CN103682303A - Lithium ion battery, active material of negative electrode thereof, and preparation method of active material - Google Patents

Lithium ion battery, active material of negative electrode thereof, and preparation method of active material Download PDF

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Publication number
CN103682303A
CN103682303A CN201310554493.9A CN201310554493A CN103682303A CN 103682303 A CN103682303 A CN 103682303A CN 201310554493 A CN201310554493 A CN 201310554493A CN 103682303 A CN103682303 A CN 103682303A
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lithium ion
ion battery
active material
anode active
manganese dioxide
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CN103682303B (en
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陈敬波
尚玉明
王要武
何向明
李建军
王莉
高剑
徐盛明
方谋
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Tsinghua University
Jiangsu Huadong Institute of Li-ion Battery Co Ltd
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Tsinghua University
Jiangsu Huadong Institute of Li-ion Battery Co Ltd
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Priority to PCT/CN2014/089740 priority patent/WO2015067136A1/en
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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
    • H01M4/502—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/02—Oxides; Hydroxides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/13—Nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • 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 provides an active material of a negative electrode of a lithium ion battery. The active material comprises a manganese dioxide nano tube. The invention provides a preparation method of the active material. The preparation method comprises the steps of mixing potassium permanganate, hydrogen chloride and a surfactant, polyvinylpyrrolidone, in water to form a mixed solution; and carrying out hydrothermal reaction on the mixed solution in a hydrothermal kettle at the reaction temperature of 120 DEG C-180 DEG C so as to generate the manganese dioxide nano tube. The invention provides the lithium ion battery. The active material of the negative electrode of the lithium ion battery comprises the manganese dioxide nano tube.

