CN106159220A - Method for preparing lithium ion battery anode material LiNi0.80 Co0.15Al0.05O 2 by two-step method - Google Patents
Method for preparing lithium ion battery anode material LiNi0.80 Co0.15Al0.05O 2 by two-step method Download PDFInfo
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- CN106159220A CN106159220A CN201510194106.4A CN201510194106A CN106159220A CN 106159220 A CN106159220 A CN 106159220A CN 201510194106 A CN201510194106 A CN 201510194106A CN 106159220 A CN106159220 A CN 106159220A
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- lithium
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- aluminum
- anode material
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- 238000000034 method Methods 0.000 title claims abstract description 49
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 22
- 229910011456 LiNi0.80Co0.15Al0.05O2 Inorganic materials 0.000 title claims abstract description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000010405 anode material Substances 0.000 title claims abstract description 18
- -1 nickel oxide cobalt aluminum Chemical compound 0.000 claims abstract description 18
- 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 9
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000005245 sintering Methods 0.000 claims description 17
- 239000000725 suspension Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 229910001868 water Inorganic materials 0.000 claims description 12
- 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
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical group [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- 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
- 239000012467 final product Substances 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 19
- 239000002245 particle Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 150000001868 cobalt Chemical class 0.000 abstract 1
- 239000008139 complexing agent Substances 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
- 229910018632 Al0.05O2 Inorganic materials 0.000 description 16
- 229910013716 LiNi Inorganic materials 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000000975 co-precipitation Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [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 description 5
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 4
- 230000004087 circulation Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910001429 cobalt ion Inorganic materials 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 229910015701 LiNi0.85Co0.10Al0.05O2 Inorganic materials 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
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 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
- 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
- 239000002253 acid Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 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
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 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
- 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
- 239000000047 product Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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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
-
- 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 LiNi0.80Co0.15Al0.05O2The 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 the nano-scale material with obvious layered structure and ordered atomic arrangement rule is obtained after high-temperature roasting. 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 method preparing anode material for lithium-ion batteries, be specifically related to a kind of two-step mode technique and prepare
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 life-span length, use safety, can fast charging and discharging, high temperature resistant,
The advantages such as specific capacity is big, environmental protection, are therefore widely used in the industry such as communication, traffic.Lithium ion cell positive
Material nickel cobalt aluminum lithium (LiNi1-x-yCoxAlyO2, also referred to as NCA) and it is LiCoO based on stratiform2、LiNiO2The material of structure
Material, is a new direction of positive electrode current investigation of materials.It has high theoretical capacity (274mAh/g), low cost,
Hypotoxicity, the advantage of Heat stability is good, be considered to be hopeful very much to apply on high-energy, high power electrokinetic cell,
Particularly electric automobile.
The method of traditional synthesis nickel cobalt aluminum lithium has high temperature solid-state method, coprecipitation, sol-gal process etc..High temperature solid-state
The method sintering temperature height time is long, wastes the energy, and granularity and pattern are difficult to control to.Zhu Xianjun etc. (Zhu Xianjun, Zhan Hui,
Zhou Yunhong .LiNi0.85Co0.10Al0.05O2Positive electrode synthesis and sign [J]. Rare Metals Materials and work
Journey, 2005,34 (12): 1862-1865) by analytical pure raw material Li OH H2O, Ni2O3, Co2O3With Al (OH)3By one
Fixed metering score another name amount, mix, grind, grind again after pre-burning, tabletting, 725 DEG C of roasting 24h in oxygen
Obtain product LiNi0.85Co0.10Al0.05O2.But granule-morphology and size are uneven, so causing cycle performance more
Typically.
Material prepared by coprecipitation is easily reunited, and in the form of sheets and polygon, physical property is the best, 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) use conventional coprecipitation to prepare
LiNi0.8Co0.2-xAlxO2(0≤x≤0.2) positive electrode.Although cycle performance still can, but initial capacity is relatively low, only
There is 160mAh/g.
