CN105514360A - Lithium-rich material Li1.87Mn0.94Ni0.19O3 as well as preparation method and application thereof - Google Patents

Lithium-rich material Li1.87Mn0.94Ni0.19O3 as well as preparation method and application thereof Download PDF

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Publication number
CN105514360A
CN105514360A CN201510975518.1A CN201510975518A CN105514360A CN 105514360 A CN105514360 A CN 105514360A CN 201510975518 A CN201510975518 A CN 201510975518A CN 105514360 A CN105514360 A CN 105514360A
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China
Prior art keywords
nickel
manganese
preparation
mixed
rich lithium
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CN201510975518.1A
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Chinese (zh)
Inventor
王云鹤
左斌
雷军
田占军
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LELING SHENGLI NEW ENERGY Co Ltd
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LELING SHENGLI NEW ENERGY Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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

Abstract

The invention discloses a lithium-rich material Li1.87Mn0.94Ni0.19O3 as well as a preparation method and an application thereof and belongs to the technical field of electrochemistry. The preparation method comprises steps as follows: 1) a mixed solution of manganese nitrate and nickel nitrate is prepared; 2) a sodium carbonate solution is gradually added to the mixture; 3) nickel and manganese mixed carbonate precipitates are obtained through stirring; 4) the mixed carbonate precipitates are separated, dried for 20-28 h at the temperature of 105-120 DEG C and sintered at the temperature of 470-530 DEG C in the air atmosphere, and nickel and manganese mixed oxide is obtained; 5) nickel and manganese mixed oxide and lithium hydroxide are uniformly mixed in the mass ratio being 1: (1.078-1.122) and sintered at the temperature of 850-950 DEG C in the air atmosphere, and the lithium-rich material Li1.87Mn0.94Ni0.19O3 is obtained. A lithium battery prepared from the cathode material has high discharge capacity, good cycle performance and high rate performance.

