CN104466108B - Used as negative electrode of Li-ion battery hollow porous spherical mixed oxide and preparation method thereof - Google Patents

Used as negative electrode of Li-ion battery hollow porous spherical mixed oxide and preparation method thereof Download PDF

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CN104466108B
CN104466108B CN201410728110.XA CN201410728110A CN104466108B CN 104466108 B CN104466108 B CN 104466108B CN 201410728110 A CN201410728110 A CN 201410728110A CN 104466108 B CN104466108 B CN 104466108B
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manganese
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carbonate
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CN104466108A (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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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • 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
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    • 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
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    • 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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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The present invention relates to used as negative electrode of Li-ion battery hollow porous spherical mixed oxide and preparation method thereof, this material is Mn2O3And NiMn2O4Even mixture, concrete chemical formula is NixMn1‑xO1.5‑0.5x(0 ＜ x ＜ 1/3).The preparation method of this hollow porous spherical mixed oxide is based on the complexing between ammonia and nickel ion thus slows down the settling velocity of nickelous carbonate, make nickelous carbonate will not destroy the spherical structure of manganese carbonate but the spherical structure of manganese carbonate is had certain modification, and then form the spherical mixture (Ni of uniform nickelous carbonate and manganese carbonatexMn1‑xCO3, 0 ＜ x ＜ 1/3), then use the method for high temp. sectional roasting to obtain prepared used as negative electrode of Li-ion battery hollow porous spherical mixed oxide.Compared with prior art, the inventive method is simple to operate, be applicable to industrialized mass；Utilize hollow porous spherical mixed oxide disclosed in this invention can be effectively improved high rate during charging-discharging and the cycle life of lithium ion battery negative.

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 that one possesses high-energy-density, high power density, high safety performance, long circulation life etc. The energy conversion device of advantage, have be applied in electric automobile and large scale electric network great potential (Science, 311(2006)977-980；Nature, 414 (2001) 359-367).The negative pole that the most commercial lithium ion battery uses Material is mainly material with carbon element, such as native graphite, MCMB (MCMB), pitch coke etc..But its reason Opinion specific capacity is relatively low, only 372mAh g-1, and its high rate performance and security performance are poor.Metal-oxide Material becomes one have very much replacement lithium ion battery because it has high specific discharge capacity and volume and capacity ratio The Novel anode material (Nature, 407 (2000) 496-499) of carbon negative pole material potentiality.The metal oxygen of report at present Compound class negative material mainly includes binary oxide (MO, M=Mn, Fe, Co, Ni or Cu), ternary point Spinel structure oxide (AB2O4, A=Mn, Fe, Co, Ni or Cu；B=Mn, Fe, Co, Ni or Cu；A ≠ B) and mixed oxide (usually binary oxide and the mixture of ternary oxide), it stores up lithium Mechanism is reacted or different with the alloying reaction of lithium, for metal from the de-/embedding lithium of traditional lithium-ion battery negative material Reversible redox reaction between lithium and oxide (Angewandte Chemie International Edition, 47(2008)2930-2946)。
But, metal-oxide still suffer from present as lithium ion battery negative material capacitance loss first big, The problems such as cyclical stability is poor, multiplying power discharging property is poor.Additionally, the metal oxide-type of report is born in current document The complicated process of preparation of pole material and cost are high, are unsuitable for actual production.
Summary of the invention
Defect that the purpose of the present invention is contemplated to overcome above-mentioned prior art to exist and provide one effectively to change The heavy-current discharge performance of kind lithium ion battery and the used as negative electrode of Li-ion battery mixed oxide material of cyclical stability Material and preparation method thereof.
The purpose 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, it is characterised in that this material is the homogeneous mixture of Mn2O3 and NiMn2O4, specifically chemistry Formula is NixMn1-xO1.5-0.5x(0 ＜ x ＜ 1/3).