Sol-gal process is difficult to control to granule-morphology, and is easily formed reunion.(Chang Joo Han, the 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 acrylic acid as chelating agent, lithium, nickel, cobalt
Acetate and aluminum nitrate be that nickel cobalt aluminum lithium material prepared by raw material.But owing to particle size is relatively big, and it is tight to reunite
Weight, so cycle performance is the most general.
Current domestic synthesis nickel cobalt aluminum lithium mainly uses coprecipitation and spray drying method.
Use coprecipitation has the following patent.Chinese patent CN201010624564.4 disclose a kind of lithium from
The preparation method of sub-anode material nickel cobalt lithium aluminate, uses metal salt solution and the precipitant precipitation synthesis nickel cobalt of nickel cobalt aluminum
Aluminum presoma.Aluminium ion is more difficult forms homogeneous coprecipitation with nickel cobalt ion, is extremely difficult to nickel cobalt aluminium element equally distributed
Purpose, it will cause aluminum skewness in nickel cobalt lithium aluminate material, affect the electrical property of material, especially circulate
Performance.Also the nickel cobalt aluminum complex hydroxide using complex coprecipitation method to prepare on this basis or carbonate is had to sink
Form sediment, then after being mixed by a certain percentage with lithium source by this presoma, high temperature sintering forms in oxygen atmosphere.Such as China is specially
Profit CN20130055624.9, etc..Due to the introducing of Al3+, it is difficult to form single layer structure, lattice with nickel cobalt
Order is deteriorated, and causes granule spherical morphology to be deteriorated, and mobility declines, and the presoma tap density obtained is relatively low.
Use spray drying method has following patent.Chinese patent CN201410206372.X proposes a kind of employing two
Step is spray-dried the method for preparation nickel cobalt lithium aluminate cathode material.Ball milling to be coordinated and long in oxygen atmosphere time
Between high-temperature roasting, complex process and energy consumption is the biggest.
Chinese patent CN201310697497.2 proposes a kind of lithium ion battery nickel cobalt aluminum complex ternary positive electrode
Preparation method.With this patent similarly, crystallization process is used to be initially formed Ni0.75Co0.15Al0.1(OH)2.05Presoma.But
Being that this patent is follow-up uses the high-temperature roasting synthesis final material of NCA.This patent does not control presoma pattern,
And follow-up use solid reaction process, it is more difficult to control particle scale and pattern.
Summary of the invention
It is an object of the invention to provide a kind of two-step mode technique and prepare anode material for lithium-ion batteries
LiNi0.80Co0.15Al0.05O2Method.The method materials wide material sources, low cost, it is easy to control, the material of formation
Granule is the most tiny, excellent electrochemical performance.This method is applicable to industrialization large-scale production.
Realization the technical scheme is that
A kind of two-step method prepares anode material for lithium-ion batteries LiNi0.80Co0.15Al0.05O2Method, including following enforcement
Step:
(1) by soluble in water, in room to the nickel source of certain stoichiometric proportion, cobalt source, aluminum source, hydrolytic reagent and surfactant
The lower stirring of temperature obtains mixed solution, is transferred in reactor, in 110-130 DEG C of hydro-thermal reaction 6～10h；
(2) precipitation in reactor is taken out, dried grind into powder；
(3) by gained powder 300 DEG C of sintering 3～4h in atmosphere, naturally cool to room temperature, obtain bar-shaped cobalt nickel oxide aluminum；
(4) by soluble in water, in room to step (3) gained cobalt nickel oxide aluminum and the lithium source of certain stoichiometric proportion and citric acid
The lower stirring of temperature obtains suspension, and in 80～90 DEG C of stirring in water bath, this suspension is obtained gel；
(5) grind into powder after gel drying；
(6) by sintering 2～4h at powder placement in atmosphere 750 DEG C, naturally cool to room temperature, to obtain final product
LiNi0.80Co0.15Al0.05O2。
Wherein, in step (1), described nickel source, cobalt source, aluminum source, the mol ratio of hydrolytic reagent are 0.80:0.15:0.05:1；
Described nickel source is nickel nitrate；Cobalt source is cobalt nitrate；Aluminum source is aluminum nitrate；Hydrolytic reagent is ammonium oxalate, surfactant
For triethanolamine；In mixed solution, hydrolytic reagent concentration is 0.35M；Surfactant is 1:40 with the volume ratio of water.
