CN105047898A - Twin-spherical lithium-rich cathode material of lithium ion secondary battery and preparation method thereof - Google Patents
Twin-spherical lithium-rich cathode material of lithium ion secondary battery and preparation method thereof Download PDFInfo
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- CN105047898A CN105047898A CN201510305521.2A CN201510305521A CN105047898A CN 105047898 A CN105047898 A CN 105047898A CN 201510305521 A CN201510305521 A CN 201510305521A CN 105047898 A CN105047898 A CN 105047898A
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- lithium
- twin
- secondary battery
- lithium ion
- ion secondary
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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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
- 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
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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
- H01M4/48—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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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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- Battery Electrode And Active Subsutance (AREA)
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Abstract
The invention belongs to the technical field of a lithium ion battery, in particular relates to a twin-spherical lithium-rich cathode material of a lithium ion secondary battery and a preparation method thereof. The cathode material Li<1.13>Ni<0.3>Mn<0.57>O2 of the lithium ion secondary battery is an uniform twin-spherical lithium-rich material at a size of about 2 micrometers formed by symbiotically bonding two balls with diameter of about 1 micrometer. A simple chemical precipitation and mixed sintering method is adopted to prepare the twin-spherical lithium-rich cathode material, synthesis is simple, and cost is low. Electrochemical characterization is carried out on the material, the cyclic performance of the material can be obviously improved, the material is stable in structure during the constant-current discharging and charging cyclic process, and mean voltage attenuation is extremely low.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of twin spherical lithium ion secondary battery lithium-rich anode material and preparation method thereof.
Background technology
Lithium ion battery because its energy density is high, self-discharge rate is little, have extended cycle life, the many advantages such as memory-less effect, become in portable main flow for the energy.The performance of lithium ion battery is often determined by the performance of its positive electrode.
Stratified material cobalt acid lithium (LiCoO
2) because operating voltage is high, discharge and recharge steady, conductivity high is widely used on portable set.But because it is expensive, overcharge resistant ability is poor, have certain toxicity, be difficult to produce motive-power battery.Commercial motive-power battery positive electrode is mainly LiFePO4 (LiFePO
4), its abundant raw material, cost are low, but the capacity of ferric phosphate lithium cell is not high and conductivity is poor.In order to reduce costs, improve specific capacity, in recent years, lithium-rich anode material receives to be paid attention to widely.It has higher specific discharge capacity, abundant raw material source, cheap.At present, still there are some problems in lithium-rich anode material, in its low, cyclic process of coulombic efficiency first, capacity attenuation is fast, high rate performance is on the low side, all need to do further to improve research, in cyclic process, the sharp-decay of mean voltage can cause the reduction of energy density, also limit its commercial applications to a great extent.
Summary of the invention
The object of the present invention is to provide that a kind of raw material is cheap, preparation technology is simple, synthesize twin spherical looks and the lithium ion secondary battery anode material Li be greatly improved to material circulation stability
1.13ni
0.3mn
0.57o
2preparation method, its step is as follows:
1) by MnSO
4h
2o and Na
2cO
3after 1:1 weighs in molar ratio, be dissolved in deionized water respectively, stir 10 ~ 20min, form settled solution; Under stirring, to MnSO
4pour the absolute ethyl alcohol of its volume 10 ~ 15% in solution into, pour Na into subsequently
2cO
3solution, Keep agitation 1 ~ 6h, after centrifugal several distinguished by deionized water and absolute ethyl alcohol, at 50 ~ 80 DEG C, vacuum drying treatment 6 ~ 12h, obtains MnCO
3powder;
2) by gained MnCO
3powder processes 3 ~ 6h under air, 400 ~ 500 DEG C of (programming rate 1 ~ 5 DEG C/min) conditions, obtains black MnO after being naturally down to room temperature
2pressed powder;
3) by Li
1.13ni
0.3mn
0.57o
2in chemical formula, Li, Ni, Mn stoichiometric proportion takes LiOHH
2o (in order to compensate the volatilization under lithium high temperature, excessive a little 2 ~ 5%), Ni (NO
3)
26H
2jointly be dissolved in deionized water after O, add MnO
2powder, under 40 ~ 80 DEG C of conditions, stirs until evaporate to dryness deionized water;
4) by step 3) product processes 6 ~ 18h, thus obtains lithium ion secondary battery anode material Li of the present invention under 800 ~ 950 DEG C of conditions
1.13ni
0.3mn
0.57o
2.
