CN104466132A - Niobium-doped lithium ion battery cathode material and preparation method thereof - Google Patents

Niobium-doped lithium ion battery cathode material and preparation method thereof Download PDF

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Publication number
CN104466132A
CN104466132A CN201410712792.5A CN201410712792A CN104466132A CN 104466132 A CN104466132 A CN 104466132A CN 201410712792 A CN201410712792 A CN 201410712792A CN 104466132 A CN104466132 A CN 104466132A
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niobium
lithium
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余志勇
刘韩星
王壮
卢梦云
李文姬
郑振宁
吴莎
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Wuhan University of Technology WUT
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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
    • 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
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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 relates to a niobium-doped cathode material for a lithium ion battery and a preparation method of the niobium-doped cathode material. The preparation method comprises the following steps: (1) weighing a lithium source, a manganese source, a niobium source and a cobalt source according to a molar ratio; (2) dissolving the lithium source, the manganese source and the cobalt source into de-ionized water; dissolving the lithium source into a citric acid water solution and uniformly mixing; (3) adjusting the pH of the mixed solution obtained in the step (2) to 8-9 with ammonia water and stirring under a water bath condition to obtain sol; (4) drying the sol obtained in the step (3) in a drying oven to obtain gel; foaming the gel in the drying oven and cooling and grinding to obtain powder; and (5) carrying out calcining treatment on the powder ground in the step (4) to prepare Li1.8Mn0.8-xNbxCo0.2O2.8. The niobium-doped cathode material of the lithium ion battery has the beneficial effects that the circulating stability of the material is effectively improved. The preparation method is simple in process and is easy to control, and has the obvious effect on the aspect of improving the circulating stability of the Li1.8Mn0.8-xNbxCo0.2O2.8 material.

