CN106159220B - two-step method for preparing lithium ion battery anode material L iNi0.80Co0.15Al0.05O2Method (2) - Google Patents
two-step method for preparing lithium ion battery anode material L iNi0.80Co0.15Al0.05O2Method (2) Download PDFInfo
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- CN106159220B CN106159220B CN201510194106.4A CN201510194106A CN106159220B CN 106159220 B CN106159220 B CN 106159220B CN 201510194106 A CN201510194106 A CN 201510194106A CN 106159220 B CN106159220 B CN 106159220B
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- lithium
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- ion batteries
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- 238000000034 method Methods 0.000 title claims abstract description 45
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 23
- 239000010405 anode material Substances 0.000 title claims abstract description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 14
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 229910011456 LiNi0.80Co0.15Al0.05O2 Inorganic materials 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- 239000004411 aluminium Substances 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical group [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- KSHLPUIIJIOBOQ-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[Co++].[Ni++] Chemical compound [O--].[O--].[O--].[O--].[Co++].[Ni++] KSHLPUIIJIOBOQ-UHFFFAOYSA-N 0.000 claims description 8
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- AMDUMQZTBRMNMG-UHFFFAOYSA-N nickel nitric acid Chemical group [Ni].O[N+]([O-])=O AMDUMQZTBRMNMG-UHFFFAOYSA-N 0.000 claims 1
- 229910018632 Al0.05O2 Inorganic materials 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 16
- 239000002245 particle Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- -1 nickel oxide cobalt aluminum Chemical compound 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract description 2
- 239000008139 complexing agent Substances 0.000 abstract description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 150000001868 cobalt Chemical class 0.000 abstract 1
- 239000002086 nanomaterial Substances 0.000 abstract 1
- 150000002815 nickel Chemical class 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 230000002441 reversible effect Effects 0.000 abstract 1
- 229910013716 LiNi Inorganic materials 0.000 description 18
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 238000005245 sintering Methods 0.000 description 8
- 238000000975 co-precipitation Methods 0.000 description 7
- 239000003643 water by type Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 4
- FCVHBUFELUXTLR-UHFFFAOYSA-N [Li].[AlH3] Chemical compound [Li].[AlH3] FCVHBUFELUXTLR-UHFFFAOYSA-N 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910001429 cobalt ion Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000003836 solid-state method Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000186216 Corynebacterium Species 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910015701 LiNi0.85Co0.10Al0.05O2 Inorganic materials 0.000 description 1
- 229910014330 LiNi1-x-yCoxAlyO2 Inorganic materials 0.000 description 1
- 229910014360 LiNi1−x−yCoxAlyO2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 1
- PZFKDUMHDHEBLD-UHFFFAOYSA-N oxo(oxonickeliooxy)nickel Chemical compound O=[Ni]O[Ni]=O PZFKDUMHDHEBLD-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- H01M4/485—Selection 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
the invention discloses a two-step method for preparing a lithium ion battery anode material L iNi0.80Co0.15Al0.05O2The method of (1). Firstly, carrying out hydrothermal reaction on nickel salt, cobalt salt and aluminum salt with a hydrolytic agent and a surfactant to form a nickel oxide cobalt aluminum precursor material; then adding a lithium source and a complexing agent to obtain gel; then obtaining an obvious laminated structure after high-temperature roastingAnd the atoms are arranged orderly in a nanoscale material. The method has the advantages of wide raw material source, simple operation process, low required equipment cost, low calcination temperature, production cost saving, fine and uniform particle size of the synthesized nickel-cobalt-aluminum-lithium, high crystallinity, better reversible capacity and good cycle life, and can meet the requirements of practical production application of the lithium ion battery.
Description
Technical field
The present invention relates to a kind of methods preparing anode material for lithium-ion batteries, and in particular to a kind of two-step mode technique preparation
Anode material for lithium-ion batteries LiNi0.80Co0.15Al0.05O2Method, belong to battery material preparation field.
