CN105470499A - Preparation method for improving compaction density of NCA cathode material for lithium-ion battery - Google Patents

Preparation method for improving compaction density of NCA cathode material for lithium-ion battery Download PDF

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Publication number
CN105470499A
CN105470499A CN201510878319.9A CN201510878319A CN105470499A CN 105470499 A CN105470499 A CN 105470499A CN 201510878319 A CN201510878319 A CN 201510878319A CN 105470499 A CN105470499 A CN 105470499A
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China
Prior art keywords
nca
lithium
fused
cathode
nickel cobalt
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CN201510878319.9A
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Chinese (zh)
Inventor
沈晓彦
牛翱翔
冯力
黄金健
李玲俐
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江苏海四达电源股份有限公司
江苏省新动力电池及其材料工程技术研究中心有限公司
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Priority to CN201510878319.9A priority Critical patent/CN105470499A/en
Publication of CN105470499A publication Critical patent/CN105470499A/en

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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection 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
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a preparation method for improving compaction density of a cathode material lithium nickel cobalt aluminum oxide (NCA) for a lithium-ion battery, in particular a method for preparing a high-compaction density lithium nickel cobalt aluminum oxide ternary material by mixing a conventional lithium nickel cobalt aluminum oxide (LiNi<0.8>Co<0.15>Al<0.05>O<2>) ternary material with a lithium nickel cobalt aluminum oxide (LiNi<0.8>Co<0.15>Al<0.05>O<2>) ternary material prepared through a molten salt medium method. The method comprises the following steps: (a) preparing a conventional lithium nickel cobalt aluminum oxide cathode material LiNi<0.8>Co<0.15>Al<0.05>O<2>; (b) preparing the lithium nickel cobalt aluminum oxide cathode material LiNi<0.8>Co<0.15>Al<0.05>O<2> by the molten salt medium method; and (c) mixing the conventional ternary cathode material with the ternary cathode material prepared by the molten salt medium method in a three-dimensional cone mixer at a certain mass ratio. The material prepared by the method not only has high compaction density, but also has relatively high gram capacity and cycle performance and good high temperature storage performance.

Description

A kind of preparation method improving lithium ion battery NCA positive electrode compacted density

Technical field

What the present invention relates to is anode material for lithium-ion batteries technical field, is specifically related to a kind of preparation method improving NCA positive electrode compacted density.

Background technology

Lithium ion battery has the advantage such as high energy density, high discharge platform, is widely used in 3C electronic product, electric tool and energy-storage battery field.Along with the development of lithium battery technology, every profession and trade requires more and more higher to performance of lithium ion battery, the future developments such as lithium ion battery product is tending towards light to high power capacity, quality day by day, high rate performance and good cycle, especially high-energy-density direction.

High Energy Density Materials, compacted density and gram volume mainly by improving material realize.LiCoO 2it is current the most widely used positive electrode, although it has larger compacted density, but himself gram volume as compared to NCM with NCA not high, usually its gram volume is improved in the mode promoting charging/discharging voltage, but material structure unstable and can along with a large amount of side reactions under high voltage under high voltage; For NCM, its compacted density is lower, although cause its gram volume high, volume energy density is not high; NCA itself has larger compacted density and gram volume is large, is a kind of good high Energy Density Materials.

Usually the NCA compacted density prepared is at 3.55-3.65g/cm 3.The NCA regular appearance that fused-salt medium method prepares, and be a monocrystal particle, the density larger than having with secondary spherical Particle Phase.The mode that this experiment carries out grating by the NCA that bulky grain secondary spherical NCA and fused-salt medium method prepare regular appearance improves compacted density.

Summary of the invention

Technical problem to be solved by this invention is, providing a kind of by improving the compacted density of NCA ternary material, can improve the preparation method of the blending and modifying NCA tertiary cathode material of the electrical properties such as lithium ion battery energy density.

