CN104466108A - Hollow porous spherical mixed oxide for lithium ion battery negative electrode and preparation method of hollow porous spherical mixed oxide - Google Patents

Hollow porous spherical mixed oxide for lithium ion battery negative electrode and preparation method of hollow porous spherical mixed oxide Download PDF

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CN104466108A
CN104466108A CN201410728110.XA CN201410728110A CN104466108A CN 104466108 A CN104466108 A CN 104466108A CN 201410728110 A CN201410728110 A CN 201410728110A CN 104466108 A CN104466108 A CN 104466108A
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mixed oxide
hollow porous
ion battery
negative electrode
porous spherical
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CN104466108B (en
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马忠
原鲜霞
李琳
马紫峰
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Shanghai Jiaotong University
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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
    • H01M4/364—Composites as mixtures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
    • 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
    • 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 hollow porous spherical mixed oxide for a lithium ion battery negative electrode and a preparation method of the hollow porous spherical mixed oxide. The material is a uniform nano-mixture of Mn2O3 and NiMn2O4, and a specific chemical formula is NixMn<1-x>O<1.5-0.5x> (x is more than 0 and less than 1/3). The preparation method of the hollow porous spherical mixed oxide comprises the steps that based on complexing action of ammonia water and nickel ions, the precipitation speed of nickel carbonate is reduced, so that a spherical structure of the manganese carbonate cannot be destroyed by the nickel carbonate and has a certain modification function on a spherical structure of the manganese carbonate to form a uniform spherical mixture (NixMn<1-x>CO3, x is more than 0 and less than 1/3) of the nickel carbonate and the manganese carbonate; the prepared hollow porous spherical mixed oxide for the lithium ion battery negative electrode is obtained by using a high-temperature segmental roasting process. Compared with the prior art, the method is easy to operate and suitable for industrial large batch production; by utilizing the hollow porous spherical mixed oxide, the large-current charging/discharging performance of the lithium ion battery negative electrode can be effectively improved, and the and the cycle life of the lithium ion battery negative electrode can be effectively prolonged.

Description

Used as negative electrode of Li-ion battery hollow porous spherical mixed oxide and preparation method thereof
Technical field
The invention belongs to nano material and technical field of chemical power, be specifically related to a kind of used as negative electrode of Li-ion battery hollow porous spherical mixed oxide and preparation method thereof.
Background technology
Lithium ion battery is a kind of energy conversion device possessing the advantages such as high-energy-density, high power density, high safety performance, long circulation life, there are the great potential (Science, 311 (2006) 977-980 that are applied in electric automobile and large scale electric network; Nature, 414 (2001) 359-367).The negative material that the lithium ion battery of current commercialization adopts is mainly material with carbon element, as native graphite, MCMB (MCMB), pitch coke etc.But its theoretical specific capacity is lower, be only 372mAh g -1, and its high rate performance and security performance poor.Metal oxide materials has high specific discharge capacity and volume and capacity ratio because of it and becomes a kind of Novel anode material (Nature, 407 (2000) 496-499) very with alternative carbon negative electrode material of lithium ion cell potentiality.The metal oxide-type negative material of current report mainly comprises binary oxide (MO, M=Mn, Fe, Co, Ni or Cu), ternary spinel strucutre oxides (AB2O4, A=Mn, Fe, Co, Ni or Cu; B=Mn, Fe, Co, Ni or Cu; A ≠ B) and mixed oxide (being generally the mixture of binary oxide and ternary oxide), the taking off of its storage lithium mechanism and traditional lithium-ion battery negative material/embedding lithium reacts or different with the alloying reaction of lithium, for the Reversible redox reaction (Angewandte Chemie International Edition, 47 (2008) 2930-2946) between lithium metal and oxide.
But metal oxide is still faced with the problems such as capacitance loss is large, cyclical stability is poor, multiplying power discharging property is poor first at present as lithium ion battery negative material.In addition, the complicated process of preparation of the metal oxide-type negative material reported in current document and cost is high, is unsuitable for actual production.
Summary of the invention
Object of the present invention is exactly provide a kind of effectively can improve the heavy-current discharge performance of lithium ion battery and the used as negative electrode of Li-ion battery mixed oxide material of cyclical stability and preparation method thereof to overcome defect that above-mentioned prior art exists.
Object of the present invention can be achieved through the following technical solutions: used as negative electrode of Li-ion battery hollow porous spherical mixed oxide, is characterized in that, this material is the homogeneous mixture of Mn2O3 and NiMn2O4, and concrete chemical formula is Ni xmn 1-xo 1.5-0.5x(0 < x < 1/3).