Background technology
For lithium ion battery compares lead-acid battery, have long lifespan, it is safe to use, can fast charging and discharging, high temperature resistant, ratio
The advantages that capacity is big, environmentally protective, therefore it is widely used in the industries such as communication, traffic.Lithium ion battery anode material nickel cobalt
Aluminium lithium (LiNi1-x-yCoxAlyO2, also referred to as NCA) and it is the LiCoO based on stratiform2、LiNiO2The material of structure is positive electrode current
One new direction of investigation of materials.It has good excellent of high theoretical capacity (274mAh/g), low cost, hypotoxicity, thermal stability
Point is considered being hopeful very much to apply on high-energy, high power power battery, especially electric vehicle.
The method of traditional synthesis nickel cobalt aluminium lithium has high temperature solid-state method, coprecipitation, sol-gal process etc..High temperature solid-state method
The calcination temperature high time is long, waste of energy, and granularity and pattern are difficult to control.(Zhu Xianjun, Zhan Hui, the Zhou Yunhong such as Zhu Xianjun
.LiNi0.85Co0.10Al0.05O2Positive electrode synthesizes and characterizes [J] Rare Metals Materials and engineering, 2005,34 (12):1862-
It 1865) will analysis pure raw material LiOHH2O, Ni2O3, Co2O3With Al (OH)3It also known as measures, mix, grind by certain metering score
Mill, grinds, tabletting again after pre-burning, and 725 DEG C of roastings are for 24 hours up to product LiNi in oxygen0.85Co0.10Al0.05O2.But particle
Morphology and size is uneven, so causing cycle performance more general.
Material prepared by coprecipitation is easy to reunite, and in the form of sheets and polygonal, physical property is bad, and practical value is little.
(Hui Cao, Baojia Xia, Naixin Xu, the et al.Structural and electrochemical such as H.Cao
characteristics of Co and Al co-doped lithium nickelate cathode materials for
lithium-ion batteries[J],Journal of Alloys and Compounds,2004,376:282-286) adopt
It is prepared for LiNi with conventional coprecipitation0.8Co0.2-xAlxO2(0≤x≤0.2) positive electrode.Although cycle performance is fine,
Initial capacity is relatively low, only 160mAh/g.
Sol-gal process is difficult to control granule-morphology, and is easily formed and reunited.(Chang the Joo Han, Jang such as C.J.Han
Hyuk Yoon,Ho Jang,et al.Electrochemical properties of LiNi0.8Co0.2- xAlxO2prepared by a sol-gel method[J].J Power Sources.2004,136:132-138) with propylene
Acid is complexing agent, and lithium, nickel, the acetate of cobalt and aluminum nitrate are that raw material has prepared nickel cobalt aluminium lithium material.But due to particle ruler
It is very little larger, and it is serious to reunite, so cycle performance is more general.
Domestic synthesis nickel cobalt aluminium lithium mainly uses coprecipitation and spray drying process at present.
There is the following patent using coprecipitation.Chinese patent CN201010624564.4 discloses a kind of lithium ion
The preparation method of anode material nickel cobalt lithium aluminate, using metal salt solution and precipitating reagent the precipitation synthesis nickel cobalt aluminium forerunner of nickel cobalt aluminium
Body.Aluminium ion is more difficult to form homogeneous coprecipitation with nickel cobalt ion, is extremely difficult to the equally distributed purpose of nickel cobalt aluminium element, it will lead
It causes aluminium to be unevenly distributed in nickel cobalt aluminic acid lithium material, influences the electrical property of material, especially cycle performance.Also have basic herein
The upper nickel cobalt aluminum complex hydroxide or carbonate deposition prepared using complexing-coprecipitation, then this presoma is pressed with lithium source
After certain proportion mixing, it is sintered in oxygen atmosphere high temperature.Such as Chinese patent CN20130055624.9, etc..Due to Al3+
Introducing, be difficult to be formed single layer structure with nickel cobalt, lattice order is deteriorated, and particle spherical morphology is caused to be deteriorated, flowing
Property decline, obtained presoma tap density is relatively low.
There is following patent using spray drying process.Chinese patent CN201410206372.X proposes a kind of using two steps
The method that spray drying prepares nickel cobalt lithium aluminate cathode material.Wherein to coordinate ball milling and the long-time high temperature in oxygen atmosphere
Roasting, complex process and energy consumption is very big.