Description

Lithium ion battery anode active material and preparation method thereof and lithium ion battery
Technical field
The present invention relates to a kind of lithium ion battery anode active material and preparation method thereof and lithium ion battery.
Background technology
The business-like negative material of lithium ion battery adopts graphite mostly, but the theory of graphite material storage lithium specific capacity only has 372mAh/g.For meeting the demand of high-capacity lithium ion cell, the graphite cathode material of researching and developing the alternative current commercial applications of novel height ratio capacity lithium ion battery negative material seems very urgent and necessary.
Since people's reported first transition metal oxide (TMOs such as Poizot in 2000, transition metal oxides), as since lithium ion battery negative material, transition metal oxide and other transistion metal compounds (TMX) are quite concerned as lithium ion battery negative material.The oxide of transition metal, as Fe, Ni, Co, Cu etc., generally has similar electrochemical behavior.Its removal lithium embedded mechanism is generally: during embedding lithium, Li is embedded in transition metal oxide, by displacement reaction, generates metal nanoparticle, and is evenly embedded in the Li of generation 2in O matrix; During de-lithium, reversible generation transition metal oxide and lithium again.
In these transition metal oxides, the oxide of manganese metal, as MnO, Mn 3o 4, Mn 2o 3, MnO 2deng, be widely used in all kinds of electrochemical energy storage equipment and excite wide spread interest.The oxide of manganese has numerous structures, and its electrochemical behavior depends on oxidation state, nanostructure and form strongly.According to theory, calculate MnO, Mn 3o 4, Mn 2o 3, MnO 2theory storage lithium specific capacity be respectively 755,936,1018,1232mAh/g.So MnO 2specific capacity the highest.Traditionally, MnO 2positive electrode as disposable lithium-battery in field of batteries is widely used, because its lower reversible capacity and poor cyclical stability cannot be applied to secondary lithium battery.
In recent years, due to MnO 2there is higher theoretical specific capacity, and abundant natural resources, to MnO 2research as lithium ion battery negative material has the trend increasing, yet, MnO 2chemical property far away cannot be satisfactory, and reversible specific capacity is lower first, and what more cannot make us accepting is cycle performance extreme difference, and repeatedly after circulation, capacity attenuation is rapid.Even there is researcher to suspect MnO 2whether there is electro-chemical activity, can be applied to secondary lithium battery.
Summary of the invention
In view of this, necessary a kind of lithium ion battery anode active material and preparation method thereof and the lithium ion battery of providing, this lithium ion battery anode active material has higher reversible specific capacity first and excellent cycle performance, can be used for secondary lithium battery.
A lithium ion battery anode active material, comprises manganese dioxide nano pipe.
A preparation method for lithium ion battery anode active material, it comprises the following steps: potassium permanganate, hydrogen chloride and surfactant polyvinylpyrrolidone are mixed to form to a mixed liquor in water; And this mixed liquor is carried out in water heating kettle to hydro-thermal reaction, reaction temperature is 120 ℃ ~ 180 ℃, generates manganese dioxide nano pipe.
A lithium ion battery, the negative active core-shell material of this lithium ion battery comprises manganese dioxide nano pipe.
Compared to prior art, the present invention synthesizes the manganese dioxide of nanotube form as negative active core-shell material, and reversible specific capacity is 3 times of left and right of graphite, compares also not a halfpenny the worse with a lot silicon-carbon cathode materials, and stable cycle performance, demonstrates good application prospect.
Accompanying drawing explanation
Fig. 1 is that the embodiment of the present invention adopts the synthetic negative active core-shell material MnO of hydro thermal method 2xRD figure.
Fig. 2 is that the embodiment of the present invention adopts the synthetic negative active core-shell material MnO of hydro thermal method 2sEM figure.
Fig. 3 is that the embodiment of the present invention adopts the synthetic negative active core-shell material MnO of hydro thermal method 2charge and discharge cycles curve.
Embodiment
Below in conjunction with the accompanying drawings and the specific embodiments lithium ion battery anode active material provided by the invention and preparation method thereof and lithium ion battery are described in further detail.
The embodiment of the present invention provides a kind of lithium ion negative active core-shell material, comprises manganese dioxide (MnO 2) nanotube.
Particularly, this MnO 2the diameter of nanotube is about 50 nanometer～200 nanometers.This MnO 2the pipe thickness of nanotube is about 5 nanometer～30 nanometers.This MnO 2nanotube is linear structure.This MnO 2nanotube still can be greater than 800mAh/g as reversible specific capacity (being charge ratio capacity) after lithium ion battery anode active material constant current charge-discharge circulation 80 times.
The embodiment of the present invention provides a kind of preparation method of lithium ion negative active core-shell material, and it comprises the following steps:
S1, by potassium permanganate (KMnO 4), hydrogen chloride (HCl) and surfactant polyvinylpyrrolidone (PVP) be mixed to form mixed liquor in water; And
S2 carries out this mixed liquor hydro-thermal reaction in water heating kettle, and reaction temperature is 120 ℃ ~ 180 ℃, generates MnO 2nanotube.
Particularly, in this step S1, potassium permanganate can be dissolved in the water and be configured to solution, then this liquor potassic permanganate is mixed with hydrochloric acid solution, then add PVP as surfactant, form the described mixed liquor that contains potassium permanganate, HCl and PVP.In this mixed liquor, the mol ratio of potassium permanganate and HCl can be 1:10 ~ 4:1, PVP add quality optimization be potassium permanganate quality 0.01% ~ 10%, more preferably 0.1% ~ 1%.In this mixed liquor, the concentration of potassium permanganate is preferably 0.01 mol/L ~ 1 mol/L.