A kind of preparation method of used as negative electrode of Li-ion battery hollow porous spherical mixed oxide, the method is based on the complexing between ammoniacal liquor and nickel ion thus slow down the settling velocity of nickelous carbonate, make nickelous carbonate can not destroy the spherical structure of manganese carbonate but have certain modification to the spherical structure of manganese carbonate, and then form the spherical mixture (Ni of uniform nickelous carbonate and manganese carbonate xmn 1-xcO 30 < x < 1/3), then adopt the high temp. sectional method of roasting based on heterogeneous sintering and oersted Wa Erde slaking principle (Ostwald ripening) to obtain prepared used as negative electrode of Li-ion battery hollow porous spherical mixed oxide;
The method specifically comprises following step: adopt carbonic hydroammonium as coprecipitator, using nickel source and manganese source solution as source metal solution, utilize coprecipitation to make the nickel source in solution and manganese source precipitation obtain the mixture of nickelous carbonate and manganese carbonate, then adopt high temp. sectional roasting to obtain prepared used as negative electrode of Li-ion battery hollow porous spherical mixed oxide.
Described nickel source is the one in nickel nitrate, nickelous sulfate or nickel acetate; Manganese source is the one in manganese nitrate, manganese sulfate, manganese acetate or manganese oxalate; Wherein the mol ratio in nickel source and manganese source is 1: 10-3: 1.
The mol ratio of described carbonic hydroammonium and source metal (nickel source and manganese source sum) is 5: 1-15: 1.
The solvent composition of described source metal solution is ethanol water, and wherein the volume ratio of second alcohol and water is 1: 5-1: 15, and the ratio of the water in source metal and solvent is 1mmol: 50mL-1mmol: 100mL.
The process of described coprecipitation is stirring reaction 9-24h at 40-50 DEG C.
Described baking inphases is two-stage roasting process, and first paragraph is 400-600 DEG C, and heating rate is 2-5 DEG C/min, and roasting time is 1-5h; Second segment is 800-1000 DEG C, and heating rate is 1-5 DEG C/min, and roasting time is 1-5h.
Compared with prior art, the present invention has the following advantages:
(1) preparation method of used as negative electrode of Li-ion battery mixed oxide material disclosed in this invention is simple, is conducive to industrialization large-scale production;
(2) hollow porous spherical mixed oxide provided by the present invention is utilized, because its hollow porous micro sphere structure be made up of multiple nanometer blocks can provide enough electrode/electrolyte contacts area, the electrochemical kinetics accelerating reversible transition reaction between lithium metal and oxide and the transmission speed of electronics and ion, the structural stability improved in cyclic process, can obviously improve its heavy-current discharge performance and cyclical stability as lithium ion battery negative material.
Accompanying drawing explanation
Fig. 1 is the NiCO prepared by reference examples 1 3the SEM figure of material;
Fig. 2 is the MnCO prepared by reference examples 2 3the SEM figure of material;
Fig. 3 is the Ni prepared by reference examples 3 0.33mn 0.67cO 3the SEM figure of material;
Fig. 4 is the Ni prepared by embodiment 1 0.14mn 0.86cO 3the SEM figure of material;
Fig. 5 is the hollow porous spherical Ni prepared by embodiment 1 0.14mn 0.86o 1.43the SEM figure of material;
Fig. 6 is the hollow porous spherical Ni prepared by embodiment 1 0.14mn 0.86o 1.43the XRD figure of material;
Fig. 7 is the hollow porous spherical Ni prepared by embodiment 1 0.14mn 0.86o 1.43material is used for the high rate performance figure of lithium ion battery negative;
Fig. 8 is the hollow porous spherical Ni prepared by embodiment 1 0.14mn 0.86o 1.43material is used for the cycle performance figure of lithium ion battery negative.
Embodiment
Below in conjunction with accompanying drawing, the preparation method to used as negative electrode of Li-ion battery mixed oxide material disclosed in this invention is described further.