Description

Anode material for lithium-ion batteries of a kind of niobium doping and preparation method thereof
Technical field
The invention belongs to field of lithium ion battery, be specifically related to anode material for lithium ion battery of a kind of niobium doping and preparation method thereof.
Background technology
Solid-solution material xLi 2mnO 3(1-x) LiMO 2it is high that (M=Mn, Ni, Co etc.) have charging and discharging capacity, low price, and the thermally-stabilised advantage such as good is current field of lithium ion battery study hotspot.This kind of material is often called as rich lithium Layered Structural Positive Electrode Materials, is considered to the important candidate material being expected to improve further lithium ion battery energy density.
It has been generally acknowledged that, within the scope of 2.0 ~ 4.4V charging/discharging voltage, Li 2mnO 3present electrochemicaUy inert.When voltage is raised to more than 4.5V, Li 2mnO 3electro-chemical activity can be had.It is generally acknowledged, the height ratio capacity characteristic that this series of solid solutions more than material 4.5V shows with in lithium ion deintercalation process along with lattice deoxidation process relevant.But this de-lithium deoxidation process reduces electrode material structural stability, thus affects the cyclical stability of material.
Research shows that Surface coating can improve rich lithium material cycle of higher pressure stability to a certain extent.As the researchs such as Sun-Ho Kang find to adopt Li-Ni-PO 4coatedly can improve rich lithium material 0.5Li 2mnO 30.5LiNi 0.44co 0.25mn 0.31o 2cyclical stability [Sun-Ho Kang, Michael M.Thackeray, Electrochem.Commun., 2009,11 (4): 748 – 751].J.M.Zheng etc. utilize AlF 3be coated on and improve Li [Li to a certain extent 0.2mn 0.54ni 0.13co 0.13] O 2the cyclical stability [J.M.Zheng, Z.R.Zhang, X.B.Wu, Z.X.Dong, Z.Zhu and Y.Yang, J.Electrochem.Soc.2008155 (10): A775-A782] of material.But improved the cyclical stability of rich lithium material by cladding process, its process procedure is comparatively complicated, and be difficult to control.
Summary of the invention
Anode material for lithium ion battery that the object of the present invention is to provide a kind of niobium to adulterate and preparation method thereof, improved the cyclical stability of rich lithium Layered Structural Positive Electrode Materials by niobium doping vario-property, overcome the problem that in the cyclic process of rich lithium Layered Structural Positive Electrode Materials, capacity attenuation is too fast.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of anode material for lithium-ion batteries of niobium doping, its chemical formula is: Li 1.8mn 0.8-xnb xco 0.2o 2.8, wherein 0.02≤x≤0.04.
The preparation method of the anode material for lithium-ion batteries of described niobium doping, comprises following steps:
1) according to the molar ratio weighing lithium source of 1.8:0.8-x:x:0.2, manganese source, niobium source and cobalt source, wherein 0.02≤x≤0.04;
2) the lithium source will taken respectively, manganese source and cobalt source are dissolved in deionized water, and niobium source is dissolved in aqueous citric acid solution, and is mixed by two kinds of solution;
3) ammoniacal liquor regulating step 2) pH to 8 ~ 9 of mixed solution that obtain, stir under water-bath and obtain colloidal sol;
4) by step 3) gained colloidal sol first dries in an oven and obtains gel, and then foam in an oven, after cooling, grinding obtains powder;
5) through step 4) gained powder carries out calcination processing and is prepared into Li after grinding 1.8mn 0.8-xnb xco 0.2o 2.8.
By such scheme, step 1) in lithium source, manganese source, niobium source and cobalt source are respectively lithium nitrate, manganese nitrate, niobium hydroxide and cobalt acetate.
By such scheme, step 2) metal cation mol ratio total in citric acid and mixed solution in gained mixed solution is 2:1.
By such scheme, step 5) described in calcine technology for first to calcine 5min at 500 DEG C, then at 800 DEG C ~ 900 DEG C, calcine 10h ~ 15h.
Beneficial effect of the present invention is: by the method for niobium doping vario-property, utilize Nb-O high in conjunction with energy, improve the structural stability in material charge and discharge process, thus effectively improve the cyclical stability of this material.This preparation method technique is simple, is easy to control, at raising Li 1.8mn 0.8co 0.2o 2.8the cyclical stability aspect successful of material.Such as when employing 3% niobium adulterates, by the positive electrode prepared by the present invention, when current density is 20mA/g, first discharge specific capacity is 97mAh/g, increase gradually along with capacity is carried out in circulation, kept stable after 20 times, after 30 circulations, capacity remains on 192mAh/g; And unadulterated Li 1.8mn 0.8co 0.2o 2.8material, when current density is 20mAh/g, first discharge specific capacity is respectively 195mAh/g, and after 30 circulations, capacity attenuation is 165mAh/g, and the electrode material after doping shows better cyclical stability.
Accompanying drawing explanation
Fig. 1 is different N b content Li doped 1.8mn 0.8-xnb xco 0.2o 2.8xRD figure;
Fig. 2 is different N b content Li doped 1.8mn 0.8-xnb xco 0.2o 2.8sEM figure;