A kind of lithium ion secondary battery anode material of the present invention, it is characterized in that being prepared by said method, obtain the size that linked by the ball symbiosis of two diameters about 1 μm at the homogeneous twin spherical precursor material of about 2 μm, and well pattern and size is kept in follow-up reaction, prepare the rich lithium material of homogeneous twin spherical looks.
The invention has the beneficial effects as follows:
(1) the rich lithium material Li prepared
1.13ni
0.3mn
0.57o
2for twin spherical looks, purity is high, reproducible.
(2) equipment of preparation use is simple, and do not have the use of expensive device, raw material are cheap and easy to get, with low cost.
(3) technique is very simple, and repeatability better, both can be used for experimental implementation, and was well suited for again industrial large-scale production.
(4) anode material for lithium-ion batteries that prepared by the present invention has circulation ratio performance stable especially, and mean voltage is stablized, the phenomenon of the mean voltage rapid decay not having usual rich lithium material to show.
The present invention adopts the method for simple chemical precipitation, mixed sintering, has prepared the lithium-rich anode material of twin spherical looks, has synthesized simple, with low cost.Electrochemical Characterization has been carried out to material, the cycle performance of material be improved significantly, material is Stability Analysis of Structures in constant current charge-discharge cyclic process, and mean voltage decay is minimum.
Accompanying drawing explanation
In order to the technical scheme that is illustrated more clearly in the present invention and the performance preparing material thereof, provide relevant indicators below.
Fig. 1 is MnCO prepared by embodiment 1
3material and final rich lithium material Li
1.13ni
0.3mn
0.57o
2scanning electron microscope (SEM) photograph (SEM).Figure (a) is MnCO under 2 μm of scales
3scanning electron microscope (SEM) photograph (SEM).Figure (b) is Li under 2 μm of scales
1.13ni
0.3mn
0.57o
2scanning electron microscope (SEM) photograph (SEM).The Li of final preparation can be found out from scanning electron microscopic picture
1.13ni
0.3mn
0.57o
2twin spherical looks keep better, and size is comparatively even, soilless sticking.
Fig. 2 is Li prepared by embodiment 1
1.13ni
0.3mn
0.57o
2x-ray diffraction (XRD) collection of illustrative plates of material.Can draw from X-ray diffraction (XRD) collection of illustrative plates, X-ray diffraction (XRD) the collection of illustrative plates free from admixture peak of prepared material occurs, namely proves that the material prepared is the rich lithium material Li of pure phase
1.13ni
0.3mn
0.57o
2.
Fig. 3 is Li prepared by embodiment 1
1.13ni
0.3mn
0.57o
2as anode material for lithium-ion batteries, lithium sheet as to electrode, the cycle performance figure of the half-cell of making.As can be seen from the figure, under the current density of 40mA/g, the first discharge specific capacity of material is 212.4mAh/g, after 50 circulations, specific discharge capacity still can reach 208.6mAh/g, and specific discharge capacity conservation rate is 98.2%, and therefrom illustrative material has extraordinary cyclical stability.
Fig. 4 is Li prepared by embodiment 1
1.13ni
0.3mn
0.57o
2as positive electrode, lithium sheet as to electrode, the constant current test high rate performance figure of half-cell respectively under the different current density of 40mA/g, 100mA/g, 200mA/g, 500mA/g, 1A/g, 2A/g, 100mA/g of making.As can be seen from the figure, material is stable circulation under the test of each current density, and under the high electric current of 1A/g and 2A/g, the specific capacity of material still can reach 127mAh/g and 87mAh/g respectively, demonstrates material and has more outstanding high rate performance.
Fig. 5 is Li prepared by embodiment 1
1.13ni
0.3mn
0.57o
2positive electrode under 40mA/g current density, the variation diagram of constant current cycle 50 mean voltage.The mean voltage of material changes minimum in cyclic process as we can see from the figure, and only decayed after 50 circulations 0.058V, and compared to the battery of rich lithium material assembling prepared by usual method, the stability of battery is very excellent.
