CN105977466A - Conductive oxide coated lithium ion battery tri-element anode material and preparation method thereof - Google Patents

Conductive oxide coated lithium ion battery tri-element anode material and preparation method thereof Download PDF

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CN105977466A
CN105977466A CN201610507541.2A CN201610507541A CN105977466A CN 105977466 A CN105977466 A CN 105977466A CN 201610507541 A CN201610507541 A CN 201610507541A CN 105977466 A CN105977466 A CN 105977466A
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lithium
ion battery
lithium ion
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刘争伟
常敬杭
唐泽勋
商士波
杨涛
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HUNAN SOUNDDON NEW ENERGY CO Ltd
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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
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • 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
    • H01M4/52—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • 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
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    • 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

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Abstract

The invention discloses a conductive oxide coated lithium ion battery tri-element anode material and a preparation method thereof. A structural formula of the material is LixNi1-y-zCoyMzO2/TinO2n-1, wherein x is greater than or equal to 1 and less than or equal to 1.2, y is greater than or equal to 0 and less than or equal to 1/3, and z is greater than or equal to 0 and less than or equal to 1/3. The preparation method includes: combining a solid-phase method with a liquid-phase method to fully coating the surface of a tri-element anode active material with nanoscale titanium oxide particles. Conductivity of the tri-element anode material coated with titanium oxide is improved remarkably. Titanium oxide high in chemical stability inhibits reaction between the surface of anode material and an electrolyte, so that thermostability of the tri-element anode material is improved while service life of the same is prolonged. Elements are more uniformly distributed inside the anode material through doping by the liquid-phase method, so that internal structure of the anode material is further stabilized, and cyclicity, safety and storability of the tri-element anode material in battery application are improved.

Description

A kind of ternary cathode material of lithium ion battery of electroconductive oxide cladding and preparation method thereof
Technical field
The present invention relates to anode material for lithium ion battery, particularly to ternary cathode material of lithium ion battery that a kind of electroconductive oxide is coated with and preparation method thereof.
Background technology
Lithium ion battery is widely used in portable energy-storing equipment at present, and its demand the most constantly increases in traditional consumer electronics field.In recent years, due to the guiding kept under strict control environmental conservation aspect and in terms of country's new forms of energy policy, the energy storage field such as electric tool, LEV, new-energy automobile was more and more stronger to the demand of lithium ion battery.Data show that the first quarter in 2015 China's lithium battery electric core yield is 7,216,000,000 Wh, increase by 30.8% on a year-on-year basis.The lithium battery yield being wherein applied to electric automobile is 1,656,000,000 Wh, increases by 126% on a year-on-year basis, is to increase maximum demand end.
Currently, the tertiary cathode material of nickelic series is because of its high power capacity, and good cycle, the advantage such as moderate cost has attracted extensive concern, and studies more with nickel-cobalt-manganternary ternary anode material, and nickel cobalt aluminum tertiary cathode material is main, and marketization application the most.But many research shows, the tertiary cathode material of stratiform is during long-term removal lithium embedded, the increase in lithium room easily causes cation mixing and lattice subsides, and active material less stable under the conditions of inside battery high temperature high working voltage, accelerate electrolyte the erosion of positive electrode to cause transition metal dissolving, deoxidation gassing, produces the harmful phenomenon such as big calorimetric, electrolyte is decomposed and reduces lithium ion and electron conductivity simultaneously, is degrading cycle performance of battery and battery security is produced impact.
Generally utilize cladding various metallic elements that positive electrode is protected; as Chinese patent CN104600290A disclose a kind of tertiary cathode material is placed in the common metal solution such as aluminum, zinc again with aqueous slkali as precipitant; metallic element in metal salt solution is deposited on positive electrode surface carry out high-temperature calcination and obtain Surface coating and have the positive electrode of metal-oxide, then carries out carbon cladding by being mixed into carbon source.But the metal-oxide of cladding belongs to inert compound, substantially belongs to electronic body and reduces positive electrode electric conductivity, capacity and high rate performance is the most necessarily caused to decline, and the coated with carbon at high temperature easy oxygen generation exothermic reaction with precipitation: C+O2=CO2Promoting that balance moves to right and causes more oxygen lack, accelerate subsiding of lattice in positive electrode, reduce the cyclicity of battery, liberated heat then causes decomposing further of electrolyte.