Fig. 3 is Li under 20mA/g current density 1.8mn 0.8-xnb xco 0.2o 2.8the cycle performance of (0.02≤x≤0.04).
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, below in conjunction with accompanying drawing and specific embodiment, the present invention is described in detail.
Comparative example
Take 12.4103 grams of lithium nitrates, 14.3158 grams of manganese nitrates and 3.5404 grams of cobalt acetates are dissolved in 100 grams of deionized waters, take citric acid 107.5891 grams and are dissolved in 60 grams of deionized waters.Above-mentioned two kinds of solution are mixed rear ammoniacal liquor and regulate mixed solution pH to 8 ~ 9.Stir under 80 DEG C of water-baths after 8h obtains colloidal sol and dry at 80 DEG C, the 8h that then foams at 150 DEG C obtains foaming shape atrament; Dry gel powder after grinding is first calcined 5min at 500 DEG C, and then at 800 DEG C, calcines 10h obtain Li 1.8mn 0.8co 0.2o 2.8.
By positive active material Li 1.8mn 0.8co 0.2o 2.8mix by the mass ratio of 80:10:10 with acetylene black and polyvinylidene fluoride, be dissolved in 1-METHYLPYRROLIDONE, stir into pasted positive coating, be evenly coated on stainless steel substrate.The positive plate coated is placed in vacuum drying chamber, and at 80 DEG C, vacuumize was assembled for battery after 12 hours.CR2025 type button cell is assembled in the MBRAUN glove box being full of high-purity argon gas.Wherein negative pole adopts that metal lithium sheet, electrolyte are EC:DMC (mol ratio 3:7), barrier film is Celgard.
Adopt the charge-discharge performance (voltage range 2.0-4.8V, current density 20mA/g) of Land CT2001A battery test system characterizing battery.Test result shows, Li 1.8mn 0.8co 0.2o 2.8first discharge specific capacity be 195mAh/g, 30 times circulation after specific discharge capacity decay to 165mAh/g.
Embodiment 1
Take 12.4103 grams of lithium nitrates, 13.9579 grams of manganese nitrates and 3.5404 grams of cobalt acetates are dissolved in 100 grams of deionized waters.Taking citric acid 107.5891 grams is dissolved in 60 grams of deionized waters, after by 3.5589 grams of Nb (OH) 5be melted in aqueous citric acid solution.Above-mentioned two kinds of solution are mixed rear ammoniacal liquor and regulate mixed solution pH to 8 ~ 9.Stir under 80 DEG C of water bath after 8h obtains colloidal sol and dry at 80 DEG C, the 8h that then foams at 150 DEG C obtains foaming shape atrament; Dry gel powder after grinding is first calcined 5min at 500 DEG C, and then at 800 DEG C, calcines 10h obtain Li 1.8mn 0.78nb 0.02co 0.2o 2.8.
Adopt the method identical with comparative example to prepare CR2025 type button cell, charge-discharge test (voltage range 2.0-4.8V, current density 20mA/g) is carried out to it.Be illustrated in figure 1 in the embodiment of the present invention XRD figure of the different content Nb that adulterates, after doping, thing is not subject to too large impact mutually as seen from the figure, and lattice constant comparatively comparative example increases to some extent, and comparatively comparative example is good for the lamellarity of material.As Fig. 2 (b) is depicted as in the embodiment of the present invention SEM figure of the different content Nb that adulterates, sample powder reuniting obviously weakens as seen from the figure, and particle diameter reduces.Be illustrated in figure 3 in the embodiment of the present invention cycle charge-discharge resolution chart of the sample of the different content Nb that adulterates, Li as seen from the figure 1.8mn 0.78nb 0.02co 0.2o 2.8first discharge specific capacity be 113mAh/g, increase gradually along with capacity is carried out in circulation, kept stable after 20 times, 30 times circulation after specific discharge capacity remain 185mAh/g, cyclical stability comparatively comparative example is good.
Embodiment 2
Take 12.4103 grams of lithium nitrates, 13.779 grams of manganese nitrates and 3.5404 grams of cobalt acetates are dissolved in 100 grams of deionized waters.Taking citric acid 107.5891 grams is dissolved in 60 grams of deionized waters, after by 5.3383 grams of Nb (OH) 5be melted in aqueous citric acid solution.Two kinds of solution are mixed rear ammoniacal liquor and regulate mixed solution pH to 8 ~ 9.Stir under 80 DEG C of water bath after 8h obtains colloidal sol and dry at 80 DEG C, the 8h that then foams at 150 DEG C obtains foaming shape atrament; Dry gel powder after grinding is first calcined 5min at 500 DEG C, and then at 800 DEG C, calcines 10h obtain Li 1.8mn 0.77nb 0.03co 0.2o 2.8.
Adopt the method identical with comparative example to prepare CR2025 type button cell, charge-discharge test (voltage range 2.0-4.8V, current density 20mA/g) is carried out to it.Be illustrated in figure 1 in the embodiment of the present invention XRD figure of the different content Nb that adulterates, after doping, thing is not subject to too large impact mutually as seen from the figure, and lattice constant comparatively comparative example increases to some extent, and comparatively comparative example is good for the lamellarity of material.As Fig. 2 (c) is depicted as in the embodiment of the present invention SEM figure of the different content Nb that adulterates, sample powder reuniting obviously weakens as seen from the figure, and particle diameter reduces.Be illustrated in figure 3 in the embodiment of the present invention cycle charge-discharge resolution chart of the sample of the different content Nb that adulterates, Li as seen from the figure 1.8mn 0.77nb 0.03co 0.2o 2.8first discharge specific capacity be 97mAh/g, increase gradually along with capacity is carried out in circulation, kept stable after 20 times, 30 times circulation after specific discharge capacity remain 192mAh/g, cyclical stability comparatively comparative example is good.