Reference examples 1
First Ni (the NO of 5mmol is weighed 3) 26H 2o, the absolute ethyl alcohol then measuring 35mL joins in the deionized water of 350mL in the lump, and vigorous stirring obtains A liquid after above-mentioned salt all dissolves; In the deionized water of another part of 350mL, add the NH of 50mmol simultaneously 4hCO 3and after vigorous stirring, obtain B liquid.Subsequently B liquid to be joined in A liquid and vigorous stirring, then heat reactant liquor to 45 DEG C and maintain 9h.After stopping reaction, reacting liquid filtering is used a large amount of washed with de-ionized water, obtain green solid (NiCO with final vacuum 60 DEG C of dryings 3).Figure 1 shows that the NiCO of preparation 3the SEM figure of material, as can be seen from the figure NiCO 3material is Powdered.
Reference examples 2
First the MnSO of 5mmol is weighed 4h 2o, the absolute ethyl alcohol then measuring 35mL joins in the deionized water of 350mL in the lump, and vigorous stirring obtains A liquid after above-mentioned salt all dissolves; In the deionized water of another part of 350mL, add the NH of 50mmol simultaneously 4hCO 3and after vigorous stirring, obtain B liquid.Subsequently B liquid to be joined in A liquid and vigorous stirring, then heat reactant liquor to 45 DEG C and maintain 9h.After stopping reaction, reacting liquid filtering is used a large amount of washed with de-ionized water, obtain white solid (MnCO with final vacuum 60 DEG C of dryings 3).Fig. 2 is the MnCO being depicted as preparation 3the SEM figure of material, as can be seen from the figure MnCO 3material is spherical in shape.
Reference examples 3
First Ni (the NO of 1.67mmol is weighed 3) 26H 2the MnSO of O and 3.33mmol 4h 2o, the absolute ethyl alcohol then measuring 35mL joins in the deionized water of 350mL in the lump, and vigorous stirring obtains A liquid after above-mentioned salt all dissolves; In the deionized water of another part of 350mL, add the NaHCO of 50mmol simultaneously 3and after vigorous stirring, obtain B liquid.Subsequently B liquid to be joined in A liquid and vigorous stirring, then heat reactant liquor to 45 DEG C and maintain 9h.After stopping reaction, reacting liquid filtering is used a large amount of washed with de-ionized water, obtain light green solid (Ni with final vacuum 60 DEG C of dryings 0.33mn 0.67cO 3).Fig. 3 is the Ni being depicted as preparation 0.33mn 0.67cO 3the SEM figure of material, as can be seen from the figure Ni 0.33mn 0.67cO 3material is Powdered.
Embodiment 1
First Ni (the NO of 1.67mmol is weighed 3) 26H 2the MnSO of O and 3.33mmol 4h 2o, the absolute ethyl alcohol then measuring 35mL joins in the deionized water of 350mL in the lump, and vigorous stirring obtains A liquid after above-mentioned salt all dissolves; In the deionized water of another part of 350mL, add the NH of 50mmol simultaneously 4hCO 3and after vigorous stirring, obtain B liquid.Subsequently B liquid to be joined in A liquid and vigorous stirring, then heat reactant liquor to 45 DEG C and maintain 9h.After stopping reaction, reacting liquid filtering is used a large amount of washed with de-ionized water, obtain light green solid (Ni with final vacuum 60 DEG C of dryings 0.14mn 0.86cO 3).Gained solid is positioned in Muffle furnace and rises to 600 DEG C of roasting 3h with the heating rate of 2 DEG C/min, then continues to rise to 900 DEG C of roasting 2h with the heating rate of 2 DEG C/min and obtains prepared Porous hollow Ni 0.14mn 0.86o 1.43microballoon (0.29Mn 2o 3/ 0.14NiMn 2o 4).
Fig. 4 is prepared mixed oxide Ni 0.14mn 0.86cO 3the SEM figure of microballoon.Comparison diagram 1-3 can draw, Ni 0.14mn 0.86cO 3microballoon is that main body is formed based on manganese carbonate microballoon, and the complexing between nickel ion and ammoniacal liquor effectively can slow down the settling velocity of nickelous carbonate, thus can not destroy the spherical morphology of manganese carbonate, but plays modification to the microballoon of manganese carbonate.Fig. 5 is prepared Ni 0.14mn 0.86cO 3scanning electron microscope (SEM) photograph, as can be seen from the figure prepared mixed oxide be hollow cellular, and mixed oxide microballoon is formed by many nano block accumulations, and wherein nano block is stratiform pattern.Prepared Ni 0.14mn 0.86cO 3xRD spectra see Fig. 6, with Mn 2o 3and NiMn 2o 4standard chromatogram accordance.Utilize this material as lithium ion battery negative material, effectively improve heavy-current discharge performance (Fig. 7) and the cycle performance (Fig. 8) of lithium ion battery.When current density is 800mA g -1time, the reversible specific capacity of battery reaches 588.4mA h g -1, after 150 circle circulations, its specific capacity still can reach 408mA h g -1, capability retention is 69.3%.