The preparation method of a kind of used as negative electrode of Li-ion battery hollow porous spherical mixed oxide, the method is based on ammonia And complexing between nickel ion thus slow down the settling velocity of nickelous carbonate so that nickelous carbonate will not destroy manganese carbonate Spherical structure but the spherical structure of manganese carbonate is had certain modification, and then formed uniform nickelous carbonate and Spherical mixture (the Ni of manganese carbonatexMn1-xCO3, 0 ＜ x ＜ 1/3), then use based on heterogeneous sintering and difficult to understand this The high temp. sectional method of roasting of Te Waerde ripening principle (Ostwald ripening) obtains prepared lithium-ion electric Pond negative pole hollow porous spherical mixed oxide；
The method specifically includes following step: employing ammonium hydrogen carbonate is as coprecipitator, molten with nickel source and manganese source Liquid, as source metal solution, utilizes coprecipitation to make the nickel source in solution and manganese source precipitation obtain nickelous carbonate and manganese carbonate Mixture, then use high temp. sectional roasting obtain prepared used as negative electrode of Li-ion battery hollow porous spherical mix Close oxide.
Described nickel source is the one in nickel nitrate, nickel sulfate or nickel acetate；Manganese source is manganese nitrate, manganese sulfate, vinegar One in acid manganese or manganese oxalate；Wherein the mol ratio in nickel source and manganese source is 1: 10-3: 1.
Described ammonium hydrogen carbonate is 5: 1-15: 1 with the mol ratio of source metal (nickel source and manganese source sum).
The group of solvents of described source metal solution becomes ethanol water, and wherein the volume ratio of second alcohol and water is 1: 5-1: 15, source metal is 1mmol: 50mL-1mmol: 100mL with the ratio of the water in solvent.
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, roasting time is 1-5h；Second segment is 800-1000 DEG C, and heating rate is 1-5 DEG C/min, roasting time For 1-5h.
Compared with prior art, the invention have the advantages that
(1) preparation method of used as negative electrode of Li-ion battery mixed oxide material disclosed in this invention is simple, has It is beneficial to industrialization large-scale production；
(2) hollow porous spherical mixed oxide provided by the present invention is utilized, because it is made up of multiple nanometer blocks Hollow porous micro sphere structure enough electrode/electrolyte contact area can be provided, accelerate lithium metal and oxide Between reversible transition reaction electrochemical kinetics and electronics and the transmission speed of ion, improve in cyclic process Structural stability, can be obviously improved its heavy-current discharge performance and stable circulation as lithium ion battery negative material Property.
Accompanying drawing explanation
Fig. 1 is the NiCO prepared by reference examples 13The SEM figure of material；
Fig. 2 is the MnCO prepared by reference examples 23The SEM figure of material；
Fig. 3 is the Ni prepared by reference examples 30.33Mn0.67CO3The SEM figure of material；
Fig. 4 is the Ni prepared by embodiment 10.14Mn0.86CO3The SEM figure of material；
Fig. 5 is the hollow porous spherical Ni prepared by embodiment 10.14Mn0.86O1.43The SEM figure of material；
Fig. 6 is the hollow porous spherical Ni prepared by embodiment 10.14Mn0.86O1.43The XRD figure of material；
Fig. 7 is the hollow porous spherical Ni prepared by embodiment 10.14Mn0.86O1.43Material is born for lithium ion battery The high rate performance figure of pole；
Fig. 8 is the hollow porous spherical Ni prepared by embodiment 10.14Mn0.86O1.43Material is born for lithium ion battery The cycle performance figure of pole.
Detailed description of the invention
Preparation side to used as negative electrode of Li-ion battery mixed oxide material disclosed in this invention below in conjunction with the accompanying drawings Method is described further.
Reference examples 1
First Ni (the NO of 5mmol is weighed3)2·6H2O, the dehydrated alcohol then measuring 35mL joins in the lump In the deionized water of 350mL, it is stirred vigorously, after above-mentioned salt all dissolves, obtains A liquid；Simultaneously to another The deionized water of part 350mL adds the NH of 50mmol4HCO3And after being stirred vigorously, obtain B liquid.Subsequently Being joined in A liquid by B liquid and be stirred vigorously, then reacting by heating liquid maintains 9h to 45 DEG C.After stopped reaction Clean by reacting liquid filtering and with a large amount of deionized waters, be dried to obtain green solid (NiCO with final vacuum 60 DEG C3)。 Fig. 1 show the NiCO of preparation3The SEM figure of material, as can be seen from the figure NiCO3Material is powder.