In this step S2, this mixed liquor is put into hydrothermal reaction kettle, water heating kettle is sealed and be heated to 120 ℃ ~ 180 ℃ and carry out hydro-thermal reaction, under this reaction temperature, temperature retention time is 1 hour ~ 48 hours.
Water heating kettle naturally cools to room temperature after completion of the reaction, collects the black precipitate in water heating kettle, with deionized water centrifuge washing, to remove foreign ion, then at air drying, obtains MnO 2nanotube.This MnO 2nanotube is for to obtain by this hydro-thermal reaction one-step synthesis.
In this hydro-thermal reaction, there is redox reaction in potassium permanganate and HCl, and PVP guarantees to generate the MnO with nanotube pattern as surfactant 2.
Refer to Fig. 1, the black precipitate that said method is prepared to remove foreign ion, is then carried out XRD test, with MnO with deionized water centrifuge washing after air drying 2standard x RD figure be consistent, prove that synthetic product is MnO 2.Refer to Fig. 2, above-mentioned product is carried out to SEM test, can see that having formed diameter is nano level hollow tubular structures, proves and has obtained MnO 2nanotube.
The embodiment of the present invention further provides a kind of lithium ion battery, and the negative active core-shell material of this lithium ion battery is MnO 2nanotube.This lithium ion battery anode active material MnO 2have higher first discharge specific capacity, and a stable cycle performance, capability retention is higher, and after constant current charge-discharge circulation 80 times, reversible specific capacity still can be greater than 800mAh/g.
Embodiment 1
By 1 mM of (mmol) KMnO 4with 4 mmol HCl(concentrated hydrochloric acids) be dissolved in 45 ml deionized waters formation solution, add 4 mg PVP, form mixed liquor.Then this mixed liquor is transferred in the water heating kettle inner bag of 65 ml volumes.Sealing water heating kettle is heated to 140 ℃, is incubated 12 hours.Water heating kettle naturally cools to room temperature after completion of the reaction, collects the black precipitate in still, with deionized water centrifuge washing, to remove foreign ion, then at air drying, obtains MnO 2nanotube.
By MnO 2nanotube is made negative electrode pole piece as lithium ion battery anode active material, and detailed process is: by MnO 2nanotube and conductive agent acetylene black mix, and then add binding agent PVDF solution, and solvent NMP makes slurry, are evenly applied on Copper Foil, cut into cathode pole piece after oven dry.MnO 2, acetylene black, PVDF mass ratio be 60:30:10.To contain 1mol/L LiPF 6eC/DEC (1:1, w/w) solvent be electrolyte, lithium metal is to electrode, is assembled into lithium ion battery.
Refer to Fig. 3, this lithium ion battery is carried out to the test of electrochemistry cycle performance, charging/discharging voltage scope is 0.01V ~ 3.0V, and electric current is 100mA/g.As seen from Figure 3, negative active core-shell material MnO 2first discharge specific capacity is about 1124mAh/g, and reversible specific capacity, up to 814mAh/g, still can have the reversible specific capacity of 888mAh/g after 80 circulations first.
Embodiment 2
By 1 mmol KMnO 4with 10 mmol HCl(concentrated hydrochloric acids) be dissolved in 45 ml deionized waters formation solution, add 1.6mg PVP, form mixed liquor.Then solution is transferred in the water heating kettle inner bag of 65 ml volumes.Sealing water heating kettle is heated to 120 ℃, is incubated 24 hours.Water heating kettle naturally cools to room temperature after completion of the reaction, collects the black precipitate in still, with deionized water centrifuge washing, to remove foreign ion, then at air drying, obtains MnO 2nanotube.
Embodiment 3
By 4 mmol KMnO 4with 1 mmol HCl(concentrated hydrochloric acid) be dissolved in 45 mL deionized waters formation solution, add 16mg PVP, form mixed liquor.Then this mixed liquor is transferred in the water heating kettle inner bag of 65 ml volumes.Sealing water heating kettle is heated to 180 ℃, is incubated 24 hours.Water heating kettle naturally cools to room temperature after completion of the reaction, collects the black precipitate in still, with deionized water centrifuge washing, to remove foreign ion, then at air drying, obtains MnO 2nanotube.
Embodiment 4
By 2 mmol KMnO 4with 1 mmol HCl(concentrated hydrochloric acid) be dissolved in 45 ml deionized waters formation solution, add 1mg PVP, form mixed liquor.Then this mixed liquor is transferred in the water heating kettle inner bag of 65 ml volumes.Sealing water heating kettle is heated to 160 ℃, is incubated 48 hours.Water heating kettle naturally cools to room temperature after completion of the reaction, collects the black precipitate in still, with deionized water centrifuge washing, to remove foreign ion, then at air drying, obtains MnO 2nanotube.
Embodiment 5
By 1 mmol KMnO 4with 10 mmol HCl(concentrated hydrochloric acids) be dissolved in 45 ml deionized waters formation solution, add 0.5mg PVP, form mixed liquor.Then this mixed liquor is transferred in the water heating kettle inner bag of 65 ml volumes.Sealing water heating kettle is heated to 140 ℃, is incubated 12 hours.Water heating kettle naturally cools to room temperature after completion of the reaction, collects the black precipitate in still, with deionized water centrifuge washing, to remove foreign ion, then at air drying, obtains MnO 2nanotube.
Embodiment 6
By 4 mmol KMnO 4with 1 mmol HCl(concentrated hydrochloric acid) be dissolved in 45 ml deionized waters formation solution, add 4mg PVP, form mixed liquor.Then this mixed liquor is transferred in the water heating kettle inner bag of 65 ml volumes.Sealing water heating kettle is heated to 140 ℃, is incubated 12 hours.Water heating kettle naturally cools to room temperature after completion of the reaction, collects the black precipitate in still, with deionized water centrifuge washing, to remove foreign ion, then at air drying, obtains MnO 2nanotube.
Manganese dioxide nano pipe preparation technology provided by the invention is simple, and reversible specific capacity is 3 times of left and right of graphite, compares also not a halfpenny the worsely with a lot silicon-carbon cathode materials, and stable cycle performance, demonstrates good application prospect.
In addition, those skilled in the art also can do other and change in spirit of the present invention, and certainly, the variation that these are done according to spirit of the present invention, within all should being included in the present invention's scope required for protection.