In step (1), under room temperature, stir 1h；In reactor, liquor capacity accounts for 40%；6h at hydro-thermal reaction preferably 120 DEG C.
In step (2), it is dried vacuum drying at using 60～80 DEG C.
In step (3), heating rate is 5～10 DEG C/min.
In step (4), lithium source, cobalt nickel oxide aluminum, the mol ratio of citric acid are 1.04:1:1, and lithium source is lithium nitrate.
In step (5), baking temperature is 110 DEG C～150 DEG C.
In step (6), heating rate is 5～10 DEG C/min.
The present invention, compared with its prior art, has a following remarkable advantage: the citric acid method that (1) uses, and reduces
Sintering temperature, decreases sintering time, has saved energy consumption in process of production, thus considerably reduced production
Cost；(2) the material granule uniform particle sizes obtained by the way of two step synthesis is controlled, better crystallinity degree, and concordance is high,
Thus improve the chemical property of material；(3) this method is simple, and preparation technology, equipment needed thereby are relatively simple,
Low cost, beneficially large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is the LiNi of gained in the embodiment of the present invention 10.80Co0.15Al0.05O2XRD figure.
Fig. 2 is the LiNi of gained in the embodiment of the present invention 10.80Co0.15Al0.05O2Second time 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 bar-shaped Ni of gained in the embodiment of the present invention 10.80Co0.15Al0.05The SEM figure of O.
Fig. 5 is the LiNi of gained in the embodiment of the present invention 10.80Co0.15Al0.05O2SEM figure.
Fig. 6 is the LiNi of preparation in the embodiment of the present invention 20.80Co0.15Al0.05O20.1c rate charge-discharge under the conditions of second time
Charge and discharge electrograph.
Fig. 7 is the LiNi of preparation in the embodiment of the present invention 20.80Co0.15Al0.05O21c rate charge-discharge under the conditions of 50 follow
The charge and discharge electrograph of ring.
Fig. 8 is the LiNi of preparation in the embodiment of the present invention 30.80Co0.15Al0.05O20.1c rate charge-discharge under the conditions of second time
Charge and discharge electrograph.
Fig. 9 is the LiNi of preparation in the embodiment of the present invention 30.80Co0.15Al0.05O21c rate charge-discharge under the conditions of 50 follow
The charge and discharge electrograph of ring.
Detailed description of the invention
Two-step method of the present invention prepares anode material for lithium-ion batteries LiNi0.80Co0.15Al0.05O2Method, by following reality
Execute example to be further elaborated.
Example 1
(1) mixing: the stoichiometrically nickel source of 0.80:0.15:0.05:1, cobalt source, aluminum source and ammonium oxalate, weighs respectively
Nickel nitrate 3.257g, cobalt nitrate 0.611g, aluminum nitrate 0.263g, ammonium oxalate 1.990g are dissolved in 40ml deionized water,
It is stirred at room temperature 30min so that it is be sufficiently mixed uniformly, is subsequently adding 1ml triethanolamine, continue stirring 30min,
Obtain light green color suspension.
(2) hydro-thermal reaction: suspension is transferred in 100ml reactor, in drying baker 120 DEG C reaction 6h after with
Room temperature is down to by stove.
(3) drying and sintering: taken out precipitating in reactor by filtration, is cleaned with deionized water 3～4 times, vacuum repeatedly
80 DEG C of next nights dry.Depositing abrasive is become powder.The powder obtained in atmosphere at 300 DEG C 3h complete sintering,
Obtain bar-shaped cobalt nickel oxide aluminum.