The preparation method of NCA ternary material blending and modifying positive electrode of the present invention comprises the following steps:

A. conventional three-way positive electrode Li (Ni is prepared xco yal z) O 2, concrete steps are:

A1. by Ni, Co, Al tri-metal ion species (code name: M) and the LITHIUM BATTERY LiOH in NCA ternary precursor, three-dimensional cone-type mixer is put into the mol ratio of Li/M=(1.02-1.1) ︰ 1, and it is little of evenly to add batch mixing ball mixing 4-6, wherein ratio of grinding media to material is 0.3-0.8.

A2. the material mixed is put into Muffle furnace and carry out multistage sintering, first at 400-500 DEG C of pre-burning 2-5h; After 700-800 DEG C sintering 5-10h; Naturally cool with stove afterwards, fragmentation obtains conventional three-way positive electrode Li (Ni xco yal z) O 2(x=0.75-0.85, y=0.10-0.2, z=0.04-0.06);

B. adopt fused-salt medium legal system for tertiary cathode material Li (Ni xco yal z) O 2, concrete steps are:

B1. LiOH and NCA ternary precursor is put into three-dimensional cone-type mixer with the mol ratio of Li/M=(1.02-1.1) ︰ 1, and add the mixing of batch mixing ball 4-6 hour until evenly, wherein batch mixing ball and presoma mass ratio are 0.3-0.8;

B2. by the mixture in b1 with (1-5): the ratio of 1 with NaCl at three-dimensional blender tank mixing 4-6 hour;

B3. by the mixture in b2, sintering 7-10 hour is carried out at 800-1000 DEG C; Omnipotent disintegrating machine is used to carry out fragmentation after cooling;

B4. with the NaCl in distilled water washing b3, filter; Products obtained therefrom will be filtered dry, more also fragmentation in double sintering 4-6 hour at 750 DEG C-850 DEG C;

C. by conventional NCA tertiary cathode material with to adopt the standby tertiary cathode material of fused-salt medium legal system to mix 4-6 according to the mass ratio of 6:4 to 9:1 in the mixed machine of three-dimensional cone little of evenly.

The present invention is by conventional NCA ternary material and the standby NCA ternary material blending and modifying of fused-salt medium legal system, and the NCA ternary material prepared has 3.8-3.85g/cm 3compacted density.Fused-salt medium method can provide liquid phase environment for reaction, particle can fully be grown, form the primary particle of well-grown, regular appearance, thus reduce the space of inside particles, improve particle real density, sample prepared by the method not only has higher compacted density, also has higher gram volume and good high temperature performance.

Accompanying drawing explanation

Fig. 1 schemes for adopting the standby NCA ternary material SEM of the fused-salt medium legal system mentioned by the present invention.

The gram volume data of Fig. 2 sample prepared by the present invention.

The high rate performance curve chart of Fig. 3 sample prepared by the present invention.

The cycle performance curve chart of Fig. 4 sample prepared by the present invention.

Embodiment

The present invention will be described below to enumerate specific embodiment.

Embodiment 1:

A. conventional three-way positive electrode Li (Ni is prepared 0.8co 0.15al 0.05) O 2, concrete steps are:

A1. by Ni, Co, Al tri-metal ion species (code name: M) and the LITHIUM BATTERY LiOH of NCA ternary precursor, put into the mixed machine of three-dimensional cone with the mol ratio of Li/M=1.03:1 and add batch mixing ball and mix 5 hours, wherein batch mixing ball is 0.4 with quality of material ratio.