Summary of the invention
The problem run into for tertiary cathode material, the invention provides a kind of good conductivity, oxide coated lithium ion battery positive electrode that corrosion resistance is strong and preparation method thereof, had both improved the electric conductivity on tertiary cathode material surface, had added again the corrosion resistance on positive electrode surface.
The present invention is by the following technical solutions:
The ternary cathode material of lithium ion battery of a kind of electroconductive oxide cladding, its general structure is LixNi1-y-zCoyMzO2/TinO2n-1, 1 x 1.2,0 y 1/3,0 z 1/3, n represents positive integer, and M is one or both elements in Mn, Al.
Further, also include that doped chemical, described doped chemical are one or more in one or more in Zn, Zr, Fe, Mg, Y, La, Ce, V or F, preferably Zn, Mg, La, V, more preferably La.
Further, described electroconductive oxide is sub-titanium oxide, and formula is TinO2n-1, n represents positive integer.
Further, described sub-titanium oxide is Ti4O7,Ti5O9, Ti6O11, Ti7O13In one or more.
Further, described sub-titanium oxide is nanoscale, size controlling 5～300nm, more preferably 20～100nm, particularly preferably 40nm.
The preparation method of above-mentioned ternary cathode material of lithium ion battery, comprises the following steps:
(1) nitrate or the sulfate of doped chemical are dissolved in deionized water, obtain doped chemical solution；
(2) ternary anode material precursor being scattered in step (1) gained doped chemical solution and be sufficiently stirred for, the spraying of gained mixed solution is dried to obtain spheroidal particle；
(3) by step (2) gained spheroidal particle and lithium source mixed sintering in an oxidizing atmosphere, positive electrode active matrix is obtained；
(4) grind after step (3) gained active matrix cooling room temperature, add nanometer Asia titanium dioxide powder, solid phase cladding is carried out by ball milling mixing, then ball milling product and nanometer Asia titanium dioxide powder are scattered in dispersant and add thickening agent stirring and carry out liquid phase coating, be dried to obtainEnd product, i.e.The ternary cathode material of lithium ion battery of electroconductive oxide cladding.
Further, the molar concentration of doped chemical solution is 2～10mol/L, preferably 3～8mol/L；Doped chemical is one or more in Zn, Zr, Fe, Mg, Y, La, Ce, V or F.
Further, described ternary anode material precursor is one or more in nickel cobalt manganese hydroxide, nickel cobalt manganese carbonate, nickel cobalt manganese hydrogen peroxide oxidation thing, nickel cobalt manganese phosphate, nickel cobalt aluminium hydroxide, nickel cobalt aluminum carbonate, nickel cobalt aluminum hydrogen peroxide oxidation thing and nickel cobalt aluminate or phosphate.
Further, ternary anode material precursor is 1:1～10 with the mass ratio of doped chemical solution, preferably 1:1～3.
Further, the stirring of step (2), the time is 2～8h, and speed is 50～600rpm；The inlet temperature being spray-dried is 200～320 DEG C, and outlet temperature is 100～150 DEG C.
Further, the ternary complex in spheroidal particle is 1:1.01～1.05 with the mol ratio of the lithium in lithium source；Described lithium source is one or more in lithium carbonate, Lithium hydrate, lithium fluoride, lithium chloride, lithium bromide, lithium phosphate, phosphoric acid hydrogen two lithium, lithium dihydrogen phosphate, lithium sulfate, Quilonorm (SKB), lithium nitrate, lithium oxalate, lithium formate, tert-butyl alcohol lithium, lithium benzoate and Lithium Citrate de.
Further, in step (3), oxidizing atmosphere is air or oxygen, and Ventilation Rate is 2～15L/min, preferably 3～10L/min；Sintering temperature is 600～1000 DEG C, preferably 700～900 DEG C, heating rate 2～20 DEG C/min, preferably 2～10 DEG C/min；Sintering time 2～24h, preferably 5～12h.
Further, in step (4), active matrix carries out ball milling cladding with sub-titanium oxide 100:1 in mass ratio～10, Ball-milling Time at least 1h, preferably 2～10h, further preferred 2～5h；In liquid phase coating, ball milling product is 100:0.5～8 with the mass ratio of sub-titanium oxide, and liquid phase speed of agitator 0～500rpm stirs 1～10h.