Embodiment 3
Take 12.4103 grams of lithium nitrates, 13.6 grams of manganese nitrates and 3.5404 grams of cobalt acetates are dissolved in 100 grams of deionized waters.Taking citric acid 107.5891 grams is dissolved in 60 grams of deionized waters, after by 7.1177 grams of Nb (OH) 5be melted in aqueous citric acid solution.Two kinds of solution are mixed rear ammoniacal liquor and regulate mixed solution pH to 8 ~ 9.Stir under 80 DEG C of water bath after 8h obtains colloidal sol and dry at 80 DEG C, the 8h that then foams at 150 DEG C obtains foaming shape atrament; Dry gel powder after grinding is first calcined 5min at 500 DEG C, and then at 800 DEG C, calcines 10h obtain Li 1.8mn 0.76nb 0.04co 0.2o 2.8.
Adopt the method identical with comparative example to prepare CR2025 type button cell, charge-discharge test (voltage range 2.0-4.8V, current density 20mA/g) is carried out to it.Be illustrated in figure 1 in the embodiment of the present invention XRD figure of the different content Nb that adulterates, after doping, thing is not subject to too large impact mutually as seen from the figure, and lattice constant comparatively comparative example increases to some extent, and comparatively comparative example is good for the lamellarity of material.As Fig. 2 (d) is depicted as in the embodiment of the present invention SEM figure of the different content Nb that adulterates, sample powder reuniting obviously weakens as seen from the figure, and particle diameter reduces.Be illustrated in figure 3 in the embodiment of the present invention cycle charge-discharge resolution chart of the sample of the different content Nb that adulterates, Li as seen from the figure 1.8mn 0.76nb 0.04co 0.2o 2.8first discharge specific capacity be 95mAh/g, increase gradually along with capacity is carried out in circulation, kept stable after 20 times, 30 times circulation after specific discharge capacity remain 166mAh/g, cyclical stability comparatively comparative example is good.
Embodiment 4
Take 12.4103 grams of lithium nitrates, 13.779 grams of manganese nitrates and 3.5404 grams of cobalt acetates are dissolved in 100 grams of deionized waters.Taking citric acid 107.5891 grams is dissolved in 60 grams of deionized waters, after by 5.3383 grams of Nb (OH) 5be melted in aqueous citric acid solution.Two kinds of solution are mixed rear ammoniacal liquor and regulate mixed solution pH to 8 ~ 9.Stir under 80 DEG C of water bath after 8h obtains colloidal sol and dry at 80 DEG C, the 8h that then foams at 150 DEG C obtains foaming shape atrament; Dry gel powder after grinding is first calcined 5min at 500 DEG C, and then at 900 DEG C, calcines 10h obtain Li 1.8mn 0.77nb 0.03co 0.2o 2.8.
Adopt the method identical with comparative example to prepare CR2025 type button cell, charge-discharge test (voltage range 2.0-4.8V, current density 20mA/g) is carried out to it.Test result shows, Li 1.8mn 0.77nb 0.03co 0.2o 2.8first discharge specific capacity be 96mAh/g, increase gradually along with capacity is carried out in circulation, kept stable after 20 times, 30 times circulation after specific discharge capacity remain 142mAh/g.
Embodiment 5
Take 12.4103 grams of lithium nitrates, 13.779 grams of manganese nitrates and 3.5404 grams of cobalt acetates are dissolved in 100 grams of deionized waters.Taking citric acid 107.5891 grams is dissolved in 60 grams of deionized waters, after by 5.3383 grams of Nb (OH) 5be melted in aqueous citric acid solution.Two kinds of solution are mixed rear ammoniacal liquor and regulate mixed solution pH to 8 ~ 9.Stir under 80 DEG C of water bath after 8h obtains colloidal sol and dry at 80 DEG C, the 8h that then foams at 150 DEG C obtains foaming shape atrament; Dry gel powder after grinding is first calcined 5min at 500 DEG C, and then at 800 DEG C, calcines 15h obtain Li 1.8mn 0.77nb 0.03co 0.2o 2.8.
Adopt the method identical with comparative example to prepare CR2025 type button cell, charge-discharge test (voltage range 2.0-4.8V, current density 20mA/g) is carried out to it.Test result shows, Li 1.8mn 0.77nb 0.03co 0.2o 2.8first discharge specific capacity be 69mAh/g, increase gradually along with capacity is carried out in circulation, kept stable after 10 times, 30 times circulation after specific discharge capacity remain 162mAh/g.
By the above detailed description to the embodiment of the present invention, can understand and the invention solves the high problem of conventional rich lithium Layered Structural Positive Electrode Materials capacity attenuation rate, technique is simple, prepared Li 1.8mn 0.8-xnb xco 0.2o 2.8good cycling stability.
Be understandable that, the illustrative embodiments that above execution mode is only used to principle of the present invention is described and adopts, but the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement are also considered as protection scope of the present invention.