Fig. 6 is Li prepared by embodiment 1
1.13ni
0.3mn
0.57o
2positive electrode is under 40mA/g current density, and the specific capacity made for the discharge process of battery in constant current cycle 50 processes is to the variation diagram of the differential curve (dQ/dV curve) of voltage.Respectively the differential of specific capacity to voltage is done to the discharge process of the 1st, 2,10,20,30,40,50 time.Can see that from curve chart the peak shape of curve is stable especially, almost not have anything to change, characterize in whole cyclic process, the cathode material structure framework of battery is very stable, and the stable cycle performance of this and measured battery matches.
Embodiment
Embodiment 1:
1:1 weighs MnSO in molar ratio
4h
2o (0.507g) and Na
2cO
3(0.3179g) be dissolved in 70mL deionized water respectively, stir 20min medicine is fully dissolved, formed settled solution, backward MnSO
47mL absolute ethyl alcohol and Na is poured successively in solution
2cO
3solution, stirs 3h, and centrifuge washing 3 times distinguished by deionized water and absolute ethyl alcohol, and vacuum drying treatment 8h at 60 DEG C, obtains MnCO
3powder; By MnCO
3powder transfer is to Muffle furnace (programming rate 2 DEG C/min) under air conditions, and 400 DEG C of process 5h, obtain the MnO of about 0.25g
2pressed powder.
In order to synthesize final rich lithium material, we take 0.16gMnO
2powder, and stoichiometrically take LiOHH
2o (excessive 5%, 0.1607g) and Ni (NO
3)
26H
2o (0.2817g) mixes with gained powder in deionized water, after stirring evaporate to dryness deionized water, moves into Muffle furnace, processes 12h under 850 DEG C of conditions, both obtained Li
1.13ni
0.3mn
0.57o
2electrode material, about 0.28g.
Take the rich lithium material Li of 0.075g
1.13ni
0.3mn
0.57o
2, conductive auxiliary agent (superP and conductive black), binding agent (PVDF and Kynoar) mix according to mass ratio 7.5:1.5:1, gained slurry is coated on aluminium foil, after 120 DEG C of vacuum dryings, be cut into the square positive plate of length of side 8mm.Select lithium sheet to make negative pole, conventional lithium-ion battery electrolytes elected as by electrolyte, i.e. 1mol/L lithium hexafluoro phosphate (LiPF
6)/ethylene carbonate (EC): dimethyl carbonate (DMC): the mixed liquor=1:1:8 (volume ratio) of methyl ethyl carbonate (EMC), is assembled into 2032 type button cells, and does corresponding electro-chemical test.As shown in Figure 3, current density is 40mA/g to the cycle performance of battery curve of preparation, can find out that the cycle performance of battery is very good.As shown in Figure 4, current density is 40mA/g, 100mA/g, 200mA/g, 500mA/g, 1A/g, 2A/g, 100mA/g to high rate performance figure, shows that battery has preferably high rate performance.Mean voltage situation as shown in Figure 5, stablize, and decays less by battery discharge mean voltage.Do the differential curve of specific capacity and voltage as shown in Figure 6 to battery, peak shape change is very little, and battery is stablized.
Claims (4)
1. a twin spherical lithium ion secondary battery lithium-rich anode material Li
1.13ni
0.3mn
0.57o
2preparation method,
Its step is as follows:
1) by MnSO
4h
2o and Na
2cO
3after 1:1 weighs in molar ratio, be dissolved in deionized water respectively, stir 10 ~ 20min, form settled solution; Under stirring, to MnSO
4pour the absolute ethyl alcohol of its volume 10 ~ 15% in solution into, pour Na into subsequently
2cO
3solution, Keep agitation 1 ~ 6h, after centrifugal several distinguished by deionized water and absolute ethyl alcohol, at 50 ~ 80 DEG C, vacuum drying treatment 6 ~ 12h, obtains MnCO
3powder;
2) by gained MnCO
3powder processes 3 ~ 6h under air, 400 ~ 500 DEG C of conditions, obtains black MnO after being naturally down to room temperature
2pressed powder;
3) by Li
1.13ni
0.3mn
0.57o
2in chemical formula, Li, Ni, Mn stoichiometric proportion takes LiOHH
2o, Ni (NO
3)
26H
2jointly be dissolved in deionized water after O, add MnO
2powder, under 40 ~ 80 DEG C of conditions, stirs until evaporate to dryness deionized water;
4) by step 3) product processes 6 ~ 18h, thus obtains twin spherical lithium ion secondary battery lithium-rich anode material Li under 800 ~ 950 DEG C of conditions
1.13ni
0.3mn
0.57o
2.