(4) mixing: stoichiometrically lithium source, powder and the citric acid of 1.04:1:1, weighs lithium nitrate 0.783g respectively,
Back gained powder 0.800g, citric acid 2.295g, be dissolved in 20ml deionized water, be stirred at room temperature 3h,
Make it be sufficiently mixed uniformly, obtain dark-brown suspension.
(5) chelatropic reaction: this suspension stirs in the stirring in water bath device of 85 DEG C 3h, makes moisture be evaporated, is formed solidifying
Glue.
(6) it is dried: this gel is dried at 140 DEG C in vacuum drying oven, forms loose porous solid, take out and grind
Form powder.
(7) roasting: by sintering 2h at powder placement in atmosphere 750 DEG C, naturally cool to room temperature, to obtain final product
LiNi0.80Co0.15Al0.05O2。
Fig. 1 is to prepare gained LiNi under the conditions of example 10.80Co0.15Al0.05O2XRD figure, in significantly
LiNi0.80Co0.15Al0.05O2Phase.
Fig. 2 is to prepare gained LiNi under the conditions of example 10.80Co0.15Al0.05O20.1c rate charge-discharge under the conditions of second time fill
Electric discharge figure, second time circulation specific discharge capacity reaches 180mAh/g as we know from the figure.
Fig. 3 is to prepare gained LiNi under the conditions of example 10.80Co0.15Al0.05O21c rate charge-discharge under the conditions of 50 circulations
Charge and discharge electrograph, as can be seen from the figure still reach the specific discharge capacity of 100mAh/g under high magnification.
Fig. 4 is that the SEM preparing the bar-shaped cobalt nickel oxide aluminum obtained when the first step react under the conditions of example 1 schemes, from figure
In can be seen that material is corynebacterium, length is on nanoscale.
Fig. 5 is that the LiNi obtained has been reacted in preparation under the conditions of example 10.80Co0.15Al0.05O2SEM figure, can from figure
To find out that material particle size is the most tiny.
Example 2
(1) mixing: the stoichiometrically nickel source of 0.80:0.15:0.05:1, cobalt source, aluminum source and ammonium oxalate, weighs respectively
Nickel nitrate 3.257g, cobalt nitrate 0.611g, aluminum nitrate 0.263g, ammonium oxalate 1.990g are dissolved in 40ml deionized water,
It is stirred at room temperature 30min so that it is be sufficiently mixed uniformly, is subsequently adding 1ml triethanolamine, continue stirring 30min,
Obtain light green color suspension.
(2) hydro-thermal reaction: be transferred to by suspension in 50ml reactor, with stove after 130 DEG C of reaction 8h in drying baker
It is down to room temperature.
(3) drying and sintering: taken out precipitating in reactor by filtration, is cleaned with deionized water 3～4 times, vacuum repeatedly
60 DEG C of next nights dry.Depositing abrasive is become powder.The powder obtained in atmosphere at 300 DEG C 3h complete sintering,
Obtain aluminum, cobalt ion is solid-solution in bar-shaped (Ni therein0.80Co0.15Al0.05)2O3。
(4) mixing: stoichiometrically lithium source, powder and the citric acid of 1.04:1:1, weighs lithium nitrate 0.979g respectively,
Back gained powder 1.000g, citric acid 2.869g, be dissolved in 15ml deionized water, be stirred at room temperature 3h,
Make it be sufficiently mixed uniformly, obtain dark-brown suspension.
(5) chelatropic reaction: this suspension stirs in the stirring in water bath device of 80 DEG C 3h, makes moisture be evaporated, is formed solidifying
Glue.
(6) it is dried: this gel is dried at 110 DEG C in vacuum drying oven, forms loose porous solid, take out and grind
Form powder.
(7) roasting: by sintering 3h at powder placement in atmosphere 750 DEG C, naturally cool to room temperature, to obtain final product
LiNi0.80Co0.15Al0.05O2。
Fig. 6 is to prepare gained LiNi under the conditions of example 20.80Co0.15Al0.05O20.1c rate charge-discharge under the conditions of second time fill
Electric discharge figure.