Further, ball milling product and nanometer Asia titanium dioxide powder material and be 1:1.2～2 with dispersant mass ratio；Dispersant is one or more in polyvinyl alcohol, POLYPROPYLENE GLYCOL, polystyrene alcohol etc..
Further, thickening agent consumption is the 0.5～5% of the ball milling product dry material quality with nanometer Asia titanium dioxide powder；Thickening agent is one or more in methylcellulose, hydroxypropyl methyl cellulose, sodium carboxymethyl cellulose, hydroxyethyl cellulose.Baking temperature is 100～600 DEG C, more preferably 300～600 DEG C, and drying time is 5～10h.
Compared with prior art, the present invention has the beneficial effect that:
(1) present invention is fully coated with one layer of nanometer Asia titanium oxide clad by solid phase+liquid phase coating on ternary cathode material of lithium ion battery surface, this clad electric conductivity is far above other metal-oxides close to graphite, positive electrode surface conductivity can be effectively improved, excellent anti-corrosion performance, it is possible to F in opposing electrolyte-Deng erosion, therefore can protect positive electrode under the maximum conditions such as high working voltage, hot environment well, increase the security performance of lithium ion battery, cycle performance and high rate performance.
(2) present invention is effectively increased, by liquid phase doping, the uniformity that doped chemical is distributed at material, can increase positive electrode stability of structure in charge and discharge process.
Accompanying drawing explanation
Fig. 1 is that the embodiment of the present invention 1 is coated with the nickel-cobalt-manganternary ternary anode material of sub-titanium oxide and uncoated tertiary cathode material XRD figure.
Fig. 2 is the nickel-cobalt-manganternary ternary anode material SEM figure that the embodiment of the present invention 1 is coated with sub-titanium oxide.
Fig. 3 is that the embodiment of the present invention 1 is coated with cycle performance figure under the nickel-cobalt-manganternary ternary anode material of sub-titanium oxide and comparative example nickel-cobalt-manganternary ternary anode material room temperature.
Detailed description of the invention
In order to more easily understand the present invention, further illustrate the present invention with specific embodiment below, but the present invention is not limited only to this.
Embodiment 1
With Zinc vitriol for preparation of raw material 1LZn2+Concentration is the solution of 4mol/L, by Ni0.5Co0.2Mn0.3(OH)2Ternary precursor adds Zn by the amount of solid-to-liquid ratio 1:32+Solution, stirs 3h, mixing speed 300rpm, then inlet temperature 260 DEG C, and outlet temperature 100 DEG C spray drying, by the spraying granule that obtains with lithium carbonate with Ni0.5Co0.2Mn0.3(OH)2/Li2CO3Mix for 1:1.02 molar ratio ingredient, add sintering furnace and be passed through oxygen with the Ventilation Rate of 8L/min, 3 DEG C/min heating rate, sinter 8h at 900 DEG C, obtain positive electrode active matrix.By positive electrode active matrix/Ti after the positive electrode active matrix obtained is ground4O7The amount that mass ratio is 100:3 be mixed into nanoscale Ti4O7Powder, ball milling 2h.By ball milling product and nanoscale Ti4O7Powder presses ball milling product/Ti4O7The addition nanoscale Ti that mass ratio is 100:14O7Powder is also scattered in poly-vinyl alcohol solution, and solid-to-liquid ratio is 1:2, and the amount pressing dry material quality 3% adds methylcellulose mix and blend, mixing speed 300rpm, mixing time 3h.By stirring afterproduct at 400 DEG C of dry 3h, obtain being coated with Ti4O7Doping type tertiary cathode material Li1Ni0.5Co0.2Mn0.3O2/Ti4O7。
The electrochemical property test of above-mentioned material uses following method to carry out: with the Li of synthesis in embodiment 11Ni0.5Co0.2Mn0.3O2/Ti4O7Positive electrode is positive active material, and lithium sheet is negative pole, is assembled into experimental button cell.Cathode film consist of m (active substance): m (acetylene black): m (PVDF)=90:4:6, blue electrical testing system is used to test, charging/discharging voltage is 3～4.5V, charge-discharge magnification is 1.0C, carrying out 100 cycle performance tests respectively under room temperature (25 DEG C) and high temperature (40 DEG C, 50 DEG C and 60 DEG C) environment, test result is as shown in table 1.