A2. the material mixed is put into Muffle furnace and carry out multistage sintering, first at 400 DEG C of pre-burning 5h; After 700 DEG C sintering 8h; Naturally cool with stove afterwards, fragmentation obtains conventional three-way positive electrode Li (Ni 0.8co 0.15al 0.05) O 2;

B. adopt fused-salt medium legal system for tertiary cathode material Li (Ni 0.8co 0.15al 0.05) O 2, concrete steps are:

B1. LiOH and NCA ternary precursor being put into the mixed machine of three-dimensional cone with the mol ratio of Li/M=1.03:1 and adding batch mixing ball mixes 5 little of evenly, and wherein ratio of grinding media to material is 0.4;

B2. the mixture in b1 is mixed 5 hour with NaCl at three-dimensional blender tank with the ratio of 1:3;

B3. by the mixture in b2, sintering is carried out 9 hours at 1000 DEG C; Omnipotent disintegrating machine is used to carry out fragmentation after cooling;

B4. with the NaCl in distilled water washing b3, filter; Products obtained therefrom will be filtered dry, then double sintering also fragmentation in 5 hours at 750 DEG C;

C. by conventional NCA tertiary cathode material and the tertiary cathode material that adopts fused-salt medium legal system standby, according to the mass ratio of 8:2, in the mixed machine of three-dimensional cone, mixing 5 hours is evenly.

The present invention is by conventional NCA ternary material and the standby NCA ternary material blending and modifying of fused-salt medium legal system, and the NCA ternary material prepared has 3.82-3.87g/cm 3compacted density, and embody extremely excellent spray charging precipitator and capacity restoration rate, as shown in table one, table two.

The physical and chemical indexes of sample prepared by table one the present invention

The spray charging precipitator of sample prepared by table two the present invention and capacity restoration rate

Numbering 1# 2# 3# 4# 5# Spray charging precipitator (%) 85.4 86.2 86.3 84.0 84.8 Capacity restoration rate (%) 96.9 97.7 97.8 97.5 96.7

Embodiment 2:

Conventional NCA tertiary cathode material and the tertiary cathode material that adopts fused-salt medium legal system standby is little of evenly according to mass ratio mixing 5 in the mixed machine of three-dimensional cone of 7.5:2.5.The present invention is by conventional NCA ternary material and the standby NCA ternary material blending and modifying of fused-salt medium legal system, and the NCA ternary material prepared has 3.80-3.85g/cm 3compacted density.

Embodiment 3:

Conventional NCA tertiary cathode material and the tertiary cathode material that adopts fused-salt medium legal system standby is little of evenly according to mass ratio mixing 5 in the mixed machine of three-dimensional cone of 9:1.The present invention is by conventional NCA ternary material and the standby NCA ternary material blending and modifying of fused-salt medium legal system, and the NCA ternary material prepared has the compacted density of 3.75-3.80g/cm3.

Claims (6)