Fig. 7 is to prepare gained LiNi under the conditions of example 20.80Co0.15Al0.05O21c rate charge-discharge under the conditions of 50 circulations
Charge and discharge electrograph.
Example 3
(1) mixing: the stoichiometrically nickel source of 0.80:0.15:0.05:1, cobalt source, aluminum source and ammonium oxalate, weighs respectively
Nickel nitrate 3.257g, cobalt nitrate 0.611g, aluminum nitrate 0.263g, ammonium oxalate 1.990g are dissolved in 40ml deionized water,
It is stirred at room temperature 30min so that it is be sufficiently mixed uniformly, is subsequently adding 1ml triethanolamine, continue stirring 30min,
Obtain light green color suspension.
(2) hydro-thermal reaction: suspension is transferred in 50ml reactor, in drying baker 110 DEG C reaction 10h after with
Room temperature is down to by stove.
(3) drying and sintering: taken out precipitating in reactor by filtration, is cleaned with deionized water 3～4 times, vacuum repeatedly
70 DEG C of next nights dry.Depositing abrasive is become powder.The powder obtained in atmosphere at 300 DEG C 4h complete sintering,
Obtain aluminum, cobalt ion is solid-solution in bar-shaped (Ni therein0.80Co0.15Al0.05)2O3。
(4) mixing: stoichiometrically lithium source, powder and the citric acid of 1.04:1:1, weighs lithium nitrate 1.468g respectively,
Back gained powder 1.5g, citric acid 4.303g, be dissolved in 25ml deionized water, be stirred at room temperature 3h, make
It is sufficiently mixed uniformly, obtains dark-brown suspension.
(5) chelatropic reaction: this suspension stirs in the stirring in water bath device of 90 DEG C 3h, makes moisture be evaporated, is formed solidifying
Glue.
(6) it is dried: this gel is dried at 150 DEG C in vacuum drying oven, forms loose porous solid, take out and grind
Form powder.
(7) roasting: by sintering 4h at powder placement in atmosphere 750 DEG C, naturally cool to room temperature, to obtain final product
LiNi0.80Co0.15Al0.05O2。
Fig. 8 is the LiNi being prepared under the conditions of example 30.80Co0.15Al0.05O20.1c rate charge-discharge under the conditions of
Secondary charge and discharge electrograph.
Fig. 9 is to prepare gained LiNi under the conditions of example 30.80Co0.15Al0.05O21c rate charge-discharge under the conditions of 50
The charge and discharge electrograph of circulation.
Claims (9)
1. a two-step method prepares anode material for lithium-ion batteries LiNi0.80Co0.15Al0.05O2Method, it is special
Levy and be, comprise the following steps:
(1) by soluble in water to nickel source, cobalt source, aluminum source, hydrolytic reagent and surfactant, it is stirred at room temperature and obtains
Mixed solution, is transferred in reactor, in 110-130 DEG C of hydro-thermal reaction 6～10h；
(2) precipitation in reactor is taken out, dried grind into powder；
(3) by gained powder 300 DEG C of sintering 3～4h in atmosphere, naturally cool to room temperature, obtain bar-shaped nickel oxide
Cobalt aluminum；
(4) by soluble in water to step (3) gained cobalt nickel oxide aluminum, lithium source and citric acid, it is stirred at room temperature and obtains
Suspension, obtains gel by this suspension in 80～90 DEG C of stirring in water bath；
(5) grind into powder after gel drying；
(6) by sintering 2～4h at powder placement in atmosphere 750 DEG C, naturally cool to room temperature, to obtain final product
LiNi0.80Co0.15Al0.05O2。
2. two-step method as claimed in claim 1 prepares anode material for lithium-ion batteries
LiNi0.80Co0.15Al0.05O2Method, it is characterised in that in step (1), nickel source, cobalt source, aluminum source,
The mol ratio of hydrolytic reagent is 0.80:0.15:0.05:1；Nickel source is nickel nitrate；Cobalt source is cobalt nitrate；Aluminum source is nitric acid
Aluminum；Hydrolytic reagent is ammonium oxalate；Surfactant is triethanolamine.