Embodiment 2
With five nitric hydrate zirconiums for preparation of raw material 2LZr4+Concentration is 3mol/L solution, by Ni0.8Co0.15Al0.05(OH)2Ternary precursor adds Zr by the amount of solid-to-liquid ratio 1:34+Solution, stirs 2h, mixing speed 350rpm.With inlet temperature 270 DEG C, outlet temperature 110 DEG C spray drying.Spraying granule with Lithium hydrate with Ni0.8Co0.15Al0.05(OH)2/ LiOH is the molar ratio ingredient mixing of 1:1.03, adds sintering furnace and is passed through oxygen with the Ventilation Rate of 10L/min, and 4 DEG C/min heating rate sinters 9h at 750 DEG C, obtains positive electrode active matrix.By positive electrode active matrix/Ti after the positive electrode active matrix obtained is ground5O9The amount that mass ratio is 100:4 be mixed into nanoscale Ti5O9Powder, ball milling 3h.By ball milling product and nanoscale Ti5O9Powder presses ball milling product/Ti5O9The amount that mass ratio is 100:1.5 add nanoscale Ti5O9Powder is also scattered in POLYPROPYLENE GLYCOL solution, and solid-to-liquid ratio is 1:2.4, and the amount pressing dry material quality 4% adds methylcellulose mix and blend, mixing speed 320rpm, mixing time 4h.By stirring afterproduct at 300 DEG C of dry 3h, obtain being coated with Ti5O9Doping type nickel cobalt aluminum tertiary cathode material Li1Ni0.8Co0.15Al0.05O2/Ti5O9。
Above-mentioned material uses such as the electrochemical property test of embodiment 1, and result is as shown in table 1.
Embodiment 3
With lanthanum nitrate hexahydrate for preparation of raw material 3LLa3+Concentration is the solution of 5mol/L, by Ni1/3Co1/3Mn1/3(OH)2Ternary precursor adds La by the amount of solid-to-liquid ratio 1:33+Solution, stirs 2.5h, mixing speed 400rpm, then inlet temperature 300 DEG C, and outlet temperature 150 DEG C spray drying, by the spraying granule that obtains with lithium oxalate with Ni1/3Co1/3Mn1/3(OH)2/Li2C2O4Mix for 1:1.04 molar ratio ingredient, add sintering furnace and be passed through oxygen with the Ventilation Rate of 6L/min, 5 DEG C/min heating rate, sinter 8h at 800 DEG C, obtain positive electrode active matrix.By positive electrode active matrix/Ti after the positive electrode active matrix obtained is ground6O11The amount that mass ratio is 100:2.5 be mixed into nanoscale Ti6O11Powder, ball milling 3h.By ball milling product and nanoscale Ti6O11Powder presses ball milling product/Ti6O11The addition nanoscale Ti that mass ratio is 100:1.56O11Powder is also scattered in poly-vinyl alcohol solution, and solid-to-liquid ratio is 1:3, and the amount pressing dry material quality 4% adds hydroxypropyl methyl cellulose mix and blend, mixing speed 380rpm, mixing time 2h.By stirring afterproduct at 360 DEG C of dry 2.5h, obtain being coated with Ti6O11Doping type nickel-cobalt-manganternary ternary anode material Li1Ni1/3Co1/3Mn1/3O2/Ti6O11。
Above-mentioned material uses such as the electrochemical property test of embodiment 1, and result is as shown in table 1.
Comparative example 1
With Zinc vitriol for preparation of raw material 1LZn2+Concentration is the solution of 4mol/L, by Ni0.5Co0.2Mn0.3(OH)2Ternary precursor adds Zn by the amount of solid-to-liquid ratio 1:32+Solution, stirs 2.5h, mixing speed 400rpm, and then with inlet temperature 300 DEG C, outlet temperature 150 DEG C spray drying, by the spraying granule that obtains with lithium oxalate with Ni0.5Co0.2Mn0.3(OH)2/Li2C2O4Mix for 1:1.04 molar ratio ingredient, add sintering furnace and be passed through oxygen with the Ventilation Rate of 6L/min, 5 DEG C/min heating rate, sinter 8h at 800 DEG C, obtain Li1Ni0.5Co0.2Mn0.3O2Positive electrode activity.
Above-mentioned material uses such as the electrochemical property test of embodiment 1, and result is as shown in table 1.