Embodiment 2
First the NiSO of 1.67mmol is weighed 46H 2mn (the NO of O and 3.33mmol 3) 2, the absolute ethyl alcohol then measuring 70mL joins in the deionized water of 350mL in the lump, and vigorous stirring obtains A liquid after above-mentioned salt all dissolves; In the deionized water of another part of 350mL, add the NH of 75mmol simultaneously 4hCO 3and after vigorous stirring, obtain B liquid.Subsequently B liquid to be joined in A liquid and vigorous stirring, then heat reactant liquor to 45 DEG C and maintain 9h.After stopping reaction, reacting liquid filtering is used a large amount of washed with de-ionized water, obtain light green solid with final vacuum 60 DEG C of dryings.Gained solid is positioned in Muffle furnace and rises to 600 DEG C of roasting 3h with the heating rate of 2 DEG C/min, then continues to rise to 900 DEG C of roasting 2h with the heating rate of 2 DEG C/min and obtains prepared Porous hollow mixed oxide.
Embodiment 3
First the C of 1.67mmol is weighed 4h 6o 4ni4H 2the C of O and 3.33mmol 4h 6mnO 4, the absolute ethyl alcohol then measuring 25mL joins in the deionized water of 375mL in the lump, and vigorous stirring obtains A liquid after above-mentioned salt all dissolves; In the deionized water of another part of 350mL, add the NH of 25mmol simultaneously 4hCO 3and after vigorous stirring, obtain B liquid.Subsequently B liquid to be joined in A liquid and vigorous stirring, then heat reactant liquor to 45 DEG C and maintain 9h.After stopping reaction, reacting liquid filtering is used a large amount of washed with de-ionized water, obtain light green solid with final vacuum 60 DEG C of dryings.Gained solid is positioned in Muffle furnace and rises to 600 DEG C of roasting 3h with the heating rate of 2 DEG C/min, then continues to rise to 900 DEG C of roasting 2h with the heating rate of 2 DEG C/min and obtains prepared Porous hollow mixed oxide.
Embodiment 4
First Ni (the NO of 3.75mmol is weighed 3) 26H 2the MnSO of O and 1.25mmol 4h 2o, the absolute ethyl alcohol then measuring 25mL joins in the deionized water of 250mL in the lump, and vigorous stirring obtains A liquid after above-mentioned salt all dissolves; In the deionized water of another part of 350mL, add the NH of 50mmol simultaneously 4hCO 3and after vigorous stirring, obtain B liquid.Subsequently B liquid to be joined in A liquid and vigorous stirring, then heat reactant liquor to 50 DEG C and maintain 24h.After stopping reaction, reacting liquid filtering is used a large amount of washed with de-ionized water, obtain light green solid with final vacuum 60 DEG C of dryings.Gained solid is positioned in Muffle furnace and rises to 500 DEG C of roasting 5h with the heating rate of 5 DEG C/min, then continues to rise to 800 DEG C of roasting 1h with the heating rate of 1 DEG C/min and obtains prepared Porous hollow mixed oxide.
Embodiment 5
First Ni (the NO of 0.45mmol is weighed 3) 26H 2the MnSO of O and 4.5mmol 4.H 2o, the absolute ethyl alcohol then measuring 50mL joins in the deionized water of 500mL in the lump, and vigorous stirring obtains A liquid after above-mentioned salt all dissolves; In the deionized water of another part of 350mL, add the NH of 50mmol simultaneously 4hCO 3and after vigorous stirring, obtain B liquid.Subsequently B liquid to be joined in A liquid and vigorous stirring, then heat reactant liquor to 40 DEG C and maintain 15h.After stopping reaction, reacting liquid filtering is used a large amount of washed with de-ionized water, obtain light green solid with final vacuum 60 DEG C of dryings.Gained solid is positioned in Muffle furnace and rises to 400 DEG C of roasting 1h with the heating rate of 2 DEG C/min, then continues to rise to 1000 DEG C of roasting 5h with the heating rate of 5 DEG C/min and obtains prepared Porous hollow mixed oxide.
It should be noted that, the invention is not restricted to above-described embodiment, be anyly familiar with those skilled in the art in the technical scope that the present invention discloses, the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection range of claim.