Description

A kind of rich lithium material Li 1.87mn 0.94ni 0.19o 3, its preparation method and application thereof
Technical field
The present invention relates to technical field of electrochemistry, particularly the rich lithium material Li of one 1.87mn 0.94ni 0.19o 3, its preparation method and application thereof.
Background technology
In recent years, day by day serious along with energy environment issues, and the requirement of electronic product lightness, the research of people to lithium ion battery deepens continuously.
At present, the positive electrode of lithium-ion-power cell mainly adopts LiMn2O4, LiFePO4 or multivariant oxide positive electrode, but material gram volume is low, and high temperature circulation poor stability, storge quality are poor, also needs to continue to improve.
Summary of the invention
In order to make up the deficiencies in the prior art, the invention provides a kind of rich lithium material Li 1.87mn 0.94ni 0.19o 3, its preparation method and application thereof.
Technical scheme of the present invention is:
A kind of rich lithium material Li 1.87mn 0.94ni 0.19o 3, be made up of Li element, Mn element, Ni element and O element, the mol ratio of described Li element, Mn element, Ni element and O element is 1.87:0.94:0.19:3.
Described rich lithium material Li 1.87mn 0.94ni 0.19o 3preparation method, comprise step:
1) prepare the mixed solution of manganese nitrate and nickel nitrate, the mol ratio of manganese nitrate and nickel nitrate is 4.9-5.1:1, and in mixed solution, the total concentration of manganese ion and nickel ion is 0.2-0.25mol/L;
2) in mixture, add sodium carbonate liquor gradually, the concentration of sodium carbonate liquor is 0.2-0.25mol/L, and in added carbon acid solution, the molal quantity of carbonate is equal with nickel ion molal quantity summation with manganese ion;
3) stir 15-25 hour, obtain the mixed carbonate sediment of nickel and manganese;
4) isolate mixed carbonate sediment, dry 20-28 hour at 105-120 DEG C, then in air atmosphere, at 470-530 DEG C, sinter 4-6 hour, obtain the mixed oxide of nickel and manganese;
5) by the mixed oxide of nickel and manganese and lithium hydroxide according to mass ratio 1:1.078-1.122 Homogeneous phase mixing, then at 850-950 DEG C, in air atmosphere, sinter 11-13 hour, obtain rich lithium material Li 1.87mn 0.94ni 0.19o 3.
Preferably, in step 1), the mol ratio of manganese nitrate and nickel nitrate is 5:1.
Preferably, step 2) in, the concentration of sodium carbonate liquor is equal with the total concentration of manganese ion and nickel ion.
Preferably, in step 4), in air atmosphere, at 500 DEG C, sinter 5 hours.
Preferably, in step 5), in air atmosphere, at 900 DEG C, sinter 12 hours.
Described rich lithium material Li 1.87mn 0.94ni 0.19o 3as the application of anode material for lithium-ion batteries.
Beneficial effect of the present invention is:
The invention provides a kind of new material as lithium ion cell positive, that is, rich lithium material Li 1.87mn 0.94ni 0.19o 3.This rich lithium material preparation method is simple, mild condition is controlled, raw material are based on manganese salt, not containing cobalt salt, with low cost, the rich lithium material advantages of good crystallization of gained, uniform particles, wherein the nickel element of a small amount of doping effectively can activate rich lithium composition especially, thus greatly improves charge/discharge capacity and the chemical property of this material.
When adopting this rich lithium material as lithium ion button shape cell positive electrode, through the electrochemical activation of certain number of times, its discharge capacity under the current density of 25mA/g (0.1C) up to 280mAh/g, it is current other main flow positive electrode on the market, such as LiFePO4,1.5 to 2 times of cobalt acid lithium etc.Cycle performance is good, and circulate from the 100th time to the 200th time, capability retention is 86%, is that in the similar-type products reported at present, cycle performance is relatively more outstanding.In addition, high rate performance is also comparatively excellent, under the current density of 250mA/g (1C), still can obtain the discharge capacity being greater than 170mAh/g.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the rich lithium material Li of the present invention 1.87mn 0.94ni 0.19o 3xRD collection of illustrative plates;
Fig. 2 is scanning electron microscope (SEM) photograph; Wherein, the mixed oxide that a represents the mixed carbonate sediment of nickel and manganese, b represents nickel and manganese, c represent Li 1.87mn 0.94ni 0.19o 3;
Fig. 3 is under 0.1C, the graph of a relation of cycle-index and specific discharge capacity (MAH every gram);
Fig. 4 is charging and discharging curve; Digitized representation cycle-index on line; Wherein, curve in rising trend represents charging curve, and curve on a declining curve represents discharge curve;
I-v curve figure when Fig. 5 is different cycle-index;
Fig. 6 is the circulation volume figure under different current density.
Embodiment
Embodiment 1
A kind of rich lithium material Li 1.87mn 0.94ni 0.19o 3, be made up of Li element, Mn element, Ni element and O element, the mol ratio of described Li element, Mn element, Ni element and O element is 1.87:0.94:0.19:3.
Described rich lithium material Li 1.87mn 0.94ni 0.19o 3preparation method, comprise step:
1) prepare the mixed solution 100ml of manganese nitrate and nickel nitrate, the mol ratio of manganese nitrate and nickel nitrate is 5:1, and in mixed solution, the total concentration of manganese ion and nickel ion is 0.2mol/L;
2) in mixture, add 100ml sodium carbonate liquor gradually, the concentration of sodium carbonate liquor is 0.2mol/L;
3) stir 20 hours, obtain the mixed carbonate sediment of nickel and manganese;
4) isolate mixed carbonate sediment, drying 24 hours at 110 DEG C, then in air atmosphere, sinters 5 hours at 500 DEG C, obtains the mixed oxide of nickel and manganese;
5) by the mixed oxide of nickel and manganese and lithium hydroxide according to mass ratio 1:1.1 Homogeneous phase mixing, then at 900 DEG C, in air atmosphere, sinter 12 hours, obtain rich lithium material Li 1.87mn 0.94ni 0.19o 3.
Wherein, in step 5), lithium is excessive, to supplement the volatilization under its high temperature.
As shown in Figure 1, product Li 1.87mn 0.94ni 0.19o 3the crystal structure showed under X-ray is layer structure, belongs to space group C2/m, monoclinic system.
As shown in Figure 2, the mixed oxide of the mixed carbonate sediment of nickel and manganese, nickel and manganese and Li 1.87mn 0.94ni 0.19o 3be powdered samples, uniform particles under microcosmic.
Use the present embodiment gained Li 1.87mn 0.94ni 0.19o 3as positive electrode, prepare lithium ion button shape cell, and test the electric property of made lithium ion button shape cell.
As shown in Figure 3, under 0.1C multiplying power, namely under the current density of 25 milliamperes every gram, first circulation specific discharge capacity is 76 MAH every gram; 100th circulation, specific discharge capacity is 280 MAH every gram.
As shown in Figure 4, in the discharge process of first time circulation, the voltage of battery is declining gradually, capacity improves gradually, has brought up to 76 MAH every gram, that is from 0, arrive 4.8V at the voltage range 2 of setting, this material can release the capacity of 76 MAH every gram in first electric discharge.Discharge scenario during other cycle-indexes is shown in Fig. 4.
As shown in Figure 5, the V-I curve of each circulation.Each peak that curve is seen, its magnitude of voltage represent electrochemical reaction occur voltage, and this electrochemical reaction along with the increase of cycle-index more and more obvious.
As shown in Figure 6,0.5C, namely under the current density of 125 milliamperes every gram, material carries out electrochemistry circulation, the specific discharge capacity of 220 MAH every gram can be obtained, 1C multiplying power (high magnification), namely under the current density of 250 milliamperes every gram, can obtain the specific discharge capacity of 180 MAH every gram; Discharge capacity value under other current densities is shown in Fig. 6.
Embodiment 2
A kind of rich lithium material Li 1.87mn 0.94ni 0.19o 3, be made up of Li element, Mn element, Ni element and O element, the mol ratio of described Li element, Mn element, Ni element and O element is 1.87:0.94:0.19:3.
Described rich lithium material Li 1.87mn 0.94ni 0.19o 3preparation method, comprise step:
1) prepare the mixed solution 100ml of manganese nitrate and nickel nitrate, the mol ratio of manganese nitrate and nickel nitrate is 4.9:1, and in mixed solution, the total concentration of manganese ion and nickel ion is 0.25mol/L;
2) in mixture, add 100ml sodium carbonate liquor gradually, the concentration of sodium carbonate liquor is 0.25mol/L;
3) stir 20 hours, obtain the mixed carbonate sediment of nickel and manganese;
4) isolate mixed carbonate sediment, drying 24 hours at 110 DEG C, then in air atmosphere, sinters 5 hours at 500 DEG C, obtains the mixed oxide of nickel and manganese;
5) by the mixed oxide of nickel and manganese and lithium hydroxide according to mass ratio 1:1.078 Homogeneous phase mixing, then at 900 DEG C, in air atmosphere, sinter 12 hours, obtain rich lithium material Li 1.87mn 0.94ni 0.19o 3.
Wherein, in step 5), lithium is excessive, to supplement the volatilization under its high temperature.
Embodiment 3
A kind of rich lithium material Li 1.87mn 0.94ni 0.19o 3, be made up of Li element, Mn element, Ni element and O element, the mol ratio of described Li element, Mn element, Ni element and O element is 1.87:0.94:0.19:3.
Described rich lithium material Li 1.87mn 0.94ni 0.19o 3preparation method, comprise step:
1) prepare the mixed solution 100ml of manganese nitrate and nickel nitrate, the mol ratio of manganese nitrate and nickel nitrate is 5.1:1, and in mixed solution, the total concentration of manganese ion and nickel ion is 0.2mol/L;
2) in mixture, add 100ml sodium carbonate liquor gradually, the concentration of sodium carbonate liquor is 0.2mol/L;
3) stir 20 hours, obtain the mixed carbonate sediment of nickel and manganese;
4) isolate mixed carbonate sediment, drying 24 hours at 110 DEG C, then in air atmosphere, sinters 5 hours at 500 DEG C, obtains the mixed oxide of nickel and manganese;
5) by the mixed oxide of nickel and manganese and lithium hydroxide according to mass ratio 1:1.122 Homogeneous phase mixing, then at 900 DEG C, in air atmosphere, sinter 12 hours, obtain rich lithium material Li 1.87mn 0.94ni 0.19o 3.
Wherein, in step 5), lithium is excessive, to supplement the volatilization under its high temperature.