Chinese patent CN201310697497.2 proposes a kind of lithium ion battery nickel cobalt aluminium complex ternary positive electrode
Preparation method.Similarly with this patent, Ni is initially formed using crystallisation0.75Co0.15Al0.1(OH)2.05Presoma.But this is specially
Profit subsequently synthesizes NCA final materials using high-temperature roasting.There is no control presoma patterns for the patent, and subsequently use
It is solid reaction process, it is more difficult to control particle scale and pattern.
Invention content
The purpose of the present invention is to provide a kind of two-step mode techniques to prepare anode material for lithium-ion batteries
LiNi0.80Co0.15Al0.05O2Method.The method materials derive from a wealth of sources, at low cost, easily controllable, and the material granule of formation is equal
It is even and fine small, excellent electrochemical performance.This method is applicable to industrialization large-scale production.
Realize the technical scheme is that：
A kind of two-step method prepares anode material for lithium-ion batteries LiNi0.80Co0.15Al0.05O2Method, including following implementation
Step：
(1) nickel source of certain stoichiometric ratio, cobalt source, silicon source, hydrolytic reagent and surfactant is soluble in water, in room temperature
Under stir to get mixed solution, be transferred in reaction kettle, in 110-130 DEG C of 6~10h of hydro-thermal reaction；
(2) it will precipitate and take out in reaction kettle, grind into powder after drying；
(3) gained powder is sintered 3~4h for 300 DEG C in air, naturally cools to room temperature, obtains rodlike cobalt nickel oxide
Aluminium；
(4) lithium source and citric acid of cobalt nickel oxide aluminium and certain stoichiometric ratio obtained by step (3) is soluble in water, in room
Suspension is stirred to get under temperature, this suspension is obtained into gel in 80~90 DEG C of stirring in water bath；
(5) grind into powder after gel drying；
(6) powder is placed and is sintered 2~4h at 750 DEG C in air, naturally cool to room temperature to get
LiNi0.80Co0.15Al0.05O2。
Wherein, in step (1), the nickel source, cobalt source, silicon source, the molar ratio of hydrolytic reagent are 0.80:0.15:0.05:1；
The nickel source is nickel nitrate；Cobalt source is cobalt nitrate；Silicon source is aluminum nitrate；Hydrolytic reagent is ammonium oxalate, and surfactant is three second
Hydramine；A concentration of 0.35M of hydrolytic reagent in mixed solution；The volume ratio of surfactant and water is 1:40.
In step (1), 1h is stirred at room temperature；Liquor capacity accounts for 40% in reaction kettle；6h at preferably 120 DEG C of hydro-thermal reaction.
It is dry using vacuum drying at 60~80 DEG C in step (2).
In step (3), heating rate is 5~10 DEG C/min.
In step (4), lithium source, cobalt nickel oxide aluminium, citric acid molar ratio be 1.04:1:1, lithium source is lithium nitrate.
In step (5), drying temperature is 110 DEG C~150 DEG C.
In step (6), heating rate is 5~10 DEG C/min.
The present invention has following remarkable advantage compared with its prior art：(1) citric acid method used, reduces
Sintering temperature reduces sintering time, has saved energy consumption in process of production, to considerably reduce production cost；(2)
The material granule uniform particle sizes obtained by way of the synthesis of two steps are controllable, and better crystallinity degree, consistency is high, to improve material
Chemical property；(3) this method is simple and practicable, and preparation process, required equipment are relatively simple, at low cost, is conducive to extensive
Industrialized production.
Description of the drawings
Fig. 1 is the LiNi of gained in the embodiment of the present invention 10.80Co0.15Al0.05O2XRD diagram.
Fig. 2 is the LiNi of gained in the embodiment of the present invention 10.80Co0.15Al0.05O2Second of charge and discharge electrograph.
Fig. 3 is the LiNi of gained in the embodiment of the present invention 10.80Co0.15Al0.05O2Cycle performance figure.
Fig. 4 is the rodlike Ni of gained in the embodiment of the present invention 10.80Co0.15Al0.05The SEM of O schemes.
Fig. 5 is the LiNi of gained in the embodiment of the present invention 10.80Co0.15Al0.05O2SEM figure.