Claims (7)

1. used as negative electrode of Li-ion battery hollow porous spherical mixed oxide, is characterized in that, this material is Mn 2o 3and NiMn 2o 4homogeneous mixture, concrete chemical formula is Ni xmn 1-xo 1.5-0.5x(0 < x < 1/3).
2. the preparation method of a used as negative electrode of Li-ion battery hollow porous spherical mixed oxide according to claim 1, it is characterized in that, the method is based on the complexing between ammoniacal liquor and nickel ion thus slow down the settling velocity of nickelous carbonate, make nickelous carbonate can not destroy the spherical structure of manganese carbonate but have certain modification to the spherical structure of manganese carbonate, and then form the spherical mixture (Ni of uniform nickelous carbonate and manganese carbonate xmn 1-xcO 30 < x < 1/3), then adopt the high temp. sectional method of roasting based on heterogeneous sintering and oersted Wa Erde slaking principle (Ostwald ripening) to obtain prepared used as negative electrode of Li-ion battery hollow porous spherical mixed oxide; Specifically comprise the following steps: adopt carbonic hydroammonium as coprecipitator, using nickel source and manganese source solution as source metal solution, utilize coprecipitation to make the nickel source in solution and manganese source precipitation obtain the mixture of nickelous carbonate and manganese carbonate, then adopt high temp. sectional roasting to obtain prepared used as negative electrode of Li-ion battery hollow porous spherical mixed oxide.
3. the preparation method of a kind of used as negative electrode of Li-ion battery hollow porous spherical mixed oxide according to claim 2, it is characterized in that, described nickel source is the one in nickel nitrate, nickelous sulfate or nickel acetate; Manganese source is the one in manganese nitrate, manganese sulfate, manganese acetate or manganese oxalate; Wherein the mol ratio in nickel source and manganese source is 1: 10-3: 1.
4. the preparation method of a kind of used as negative electrode of Li-ion battery hollow porous spherical mixed oxide according to claim 2, it is characterized in that, described carbonic hydroammonium and the mol ratio of source metal are 5: 1-15: 1.
5. the preparation method of a kind of used as negative electrode of Li-ion battery hollow porous spherical mixed oxide according to claim 2, it is characterized in that, the solvent composition of described source metal solution is ethanol water, wherein the volume ratio of second alcohol and water is 1: 5-1: 15, and the ratio of the water in source metal and solvent is 1mmol: 50mL-1mmol: 100mL.
6. the preparation method of a kind of used as negative electrode of Li-ion battery hollow porous spherical mixed oxide according to claim 2, is characterized in that, the process of described coprecipitation is stirring reaction 9-24h at 40-50 DEG C.
7. the preparation method of a kind of used as negative electrode of Li-ion battery hollow porous spherical mixed oxide according to claim 2, it is characterized in that, described baking inphases is two-stage roasting process, and first paragraph is 400-600 DEG C, heating rate is 2-5 DEG C/min, and roasting time is 1-5h; Second segment is 800-1000 DEG C, and heating rate is 1-5 DEG C/min, and roasting time is 1-5h.
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CN105304901A (en) * 2015-09-25 2016-02-03 北京理工大学 Nickel-carbonate-doped manganese-carbonate-based anode material for lithium ion battery and preparation method
CN106430316A (en) * 2016-09-13 2017-02-22 安庆师范大学 Preparation of hollow Mn2O3 micro-spheres and application method thereof in lithium battery
CN106784825A (en) * 2017-03-15 2017-05-31 北京理工大学 A kind of spherical nickeliferous carbonic acid manganese material and its preparation method and application
CN106935837A (en) * 2017-04-28 2017-07-07 武汉理工大学 The hollow porous ball material of di-iron trioxide/manganese sesquioxide managnic oxide and its preparation and application
CN108439474A (en) * 2018-03-12 2018-08-24 南京信息工程大学 A kind of lithium battery high-performance Ni doping MnCO3The preparation method of negative material
CN109301234A (en) * 2018-09-29 2019-02-01 中南大学 Lithium ion battery negative material transiton metal binary oxides and preparation method thereof
CN109301234B (en) * 2018-09-29 2021-05-07 中南大学 Binary metal oxide as negative electrode material of lithium ion battery and preparation method thereof
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CN115959709A (en) * 2022-10-27 2023-04-14 广西中伟新能源科技有限公司 High-aluminum-doped manganese carbonate and preparation method thereof, lithium ion battery anode material, lithium ion battery and electric equipment

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