Claims (7)

1. a rich lithium material Li 1.87mn 0.94ni 0.19o 3, it is characterized in that: be made up of Li element, Mn element, Ni element and O element, the mol ratio of described Li element, Mn element, Ni element and O element is 1.87:0.94:0.19:3.
2. rich lithium material Li as claimed in claim 1 1.87mn 0.94ni 0.19o 3preparation method, it is characterized in that, comprise step:
1) prepare the mixed solution of manganese nitrate and nickel nitrate, the mol ratio of manganese nitrate and nickel nitrate is 4.9-5.1:1, and in mixed solution, the total concentration of manganese ion and nickel ion is 0.2-0.25mol/L;
2) in mixture, add sodium carbonate liquor gradually, the concentration of sodium carbonate liquor is 0.2-0.25mol/L, and in added carbon acid solution, the molal quantity of carbonate is equal with nickel ion molal quantity summation with manganese ion;
3) stir 15-25 hour, obtain the mixed carbonate sediment of nickel and manganese;
4) isolate mixed carbonate sediment, dry 20-28 hour at 105-120 DEG C, then in air atmosphere, at 470-530 DEG C, sinter 4-6 hour, obtain the mixed oxide of nickel and manganese;
5) by the mixed oxide of nickel and manganese and lithium hydroxide according to mass ratio 1:1.078-1.122 Homogeneous phase mixing, then at 850-950 DEG C, in air atmosphere, sinter 11-13 hour, obtain rich lithium material Li 1.87mn 0.94ni 0.19o 3.
3. rich lithium material Li as claimed in claim 2 1.87mn 0.94ni 0.19o 3preparation method, it is characterized in that: in step 1), the mol ratio of manganese nitrate and nickel nitrate is 5:1.
4. rich lithium material Li as claimed in claim 2 1.87mn 0.94ni 0.19o 3preparation method, it is characterized in that: step 2) in, the concentration of sodium carbonate liquor is equal with the total concentration of manganese ion and nickel ion.
5. rich lithium material Li as claimed in claim 2 1.87mn 0.94ni 0.19o 3preparation method, it is characterized in that: in step 4), in air atmosphere, at 500 DEG C sinter 5 hours.
6. rich lithium material Li as claimed in claim 2 1.87mn 0.94ni 0.19o 3preparation method, it is characterized in that: in step 5), in air atmosphere, at 900 DEG C sinter 12 hours.
7. rich lithium material Li as claimed in claim 1 1.87mn 0.94ni 0.19o 3as the application of anode material for lithium-ion batteries.
CN201510975518.1A 2015-12-23 2015-12-23 Lithium-rich material Li1.87Mn0.94Ni0.19O3 as well as preparation method and application thereof Pending CN105514360A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1838453A (en) * 2005-03-23 2006-09-27 中南大学 Lithium-nickel-cobalt-manganese-oxygen material for lithium ion battery positive electrode and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1838453A (en) * 2005-03-23 2006-09-27 中南大学 Lithium-nickel-cobalt-manganese-oxygen material for lithium ion battery positive electrode and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DELAI YE, ET AL.: "Understanding the Origin of Li2MnO3 Activation in Li-Rich Cathode Materials for Lithium-Ion Batteries", 《ADVANCED FUNCTIONAL MATERIALS》 *

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Application publication date: 20160420