Capability retention (%) after 100 circle circulations under table 1 different temperatures
Case Active base material Doped chemical TinO2n-1 25℃ 40℃ 50℃ 60℃
Embodiment 1 LiNi0.5Co0.2Mn0.3O2 Zn Ti4O7 96.0 94.2 90.2 88.3
Embodiment 2 LiNi0.8Co0.15Al0.05O2 Zr Ti5O9 92.6 90.3 89.5 87.5
Embodiment 3 LiNi1/3Co1/3Mn1/3O2 La Ti6O11 91.0 90.1 88.4 87.6
Comparative example LiNi0.5Co0.2Mn0.3O2 Zn Nothing 88.6 82.3 79.5 70.3
From table 1 it follows that the present invention less significantly improves through the circulation volume conservation rate of the tertiary cathode material of sub-titanium-oxide-coated through the tertiary cathode material of sub-titanium-oxide-coated, the particularly raising effect under hot conditions is more significantly.

Claims (10)

1. the ternary cathode material of lithium ion battery of an electroconductive oxide cladding, it is characterised in that: its knot Structure formula is LixNi1-y-zCoyMzO2/TinO2n-1, 1 x 1.2,0 y 1/3,0 z 1/3, n represents Positive integer, M is one or both elements in Mn, Al.
The ternary cathode material of lithium ion battery of electroconductive oxide the most according to claim 1 cladding, It is characterized in that: also include doped chemical, described doped chemical be Zn, Zr, Fe, Mg, Y, La, Ce, One or more in V or F.
The ternary cathode material of lithium ion battery of electroconductive oxide the most according to claim 1 cladding, It is characterized in that: described electroconductive oxide is sub-titanium oxide, specially Ti4O7,Ti5O9, Ti6O11, Ti7O13 In one or more；Described sub-titanium oxide is nanoscale, and size controlling is 5～300nm.
4. the preparation method of the ternary cathode material of lithium ion battery described in any one of claims 1 to 3, its It is characterised by, comprises the following steps:
(1) nitrate or the sulfate of doped chemical are dissolved in deionized water, obtain doped chemical solution；
(2) ternary anode material precursor is scattered in step (1) gained doped chemical solution and fully stirs Mixing, the spraying of gained mixed solution is dried to obtain spheroidal particle；
(3) by step (2) gained spheroidal particle and lithium source mixed sintering in an oxidizing atmosphere, just obtain Pole material activity matrix；
(4) grind after step (3) gained active matrix cooling room temperature, add nanometer Asia titanium dioxide powder, Carry out solid phase cladding by ball milling mixing, then ball milling product and nanometer Asia titanium dioxide powder are scattered in dispersion In agent and add thickening agent stirring carry out liquid phase coating, be dried to obtain end product, i.e. electroconductive oxide bag The ternary cathode material of lithium ion battery covered.
The preparation method of ternary cathode material of lithium ion battery the most according to claim 4, its feature exists In, ternary anode material precursor is 1:1～10 with the mass ratio of doped chemical solution；Described doped chemical is molten The molar concentration of liquid is 2～10mol/L；Doped chemical be Zn, Zr, Fe, Mg, Y, La, Ce, V or One or more in F；Described ternary anode material precursor is nickel cobalt manganese hydroxide, nickel cobalt manganese Carbonate, nickel cobalt manganese hydrogen peroxide oxidation thing, nickel cobalt manganese phosphate, nickel cobalt aluminium hydroxide, nickel cobalt aluminum carbon One or more in hydrochlorate, nickel cobalt aluminum hydrogen peroxide oxidation thing and nickel cobalt aluminate or phosphate.
The preparation method of ternary cathode material of lithium ion battery the most according to claim 4, its feature exists In, the stirring of step (2), the time is 2～8h, and speed is 50～600rpm；The inlet temperature being spray-dried Being 200～320 DEG C, outlet temperature is 100～150 DEG C.
The preparation method of ternary cathode material of lithium ion battery the most according to claim 4, its feature exists In, the ternary complex in spheroidal particle is 1:1.01～1.05 with the mol ratio of the lithium in lithium source；Described lithium Source is lithium carbonate, Lithium hydrate, lithium fluoride, lithium chloride, lithium bromide, lithium phosphate, phosphoric acid hydrogen two lithium, phosphorus Acid dihydride lithium, lithium sulfate, Quilonorm (SKB), lithium nitrate, lithium oxalate, lithium formate, tert-butyl alcohol lithium, lithium benzoate With one or more in Lithium Citrate de.