Reference examples 2
First the MnSO of 5mmol is weighed4·H2O, the dehydrated alcohol then measuring 35mL joins 350 in the lump In the deionized water of mL, it is stirred vigorously, after above-mentioned salt all dissolves, obtains A liquid；Simultaneously to another part The deionized water of 350mL adds the NH of 50mmol4HCO3And after being stirred vigorously, obtain B liquid.Subsequently will B liquid joins in A liquid and is stirred vigorously, and then reacting by heating liquid maintains 9h to 45 DEG C.Will be anti-after stopped reaction Answer liquid to filter and use a large amount of deionized water to clean, being dried to obtain white solid (MnCO with final vacuum 60 DEG C3).Figure 2 is the MnCO showing preparation3The SEM figure of material, as can be seen from the figure MnCO3Material is spherical in shape.
Reference examples 3
First Ni (the NO of 1.67mmol is weighed3)2·6H2The MnSO of O and 3.33mmol4·H2O, then measures The dehydrated alcohol of 35mL joins in the deionized water of 350mL in the lump, is stirred vigorously, and treats that above-mentioned salt is whole A liquid is obtained after dissolving；In the deionized water of another part of 350mL, add the NaHCO of 50mmol simultaneously3 And after being stirred vigorously, obtain B liquid.Subsequently B liquid joined in A liquid and be stirred vigorously, then reacting by heating liquid 9h is maintained to 45 DEG C.By reacting liquid filtering and with the cleaning of a large amount of deionized waters after stopped reaction, with final vacuum 60 DEG C It is dried to obtain light green solid (Ni0.33Mn0.67CO3).Fig. 3 is the Ni showing preparation0.33Mn0.67CO3Material SEM figure, as can be seen from the figure Ni0.33Mn0.67CO3Material is powder.
Embodiment 1
First Ni (the NO of 1.67mmol is weighed3)2·6H2The MnSO of O and 3.33mmol4·H2O, then measures The dehydrated alcohol of 35mL joins in the deionized water of 350mL in the lump, is stirred vigorously, and treats that above-mentioned salt is whole A liquid is obtained after dissolving；In the deionized water of another part of 350mL, add the NH of 50mmol simultaneously4HCO3 And after being stirred vigorously, obtain B liquid.Subsequently B liquid joined in A liquid and be stirred vigorously, then reacting by heating liquid 9h is maintained to 45 DEG C.By reacting liquid filtering and with the cleaning of a large amount of deionized waters after stopped reaction, with final vacuum 60 DEG C It is dried to obtain light green solid (Ni0.14Mn0.86CO3).Gained solid is positioned in Muffle furnace with the liter of 2 DEG C/min Temperature speed rises to 600 DEG C of roasting 3h, then proceedes to rise to 900 DEG C of roasting 2h with the heating rate of 2 DEG C/min and obtains To prepared Porous hollow Ni0.14Mn0.86O1.43Microsphere (0.29Mn2O3/0.14NiMn2O4)。
Fig. 4 is prepared mixed oxide Ni0.14Mn0.86CO3The SEM figure of microsphere.Comparison diagram 1-3 can obtain Go out, Ni0.14Mn0.86CO3Microsphere is that main body is formed based on manganese carbonate microsphere, the network between nickel ion and ammonia The cooperation settling velocity that can effectively slow down nickelous carbonate, from the spherical morphology without destroying manganese carbonate, but right The microsphere of manganese carbonate plays modification.Fig. 5 is prepared Ni0.14Mn0.86CO3Scanning electron microscope (SEM) photograph, from figure Can be seen that prepared mixed oxide is hollow cellular, mixed oxide microsphere is piled up by many nano blocks Forming, wherein nano block is stratiform pattern.Prepared Ni0.14Mn0.86CO3XRD spectra see Fig. 6, With Mn2O3And NiMn2O4Standard chromatogram accordance.Utilize this material as lithium ion battery negative material, have Improve to effect heavy-current discharge performance (Fig. 7) and the cycle performance (Fig. 8) of lithium ion battery.Work as electric current density For 800mA g-1Time, the reversible specific capacity of battery has reached 588.4mA h g-1, its ratio after 150 circle circulations Capacity still can reach 408mA h g-1, capability retention is 69.3%.