1. one kind is improved lithium ion battery NCA anode material nickel cobalt lithium aluminate LiNi 0.8co 0.15al 0.05o 2compacted density preparation method, it is characterized in that first lithium salts and NCA presoma being mixed with certain proportion, by the pre-burning of certain hour and double sintering, the conventional nickel cobalt lithium aluminate cathode material LiNi of broken preparation 0.8co 0.15al 0.05o 2, then adopt fused-salt medium legal system for nickel cobalt lithium aluminate cathode material LiNi 0.8co 0.15al 0.05o 2, finally the tertiary cathode material that conventional three-way positive electrode is standby with adopting fused-salt medium legal system being mixed according to certain mass ratio in three-dimensional cone-type mixer, obtaining end product.
2. lithium salts according to claim 1, is characterized in that lithium salts refers to one or more of lithium carbonate, LiOH etc.
3. lithium salts according to claim 1 and NCA presoma mix with certain proportion, it is characterized in that Li in lithium salts +with in NCA presoma Ni, Co, Al tri-the molar ratio of metal ion species be that (1.02-1.1) ︰ 1, its incorporation time is 4-6 hour.
4. pre-burning according to claim 1 and double sintering, it is characterized in that calcined temperature is 400-500 DEG C, sintering time is 2-5h; Double sintering temperature is 700-800 DEG C, and sintering time is 5-10h.
5. fused-salt medium method according to claim 1, it is characterized in that one or more that fused salt refers in KCl, NaCl etc., and the composite material of fused salt with lithium salts and NCA presoma is mixed by a certain percentage, mixed proportion is (1-5): 1, and incorporation time is 4-6 hour.
6. the tertiary cathode material that conventional three-way positive electrode is standby with adopting fused-salt medium legal system according to claim 1 mixes according to certain mass ratio, it is characterized in that conventional three-way quality of materials accounts for the 60%-90% of composite material gross mass, its incorporation time is 4-6 hour.
CN201510878319.9A 2015-12-04 2015-12-04 Preparation method for improving compaction density of NCA cathode material for lithium-ion battery CN105470499A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106025179A (en) * 2016-06-30 2016-10-12 湖南桑顿新能源有限公司 Method for preparing cathode material lithium nickel cobalt aluminate for lithium ion battery by spray drying
CN106252717A (en) * 2016-10-19 2016-12-21 江苏海四达电源股份有限公司 High circulation electric vapour vehicle lithium-ion power battery and preparation method thereof
CN106328902A (en) * 2016-10-19 2017-01-11 江苏海四达电源股份有限公司 High-capacity lithium-ion power battery for electromobiles and preparation method thereof
CN107681128A (en) * 2017-08-14 2018-02-09 北大先行科技产业有限公司 A kind of anode material for lithium-ion batteries and preparation method thereof
CN108011144A (en) * 2017-10-31 2018-05-08 合肥国轩高科动力能源有限公司 A kind of recovery processing technique of ternary cathode material of lithium ion battery

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Publication number Priority date Publication date Assignee Title
CN104037404A (en) * 2014-07-01 2014-09-10 天津巴莫科技股份有限公司 Lithium nickel cobalt aluminum oxide and lithium manganese oxide composite material used for lithium ion battery and preparation method thereof
CN104393285A (en) * 2014-10-14 2015-03-04 鸿源控股有限公司 Nickel-cobalt-aluminum ternary positive electrode material and its preparation method
CN104701533A (en) * 2015-02-11 2015-06-10 江苏科捷锂电池有限公司 Preparation method of 523 ternary material blending modified positive material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104037404A (en) * 2014-07-01 2014-09-10 天津巴莫科技股份有限公司 Lithium nickel cobalt aluminum oxide and lithium manganese oxide composite material used for lithium ion battery and preparation method thereof
CN104393285A (en) * 2014-10-14 2015-03-04 鸿源控股有限公司 Nickel-cobalt-aluminum ternary positive electrode material and its preparation method
CN104701533A (en) * 2015-02-11 2015-06-10 江苏科捷锂电池有限公司 Preparation method of 523 ternary material blending modified positive material

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106025179A (en) * 2016-06-30 2016-10-12 湖南桑顿新能源有限公司 Method for preparing cathode material lithium nickel cobalt aluminate for lithium ion battery by spray drying
CN106252717A (en) * 2016-10-19 2016-12-21 江苏海四达电源股份有限公司 High circulation electric vapour vehicle lithium-ion power battery and preparation method thereof
CN106328902A (en) * 2016-10-19 2017-01-11 江苏海四达电源股份有限公司 High-capacity lithium-ion power battery for electromobiles and preparation method thereof
CN107681128A (en) * 2017-08-14 2018-02-09 北大先行科技产业有限公司 A kind of anode material for lithium-ion batteries and preparation method thereof
CN107681128B (en) * 2017-08-14 2020-10-16 北大先行科技产业有限公司 Lithium ion battery anode material and preparation method thereof
CN108011144A (en) * 2017-10-31 2018-05-08 合肥国轩高科动力能源有限公司 A kind of recovery processing technique of ternary cathode material of lithium ion battery
CN108011144B (en) * 2017-10-31 2019-09-13 合肥国轩高科动力能源有限公司 A kind of recovery processing technique of ternary cathode material of lithium ion battery

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Application publication date: 20160406