The preparation method of ternary cathode material of lithium ion battery the most according to claim 4, its feature exists In, in step (3), oxidizing atmosphere is air or oxygen, and Ventilation Rate is 2～15L/min；Sintering temperature Degree is 600～1000 DEG C, heating rate 2～20 DEG C/min；Sintering time 2～24h.
The preparation method of ternary cathode material of lithium ion battery the most according to claim 4, its feature exists In, in step (4), active matrix carries out ball milling cladding, ball milling with sub-titanium oxide 100:1 in mass ratio～10 Time is more than 1h；In liquid phase coating, ball milling product is 100:0.5～8 with the mass ratio of sub-titanium oxide, and liquid phase is stirred Mix rotating speed 0～500rpm, stir 1～10h.
The preparation method of ternary cathode material of lithium ion battery the most according to claim 4, its feature Being, in step (4), ball milling product with the material of nanometer Asia titanium dioxide powder with dispersant mass ratio is 1:1.2～2；Dispersant is one or more in polyvinyl alcohol, POLYPROPYLENE GLYCOL, polystyrene alcohol etc.； Thickening agent consumption is the 0.5～5% of the ball milling product dry material quality with nanometer Asia titanium dioxide powder；Thickening agent is One in methylcellulose, hydroxypropyl methyl cellulose, sodium carboxymethyl cellulose, hydroxyethyl cellulose or Two or more；Baking temperature is 100～600 DEG C, and drying time is 5～10h.
CN201610507541.2A 2016-06-30 2016-06-30 Conductive oxide coated lithium ion battery tri-element anode material and preparation method thereof Pending CN105977466A (en)

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CN108258224A (en) * 2018-01-22 2018-07-06 华南理工大学 A kind of tertiary cathode material of surface clad oxide and preparation method thereof
CN109326778A (en) * 2018-09-11 2019-02-12 武汉理工大学 A kind of tertiary cathode material and preparation method thereof of nickel acid lanthanum cladding
CN109411710A (en) * 2017-08-17 2019-03-01 江苏津谊新能源科技有限公司 A kind of lithium ion battery material and preparation method thereof
CN109461920A (en) * 2018-11-08 2019-03-12 成都理工大学 The nickelic layered oxide material and its preparation method and application of lanthanum aluminium doping
CN109755487A (en) * 2017-11-07 2019-05-14 中国石油化工股份有限公司 The nickle cobalt lithium manganate and preparation method thereof of the LiFePO4 cladding of metallic element doping
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CN110176587A (en) * 2019-05-28 2019-08-27 华东理工大学 A kind of vanadium ion surface doping nickel cobalt aluminium tertiary cathode material, preparation method and applications
CN111384392A (en) * 2020-03-13 2020-07-07 江门市科恒实业股份有限公司 High-nickel low-cobalt high-voltage-resistant ternary cathode material and preparation method thereof
CN111977655A (en) * 2020-08-28 2020-11-24 郑州轻工业大学 Preparation method and application of vacancy ternary metal MAX phase
CN112175415A (en) * 2020-09-24 2021-01-05 宁波润禾高新材料科技股份有限公司 Water-insoluble pigment dispersion stabilizer and preparation method thereof
CN112635735A (en) * 2020-12-21 2021-04-09 惠州亿纬锂能股份有限公司 Nickel-cobalt lithium manganate precursor with coating structure, preparation method and application thereof
CN112652751A (en) * 2020-12-23 2021-04-13 荆门市格林美新材料有限公司 Precursor for lithium ion battery with double-layer structure, positive electrode material and preparation method
CN112661205A (en) * 2020-12-31 2021-04-16 格林美股份有限公司 Multi-oxide-coated ternary lithium ion battery positive electrode material and preparation method thereof
CN112701290A (en) * 2020-12-29 2021-04-23 西安交通大学 Lithium ion battery anode with titanium suboxide as additive, battery and preparation method
JP2021176123A (en) * 2020-05-01 2021-11-04 トヨタ自動車株式会社 Positive electrode material for lithium secondary battery
CN116395760A (en) * 2023-06-09 2023-07-07 苏州精控能源科技有限公司 Multielement doped high-performance positive electrode material and preparation method thereof