Embodiment 2
First the NiSO of 1.67mmol is weighed4·6H2Mn (the NO of O and 3.33mmol3)2, then measure 70 The dehydrated alcohol of mL joins in the deionized water of 350mL in the lump, is stirred vigorously, and treats that above-mentioned salt is the most molten A liquid is obtained after solution；In the deionized water of another part of 350mL, add the NH of 75mmol simultaneously4HCO3And B liquid is obtained after being stirred vigorously.Being joined in A liquid by B liquid subsequently and be stirred vigorously, then reacting by heating liquid is extremely 45 DEG C maintain 9h.By reacting liquid filtering and with the cleaning of a large amount of deionized waters after stopped reaction, do with final vacuum 60 DEG C Dry obtain light green solid.Gained solid is positioned in Muffle furnace and rises to 600 DEG C of roastings with the heating rate of 2 DEG C/min Burn 3h, then proceed to rise to 900 DEG C of roasting 2h with the heating rate of 2 DEG C/min and obtain prepared Porous hollow Mixed oxide.
Embodiment 3
First the C of 1.67mmol is weighed4H6O4Ni·4H2The C of O and 3.33mmol4H6MnO4, then measure The dehydrated alcohol of 25mL joins in the deionized water of 375mL in the lump, is stirred vigorously, and treats that above-mentioned salt is whole A liquid is obtained after dissolving；In the deionized water of another part of 350mL, add the NH of 25mmol simultaneously4HCO3 And after being stirred vigorously, obtain B liquid.Subsequently B liquid joined in A liquid and be stirred vigorously, then reacting by heating liquid 9h is maintained to 45 DEG C.By reacting liquid filtering and with the cleaning of a large amount of deionized waters after stopped reaction, with final vacuum 60 DEG C It is dried to obtain light green solid.Gained solid is positioned in Muffle furnace and rises to 600 DEG C with the heating rate of 2 DEG C/min Roasting 3h, then proceedes 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 weighed3)2·6H2The MnSO of O and 1.25mmol4·H2O, then measures The dehydrated alcohol of 25mL joins in the deionized water of 250mL in the lump, is stirred vigorously, and treats that above-mentioned salt is whole A liquid is obtained after dissolving；In the deionized water of another part of 350mL, add the NH of 50mmol simultaneously4HCO3 And after being stirred vigorously, obtain B liquid.Subsequently B liquid joined in A liquid and be stirred vigorously, then reacting by heating liquid 24h is maintained to 50 DEG C.By reacting liquid filtering and with the cleaning of a large amount of deionized waters after stopped reaction, with final vacuum 60 DEG C It is dried to obtain light green solid.Gained solid is positioned in Muffle furnace and rises to 500 DEG C with the heating rate of 5 DEG C/min Roasting 5h, then proceedes to rise to 800 DEG C of roasting 1h with the heating rate of 1 DEG C/min and obtains in prepared porous Empty mixed oxide.
Embodiment 5
First Ni (the NO of 0.45mmol is weighed3)2·6H2The MnSO of O and 4.5mmol4.H2O, then measures 50 The dehydrated alcohol of mL joins in the deionized water of 500mL in the lump, is stirred vigorously, and treats that above-mentioned salt is the most molten A liquid is obtained after solution；In the deionized water of another part of 350mL, add the NH of 50mmol simultaneously4HCO3And B liquid is obtained after being stirred vigorously.Being joined in A liquid by B liquid subsequently and be stirred vigorously, then reacting by heating liquid is extremely 40 DEG C maintain 15h.By reacting liquid filtering and with the cleaning of a large amount of deionized waters after stopped reaction, with final vacuum 60 DEG C It is dried to obtain light green solid.Gained solid is positioned in Muffle furnace and rises to 400 DEG C with the heating rate of 2 DEG C/min Roasting 1h, then proceedes 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, any those familiar with the art exists In the technical scope that the invention discloses, the change that can readily occur in or replacement, all should contain the protection model in the present invention Within enclosing.Therefore, protection scope of the present invention should be as the criterion with scope of the claims.