Fig. 6 is the LiNi prepared in the embodiment of the present invention 20.80Co0.15Al0.05O20.1c rate charge-discharges under the conditions of
Secondary charge and discharge electrograph.
Fig. 7 is the LiNi prepared in the embodiment of the present invention 20.80Co0.15Al0.05O21c rate charge-discharges under the conditions of 50
The charge and discharge electrograph of cycle.
Fig. 8 is the LiNi prepared in the embodiment of the present invention 30.80Co0.15Al0.05O20.1c rate charge-discharges under the conditions of
Secondary charge and discharge electrograph.
Fig. 9 is the LiNi prepared in the embodiment of the present invention 30.80Co0.15Al0.05O21c rate charge-discharges under the conditions of 50
The charge and discharge electrograph of cycle.
Specific implementation mode
Two-step method of the present invention prepares anode material for lithium-ion batteries LiNi0.80Co0.15Al0.05O2Method, by following implementation
Example is further elaborated.
Example 1
(1) it mixes：Stoichiometrically 0.80:0.15:0.05:1 nickel source, cobalt source, silicon source and ammonium oxalate, weighs respectively
Nickel nitrate 3.257g, cobalt nitrate 0.611g, aluminum nitrate 0.263g, ammonium oxalate 1.990g is dissolved in 40ml deionized waters, in room temperature
Lower stirring 30min makes it be sufficiently mixed uniformly, and 1ml triethanolamines are then added, and continues to stir 30min, it is suspended to obtain light green color
Liquid.
(2) hydro-thermal reaction：Suspension is transferred in 100ml reaction kettles, is dropped with stove after 120 DEG C of reaction 6h in drying box
To room temperature.
(3) drying and sintering：Precipitation in reaction kettle is taken out by filtering, is cleaned repeatedly with deionized water 3~4 times, vacuum
80 DEG C of next night drying.Depositing abrasive is become into powder.3h completes sintering to obtained powder at 300 DEG C in air, obtains stick
Shape cobalt nickel oxide aluminium.
(4) it mixes：Stoichiometrically 1.04:1:1 lithium source, powder and citric acid, weighs lithium nitrate 0.783g respectively,
Powder 0.800g obtained by back, citric acid 2.295g are dissolved in 20ml deionized waters, 3h are stirred at room temperature, and make it fully
It is uniformly mixed, obtains dark-brown suspension.
(5) chelatropic reaction：This suspension is stirred into 3h in 85 DEG C of stirring in water bath device, moisture is made to be evaporated, forms gel.
(6) dry：This gel is dried in vacuum drying chamber at 140 DEG C, loose porous solid is formed, takes out grinding shape
At powder.
(7) it roasts：Powder is placed and is sintered 2h at 750 DEG C in air, naturally cool to room temperature to get
LiNi0.80Co0.15Al0.05O2。
Fig. 1 is preparation gained LiNi under the conditions of example 10.80Co0.15Al0.05O2XRD diagram, in apparent
LiNi0.80Co0.15Al0.05O2Phase.
Fig. 2 is preparation gained LiNi under the conditions of example 10.80Co0.15Al0.05O20.1c rate charge-discharges under the conditions of second
Secondary charge and discharge electrograph, cycle specific discharge capacity reaches 180mAh/g for the second time as we know from the figure.
Fig. 3 is preparation gained LiNi under the conditions of example 10.80Co0.15Al0.05O21c rate charge-discharges under the conditions of 50 follow
The charge and discharge electrograph of ring, as can be seen from the figure still reaches the specific discharge capacity of 100mAh/g under high magnification.
Fig. 4 is the SEM figures that the rodlike cobalt nickel oxide aluminium obtained when first step reaction is completed is prepared under the conditions of example 1, from figure
In it can be seen that material be in corynebacterium, length is on nanoscale.
Fig. 5 is the LiNi for preparing reaction under the conditions of example 1 and completing to obtain0.80Co0.15Al0.05O2SEM figure, can from figure
To find out that material particle size is uniformly tiny.