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CN106299340A (en) * 2016-10-11 2017-01-04 苏州大学 Preparation method of modified ternary cathode material
CN109411710A (en) * 2017-08-17 2019-03-01 江苏津谊新能源科技有限公司 A kind of lithium ion battery material and preparation method thereof
CN107768619A (en) * 2017-09-26 2018-03-06 格林美（无锡）能源材料有限公司 A kind of nickelic anode material of lithium battery of high power capacity monocrystalline and preparation method thereof
CN107768619B (en) * 2017-09-26 2020-04-28 格林美（无锡）能源材料有限公司 High-capacity single-crystal high-nickel lithium battery positive electrode material and preparation method thereof
CN109755487A (en) * 2017-11-07 2019-05-14 中国石油化工股份有限公司 The nickle cobalt lithium manganate and preparation method thereof of the LiFePO4 cladding of metallic element doping
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CN109326778A (en) * 2018-09-11 2019-02-12 武汉理工大学 A kind of tertiary cathode material and preparation method thereof of nickel acid lanthanum cladding
CN109461920B (en) * 2018-11-08 2022-01-11 成都理工大学 Lanthanum-aluminum-doped high-nickel layered oxide material and preparation method and application thereof
CN109461920A (en) * 2018-11-08 2019-03-12 成都理工大学 The nickelic layered oxide material and its preparation method and application of lanthanum aluminium doping
CN110061226A (en) * 2019-05-07 2019-07-26 湖南金富力新能源股份有限公司 The positive electrode of sub- titanium-oxide-coated, the preparation method of positive electrode and lithium ion battery
CN110061226B (en) * 2019-05-07 2020-04-10 湖南金富力新能源股份有限公司 Titanium suboxide-coated positive electrode material, preparation method of positive electrode material and lithium ion battery
CN110176587A (en) * 2019-05-28 2019-08-27 华东理工大学 A kind of vanadium ion surface doping nickel cobalt aluminium tertiary cathode material, preparation method and applications
CN111384392A (en) * 2020-03-13 2020-07-07 江门市科恒实业股份有限公司 High-nickel low-cobalt high-voltage-resistant ternary cathode material and preparation method thereof
CN111384392B (en) * 2020-03-13 2021-02-19 江门市科恒实业股份有限公司 High-nickel low-cobalt high-voltage-resistant ternary cathode material and preparation method thereof
JP2021176123A (en) * 2020-05-01 2021-11-04 トヨタ自動車株式会社 Positive electrode material for lithium secondary battery
CN111977655A (en) * 2020-08-28 2020-11-24 郑州轻工业大学 Preparation method and application of vacancy ternary metal MAX phase
CN112175415A (en) * 2020-09-24 2021-01-05 宁波润禾高新材料科技股份有限公司 Water-insoluble pigment dispersion stabilizer and preparation method thereof
CN112175415B (en) * 2020-09-24 2022-01-07 宁波润禾高新材料科技股份有限公司 Water-insoluble pigment dispersion stabilizer and preparation method thereof
CN112635735A (en) * 2020-12-21 2021-04-09 惠州亿纬锂能股份有限公司 Nickel-cobalt lithium manganate precursor with coating structure, preparation method and application thereof
CN112652751A (en) * 2020-12-23 2021-04-13 荆门市格林美新材料有限公司 Precursor for lithium ion battery with double-layer structure, positive electrode material and preparation method
CN112652751B (en) * 2020-12-23 2022-01-11 荆门市格林美新材料有限公司 Precursor for lithium ion battery with double-layer structure, positive electrode material and preparation method
CN112701290A (en) * 2020-12-29 2021-04-23 西安交通大学 Lithium ion battery anode with titanium suboxide as additive, battery and preparation method
CN112661205A (en) * 2020-12-31 2021-04-16 格林美股份有限公司 Multi-oxide-coated ternary lithium ion battery positive electrode material and preparation method thereof
CN116395760A (en) * 2023-06-09 2023-07-07 苏州精控能源科技有限公司 Multielement doped high-performance positive electrode material and preparation method thereof
CN116395760B (en) * 2023-06-09 2023-08-15 苏州精控能源科技有限公司 Multielement doped high-performance positive electrode material and preparation method thereof

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