Claims (7)

1. used as negative electrode of Li-ion battery hollow porous spherical mixed oxide, it is characterised in that this material is Mn2O3 And NiMn2O4Homogeneous mixture, concrete chemical formula is NixMn1-xO1.5-0.5x, wherein, 0 < x < 1/3；
The preparation method of described hollow porous spherical mixed oxide is based on the complexing between ammonia and nickel ion Thus slowing down the settling velocity of nickelous carbonate so that nickelous carbonate will not destroy the spherical structure of manganese carbonate but to manganese carbonate Spherical structure there is certain modification, and then form the spherical mixture of uniform nickelous carbonate and manganese carbonate NixMn1-xCO3, wherein, 0 < x < 1/3, then use based on heterogeneous sintering and oersted Wa Erde ripening principle The high temp. sectional method of roasting of (Ostwald ripening) obtains prepared used as negative electrode of Li-ion battery hollow porous Spherical mixed oxide；Specifically include following steps: employing ammonium hydrogen carbonate is as coprecipitator, with nickel source and manganese source Solution, as source metal solution, utilizes coprecipitation to make the nickel source in solution and manganese source precipitation obtain nickelous carbonate and carbonic acid The mixture of manganese, then uses high temp. sectional roasting to obtain prepared used as negative electrode of Li-ion battery hollow porous spherical Mixed oxide.
2. a used as negative electrode of Li-ion battery hollow porous spherical mixed oxide according to claim 1 Preparation method, it is characterised in that the method is based on the complexing between ammonia and nickel ion thus slows down nickelous carbonate Settling velocity so that nickelous carbonate will not destroy the spherical structure of manganese carbonate but the spherical structure of manganese carbonate is had one Fixed modification, and then form the spherical mixture Ni of uniform nickelous carbonate and manganese carbonatexMn1-xCO3, wherein, 0 < x < 1/3, then use based on heterogeneous sintering and oersted Wa Erde ripening principle (Ostwald ripening) High temp. sectional method of roasting obtain prepared used as negative electrode of Li-ion battery hollow porous spherical mixed oxide；Tool Body comprises the following steps: use ammonium hydrogen carbonate 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 use High temp. sectional roasting obtains prepared used as negative electrode of Li-ion battery hollow porous spherical mixed oxide.
A kind of used as negative electrode of Li-ion battery hollow porous spherical mixed oxide the most according to claim 2 Preparation method, it is characterised in that described nickel source is the one in nickel nitrate, nickel sulfate or nickel acetate；Manganese source is 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.
A kind of used as negative electrode of Li-ion battery hollow porous spherical mixed oxide the most according to claim 2 Preparation method, it is characterised in that described ammonium hydrogen carbonate is 5:1-15:1 with the mol ratio of source metal.
A kind of used as negative electrode of Li-ion battery hollow porous spherical mixed oxide the most according to claim 2 Preparation method, it is characterised in that the group of solvents of described source metal solution becomes ethanol water, wherein ethanol and The volume ratio of water is 1:5-1:15, and source metal is 1mmol:50mL-1mmol:100 with the ratio of the water in solvent mL。
A kind of used as negative electrode of Li-ion battery hollow porous spherical mixed oxide the most according to claim 2 Preparation method, it is characterised in that the process of described coprecipitation is stirring reaction 9-24h at 40-50 DEG C.
A kind of used as negative electrode of Li-ion battery hollow porous spherical mixed oxide the most according to claim 2 Preparation method, it is characterised in that described baking inphases is two-stage roasting process, 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, roasting time is 1-5h.
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CN105304901B (en) * 2015-09-25 2018-10-26 北京理工大学 A kind of manganese carbonate base negative material and preparation method of the lithium ion battery doped with nickelous carbonate
CN106430316B (en) * 2016-09-13 2017-12-05 安庆师范大学 Hollow Mn2O3The preparation of micron ball and its application process 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
CN108439474B (en) * 2018-03-12 2020-10-09 南京信息工程大学 High-performance Ni-doped MnCO for lithium battery3Preparation method of negative electrode material
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
CN111435745B (en) * 2019-12-26 2022-05-27 蜂巢能源科技有限公司 Binary lithium-rich carbonate precursor and preparation method and application thereof
CN113213542B (en) * 2021-04-26 2022-04-12 中国计量大学 Manganese sesquioxide multi-shell nano hollow sphere material and preparation and application thereof
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