Example 2
(1) it mixes：Stoichiometrically 0.80:0.15:0.05:1 nickel source, cobalt source, silicon source and ammonium oxalate, weighs respectively
Nickel nitrate 3.257g, cobalt nitrate 0.611g, aluminum nitrate 0.263g, ammonium oxalate 1.990g is dissolved in 40ml deionized waters, in room temperature
Lower stirring 30min makes it be sufficiently mixed uniformly, and 1ml triethanolamines are then added, and continues to stir 30min, it is suspended to obtain light green color
Liquid.
(2) hydro-thermal reaction：Suspension is transferred in 50ml reaction kettles, is dropped with stove after 130 DEG C of reaction 8h in drying box
To room temperature.
(3) drying and sintering：Precipitation in reaction kettle is taken out by filtering, is cleaned repeatedly with deionized water 3~4 times, vacuum
60 DEG C of next night drying.Depositing abrasive is become into powder.3h completes sintering to obtained powder at 300 DEG C in air, obtain aluminium,
Cobalt ions is solid-solution in rodlike (Ni therein0.80Co0.15Al0.05)2O3。
(4) it mixes：Stoichiometrically 1.04:1:1 lithium source, powder and citric acid, weighs lithium nitrate 0.979g respectively,
Powder 1.000g obtained by back, citric acid 2.869g are dissolved in 15ml deionized waters, 3h are stirred at room temperature, and make it fully
It is uniformly mixed, obtains dark-brown suspension.
(5) chelatropic reaction：This suspension is stirred into 3h in 80 DEG C of stirring in water bath device, moisture is made to be evaporated, forms gel.
(6) dry：This gel is dried in vacuum drying chamber at 110 DEG C, loose porous solid is formed, takes out grinding shape
At powder.
(7) it roasts：Powder is placed and is sintered 3h at 750 DEG C in air, naturally cool to room temperature to get
LiNi0.80Co0.15Al0.05O2。
Fig. 6 is preparation gained LiNi under the conditions of example 20.80Co0.15Al0.05O20.1c rate charge-discharges under the conditions of second
Secondary charge and discharge electrograph.
Fig. 7 is preparation gained LiNi under the conditions of example 20.80Co0.15Al0.05O21c rate charge-discharges under the conditions of 50 follow
The charge and discharge electrograph of ring.
Example 3
(1) it mixes：Stoichiometrically 0.80:0.15:0.05:1 nickel source, cobalt source, silicon source and ammonium oxalate, weighs respectively
Nickel nitrate 3.257g, cobalt nitrate 0.611g, aluminum nitrate 0.263g, ammonium oxalate 1.990g is dissolved in 40ml deionized waters, in room temperature
Lower stirring 30min makes it be sufficiently mixed uniformly, and 1ml triethanolamines are then added, and continues to stir 30min, it is suspended to obtain light green color
Liquid.
(2) hydro-thermal reaction：Suspension is transferred in 50ml reaction kettles, is dropped with stove after 110 DEG C of reaction 10h in drying box
To room temperature.
(3) drying and sintering：Precipitation in reaction kettle is taken out by filtering, is cleaned repeatedly with deionized water 3~4 times, vacuum
70 DEG C of next night drying.Depositing abrasive is become into powder.4h completes sintering to obtained powder at 300 DEG C in air, obtain aluminium,
Cobalt ions is solid-solution in rodlike (Ni therein0.80Co0.15Al0.05)2O3。
(4) it mixes：Stoichiometrically 1.04:1:1 lithium source, powder and citric acid, weighs lithium nitrate 1.468g respectively,
Powder 1.5g obtained by back, citric acid 4.303g are dissolved in 25ml deionized waters, 3h are stirred at room temperature, and keep it fully mixed
It closes uniformly, obtains dark-brown suspension.
(5) chelatropic reaction：This suspension is stirred into 3h in 90 DEG C of stirring in water bath device, moisture is made to be evaporated, forms gel.
(6) dry：This gel is dried in vacuum drying chamber at 150 DEG C, loose porous solid is formed, takes out grinding shape
At powder.
(7) it roasts：Powder is placed and is sintered 4h at 750 DEG C in air, naturally cool to room temperature to get
LiNi0.80Co0.15Al0.05O2。
Fig. 8 is the LiNi being prepared under the conditions of example 30.80Co0.15Al0.05O20.1c rate charge-discharges under the conditions of
Secondary charge and discharge electrograph.
