * 2018-01-25 2018-08-10 湖北师范大学 A method of in li-ion electrode materials surface coating cerium oxide
CN108550803A (en) * 2018-03-21 2018-09-18 北京旭碳新材料科技有限公司 Ternary anode material for lithium-ion batteries and preparation method thereof
CN111916697B (en) * 2020-07-14 2021-09-21 蜂巢能源科技有限公司 Cobalt-free cathode material, preparation method thereof, lithium ion battery cathode and lithium battery
CN112151797B (en) * 2020-08-21 2021-09-14 湖南长远锂科股份有限公司 Lithium-rich manganese-based positive electrode material coated by multi-metal composite oxide and preparation method thereof
CN113937262A (en) * 2021-09-22 2022-01-14 浙江钠创新能源有限公司 Metal oxide modified positive electrode material for sodium ion battery and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102107899A (en) * 2011-01-11 2011-06-29 上海理工大学 Preparation method of lamellar gamma-phase nano aluminum oxide
CN104393277A (en) * 2014-10-20 2015-03-04 上海空间电源研究所 Ternary material coated with metal oxide on surface and used for lithium ion battery, and preparation method of ternary material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102107899A (en) * 2011-01-11 2011-06-29 上海理工大学 Preparation method of lamellar gamma-phase nano aluminum oxide
CN104393277A (en) * 2014-10-20 2015-03-04 上海空间电源研究所 Ternary material coated with metal oxide on surface and used for lithium ion battery, and preparation method of ternary material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Al2O3包覆对三元正极材料结构和性能的影响;张正国等;《中国陶瓷》;20150805;第51卷(第8期);第19-22页 *

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