Claims (5)

1. an anode material for lithium-ion batteries for niobium doping, its chemical formula is: Li 1.8mn 0.8-xnb xco 0.2o 2.8, wherein 0.02≤x≤0.04.
2. the preparation method of the anode material for lithium-ion batteries of niobium doping according to claim 1, comprises following steps:
1) according to the molar ratio weighing lithium source of 1.8:0.8-x:x:0.2, manganese source, niobium source and cobalt source, wherein 0.02≤x≤0.04;
2) the lithium source will taken respectively, manganese source and cobalt source are dissolved in deionized water, and niobium source is dissolved in aqueous citric acid solution, and is mixed by two kinds of solution;
3) ammoniacal liquor regulating step 2) pH to 8 ~ 9 of mixed solution that obtain, stir under water-bath and obtain colloidal sol;
4) by step 3) gained colloidal sol first dries in an oven and obtains gel, and then foam in an oven, after cooling, grinding obtains powder;
5) through step 4) gained powder carries out calcination processing and is prepared into Li after grinding 1.8mn 0.8-xnb xco 0.2o 2.8.
3. the preparation method of the anode material for lithium-ion batteries of niobium doping as claimed in claim 2, is characterized in that step 1) in lithium source, manganese source, niobium source and cobalt source are respectively lithium nitrate, manganese nitrate, niobium hydroxide and cobalt acetate.
4. the preparation method of the anode material for lithium-ion batteries of niobium doping as claimed in claim 2, is characterized in that step 2) metal cation mol ratio total in citric acid and mixed solution in gained mixed solution is 2:1.
5. the preparation method of the anode material for lithium-ion batteries of niobium doping as claimed in claim 2, is characterized in that step 5) described in calcine technology for first to calcine 5min at 500 DEG C, then at 800 DEG C ~ 900 DEG C, calcine 10h ~ 15h.
CN201410712792.5A 2014-11-28 2014-11-28 Niobium-doped lithium ion battery cathode material and preparation method thereof Pending CN104466132A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112864392A (en) * 2021-01-28 2021-05-28 山东宏匀纳米科技有限公司 Method for preparing doping element-containing positive electrode material by solution heating method
CN113173606A (en) * 2021-04-09 2021-07-27 北京工业大学 Modification method for improving performance of lithium-rich iron-manganese-based cathode material based on density functional theory calculation

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112864392A (en) * 2021-01-28 2021-05-28 山东宏匀纳米科技有限公司 Method for preparing doping element-containing positive electrode material by solution heating method
CN113173606A (en) * 2021-04-09 2021-07-27 北京工业大学 Modification method for improving performance of lithium-rich iron-manganese-based cathode material based on density functional theory calculation
CN113173606B (en) * 2021-04-09 2022-11-22 北京工业大学 Modification method for improving performance of lithium-rich iron-manganese-based cathode material based on density functional theory calculation

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Application publication date: 20150325

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