3. two-step method as claimed in claim 1 prepares anode material for lithium-ion batteries
LiNi0.80Co0.15Al0.05O2Method, it is characterised in that in step (1), in mixed solution, hydrolytic reagent is dense
Degree is 0.35M；Surfactant is 1:40 with the volume ratio of water.
4. two-step method as claimed in claim 1 prepares anode material for lithium-ion batteries
LiNi0.80Co0.15Al0.05O2Method, it is characterised in that in step (1), under room temperature stir 1h；Reaction
In still, liquor capacity accounts for 40%；Hydro-thermal reaction 6h at 120 DEG C.
5. two-step method as claimed in claim 1 prepares anode material for lithium-ion batteries LiNi0.80Co0.15Al0.05O2
Method, it is characterised in that in step (2), be dried and use vacuum drying at 60～80 DEG C.
6. two-step method as claimed in claim 1 prepares anode material for lithium-ion batteries
LiNi0.80Co0.15Al0.05O2Method, it is characterised in that in step (3), heating rate is 5～10 DEG C/min.
7. two-step method as claimed in claim 1 prepares anode material for lithium-ion batteries
LiNi0.80Co0.15Al0.05O2Method, it is characterised in that in step (4), lithium source, cobalt nickel oxide aluminum,
The mol ratio of citric acid is 1.04:1:1, and lithium source is lithium nitrate.
8. two-step method as claimed in claim 1 prepares anode material for lithium-ion batteries
LiNi0.80Co0.15Al0.05O2Method, it is characterised in that in step (5), baking temperature is 110 DEG C～150 DEG C.
9. two-step method as claimed in claim 1 prepares anode material for lithium-ion batteries
LiNi0.80Co0.15Al0.05O2Method, it is characterised in that in step (6), heating rate is 5～10 DEG C/min.
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| US20170125809A1 (en) * | 2015-10-30 | 2017-05-04 | Samsung Sdi Co., Ltd. | Composite positive active material, method of preparing the same, and lithium secondary battery including positive electrode including the same |
| CN112563508A (en) * | 2020-12-10 | 2021-03-26 | 杭州肄康新材料有限公司 | Lithium ion battery anode material, lithium ion battery anode and lithium ion battery |
| CN114665092A (en) * | 2020-12-22 | 2022-06-24 | 深圳市研一新材料有限责任公司 | Positive electrode slurry composition, positive electrode slurry, positive electrode plate and secondary battery thereof |
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| CN103700844A (en) * | 2013-12-18 | 2014-04-02 | 江苏科捷锂电池有限公司 | Preparation method of lithium ion battery nickel, cobalt and aluminum composite ternary cathode material |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170125809A1 (en) * | 2015-10-30 | 2017-05-04 | Samsung Sdi Co., Ltd. | Composite positive active material, method of preparing the same, and lithium secondary battery including positive electrode including the same |
| US11133501B2 (en) * | 2015-10-30 | 2021-09-28 | Samsung Sdi Co., Ltd. | Composite positive active material, method of preparing the same, and lithium secondary battery including positive electrode including the same |
| CN112563508A (en) * | 2020-12-10 | 2021-03-26 | 杭州肄康新材料有限公司 | Lithium ion battery anode material, lithium ion battery anode and lithium ion battery |
| CN114665092A (en) * | 2020-12-22 | 2022-06-24 | 深圳市研一新材料有限责任公司 | Positive electrode slurry composition, positive electrode slurry, positive electrode plate and secondary battery thereof |
| CN114665092B (en) * | 2020-12-22 | 2023-06-02 | 深圳市研一新材料有限责任公司 | Positive electrode slurry composition, positive electrode slurry, positive electrode plate and secondary battery thereof |
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