2. a kind of twin spherical lithium ion secondary battery lithium-rich anode material Li as claimed in claim 1
1.13ni
0.3mn
0.57o
2preparation method, it is characterized in that: step 2) programming rate 1 ~ 5 DEG C/min.
3. a kind of twin spherical lithium ion secondary battery lithium-rich anode material Li as claimed in claim 1
1.13ni
0.3mn
0.57o
2preparation method, it is characterized in that: step 3) in, LiOHH
2o excessive 2 ~ 5%.
4. a twin spherical lithium ion secondary battery lithium-rich anode material Li
1.13ni
0.3mn
0.57o
2, it is characterized in that: be the size that linked by the ball symbiosis of two diameters about 1 μm at the homogeneous twin sphere material of about 2 μm, and prepared by any one method of claims 1 to 3.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200093632A (en) * | 2017-12-18 | 2020-08-05 | 다이슨 테크놀러지 리미티드 | Use of nickel in lithium-rich cathode materials to suppress gas evolution from the cathode materials during the charge cycle and increase the charge capacity of the cathode materials |
| US11769911B2 (en) | 2017-09-14 | 2023-09-26 | Dyson Technology Limited | Methods for making magnesium salts |
| US11817558B2 (en) | 2017-09-14 | 2023-11-14 | Dyson Technology Limited | Magnesium salts |
| US11967711B2 (en) | 2017-12-18 | 2024-04-23 | Dyson Technology Limited | Lithium, nickel, cobalt, manganese oxide compound and electrode comprising the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HUE063696T2 (en) * | 2019-08-28 | 2024-01-28 | Basf Se | Particulate material, method for its manufacture and use |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11769911B2 (en) | 2017-09-14 | 2023-09-26 | Dyson Technology Limited | Methods for making magnesium salts |
| US11817558B2 (en) | 2017-09-14 | 2023-11-14 | Dyson Technology Limited | Magnesium salts |
| KR20200093632A (en) * | 2017-12-18 | 2020-08-05 | 다이슨 테크놀러지 리미티드 | Use of nickel in lithium-rich cathode materials to suppress gas evolution from the cathode materials during the charge cycle and increase the charge capacity of the cathode materials |
| JP2021507494A (en) * | 2017-12-18 | 2021-02-22 | ダイソン・テクノロジー・リミテッド | Use of nickel in lithium-rich cathode materials to control gas generation from the cathode material during the charging cycle and increase the charge capacity of the cathode material |
| JP7153740B2 (en) | 2017-12-18 | 2022-10-14 | ダイソン・テクノロジー・リミテッド | Use of Nickel in Lithium Rich Cathode Materials to Reduce Outgassing from Cathode Materials During Charging Cycles and to Increase the Charge Capacity of Cathode Materials |
| KR102518915B1 (en) * | 2017-12-18 | 2023-04-10 | 다이슨 테크놀러지 리미티드 | Use of nickel in lithium-rich cathode materials to inhibit gas evolution from cathode materials during charge cycles and to increase charge capacity of cathode materials. |
| US11658296B2 (en) | 2017-12-18 | 2023-05-23 | Dyson Technology Limited | Use of nickel in a lithium rich cathode material for suppressing gas evolution from the cathode material during a charge cycle and for increasing the charge capacity of the cathode material |
| US11967711B2 (en) | 2017-12-18 | 2024-04-23 | Dyson Technology Limited | Lithium, nickel, cobalt, manganese oxide compound and electrode comprising the same |
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