Fig. 9 is preparation gained LiNi under the conditions of example 30.80Co0.15Al0.05O21c rate charge-discharges under the conditions of 50 follow
The charge and discharge electrograph of ring.
Claims (9)
1. a kind of two-step method prepares anode material for lithium-ion batteries LiNi0.80Co0.15Al0.05O2Method, which is characterized in that including
Following steps：
（1）Nickel source, cobalt source, silicon source, hydrolytic reagent ammonium oxalate and surfactant is soluble in water, it is stirred at room temperature and is mixed
Solution is transferred in reaction kettle, in 110-130 DEG C of 6 ~ 10h of hydro-thermal reaction；
（2）It is taken out being precipitated in reaction kettle, grind into powder after drying；
（3）Gained powder is sintered 3 ~ 4h for 300 DEG C in air, room temperature is naturally cooled to, obtains rodlike cobalt nickel oxide aluminium；
（4）By step（3）Gained cobalt nickel oxide aluminium, lithium source and citric acid are soluble in water, are stirred at room temperature to obtain suspension, will
This suspension obtains gel in 80 ~ 90 DEG C of stirring in water bath；
（5）Grind into powder after gel drying；
（6）Powder is placed and is sintered 2 ~ 4h at 750 DEG C in air, naturally cool to room temperature to get
LiNi0.80Co0.15Al0.05O2。
2. two-step method as described in claim 1 prepares anode material for lithium-ion batteries LiNi0.80Co0.15Al0.05O2Method,
It is characterized in that, step（1）In, nickel source, cobalt source, silicon source, the molar ratio of hydrolytic reagent are 0.80:0.15:0.05:1；Nickel source is nitric acid
Nickel；Cobalt source is cobalt nitrate；Silicon source is aluminum nitrate；Surfactant is triethanolamine.
3. two-step method as described in claim 1 prepares anode material for lithium-ion batteries LiNi0.80Co0.15Al0.05O2Method,
It is characterized in that, step（1）In, a concentration of 0.35M of hydrolytic reagent in mixed solution；The volume ratio of surfactant and water is 1:
40。
4. two-step method as described in claim 1 prepares anode material for lithium-ion batteries LiNi0.80Co0.15Al0.05O2Method,
It is characterized in that, step（1）In, 1h is stirred at room temperature；Liquor capacity accounts for 40% in reaction kettle；The hydro-thermal reaction 6h at 120 DEG C.
5. two-step method as described in claim 1 prepares anode material for lithium-ion batteries LiNi0.80Co0.15Al0.05O2Method,
It is characterized in that, step（2）In, it is dry using vacuum drying at 60 ~ 80 DEG C.
6. two-step method as described in claim 1 prepares anode material for lithium-ion batteries LiNi0.80Co0.15Al0.05O2Method,
It is characterized in that, step（3）In, heating rate is 5 ~ 10 DEG C/min.
7. two-step method as described in claim 1 prepares anode material for lithium-ion batteries LiNi0.80Co0.15Al0.05O2Method,
It is characterized in that, step（4）In, lithium source, cobalt nickel oxide aluminium, citric acid molar ratio be 1.04:1:1, lithium source is lithium nitrate.
8. two-step method as described in claim 1 prepares anode material for lithium-ion batteries LiNi0.80Co0.15Al0.05O2Method,
It is characterized in that, step（5）In, drying temperature is 110 DEG C ~ 150 DEG C.
9. two-step method as described in claim 1 prepares anode material for lithium-ion batteries LiNi0.80Co0.15Al0.05O2Method,
It is characterized in that, step（6）In, heating rate is 5 ~ 10 DEG C/min.
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| CN104466154A (en) * | 2014-12-10 | 2015-03-25 | 哈尔滨工业大学（威海） | Preparation method of lithium ion battery positive material nickel cobalt aluminum |
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| CN104466154A (en) * | 2014-12-10 | 2015-03-25 | 哈尔滨工业大学（威海） | Preparation method of lithium ion battery positive material nickel cobalt aluminum |
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