Claims (8)

1. a lithium ion battery anode active material, is characterized in that, comprises manganese dioxide nano pipe.
2. lithium ion battery anode active material as claimed in claim 1, is characterized in that, the diameter of this manganese dioxide nano pipe is 50 nanometer～200 nanometers.
3. lithium ion battery anode active material as claimed in claim 1, is characterized in that, the pipe thickness of this manganese dioxide nano pipe is 5 nanometer～30 nanometers.
4. lithium ion battery anode active material as claimed in claim 1, is characterized in that, this manganese dioxide nano pipe is greater than 800mAh/g as reversible specific capacity after lithium ion battery anode active material constant current charge-discharge circulation 80 times.
5. a preparation method for lithium ion battery anode active material, it comprises the following steps:
Potassium permanganate, hydrogen chloride and surfactant polyvinylpyrrolidone are mixed to form to mixed liquor in water; And
This mixed liquor is carried out in water heating kettle to hydro-thermal reaction, reaction temperature is 120 ℃ ~ 180 ℃, generates manganese dioxide nano pipe.
6. the preparation method of lithium ion battery anode active material as claimed in claim 5, is characterized in that, the mol ratio of this potassium permanganate and hydrogen chloride is 1:10 ~ 4:1.
7. the preparation method of lithium ion battery anode active material as claimed in claim 5, is characterized in that, this polyvinylpyrrolidone add quality be potassium permanganate quality 0.01% ~ 10%.
8. a lithium ion battery, is characterized in that, the negative active core-shell material of this lithium ion battery comprises manganese dioxide nano pipe.
CN201310554493.9A 2013-11-11 2013-11-11 Lithium ion battery anode active material and preparation method thereof and lithium ion battery Expired - Fee Related CN103682303B (en)

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CN104183822A (en) * 2014-08-13 2014-12-03 江苏华东锂电技术研究院有限公司 Negative active material, preparation method of negative active material, and lithium ion battery
CN104261479A (en) * 2014-09-28 2015-01-07 上海第二工业大学 Metal-doped nano manganese dioxide electrode material and preparation method thereof
WO2015067136A1 (en) * 2013-11-11 2015-05-14 江苏华东锂电技术研究院有限公司 Active material for negative electrode of lithium ion battery and preparation method therefor, and lithium ion battery
WO2016023398A1 (en) * 2014-08-13 2016-02-18 江苏华东锂电技术研究院有限公司 Negative electrode active material, preparation method therefor, and lithium-ion battery
CN106992291A (en) * 2017-04-19 2017-07-28 扬州大学 Manganese dioxide modification core shell structure-hollow microporous carbon ball coats the preparation method of nanometer sulfur molecule
CN109768262A (en) * 2019-01-25 2019-05-17 天津理工大学 A kind of cadmium modified manganese dioxide positive electrode and its preparation method and application
CN115064683A (en) * 2022-07-12 2022-09-16 中国人民解放军空军工程大学 Manganese oxide composite electrode material, preparation method thereof and application thereof in preparation of lithium ion battery cathode material

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CN101698512A (en) * 2009-10-23 2010-04-28 济南大学 Method for preparing nano manganese dioxide of different crystal forms and appearances by adopting microwave hydrothermal method
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Cited By (10)

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WO2015067136A1 (en) * 2013-11-11 2015-05-14 江苏华东锂电技术研究院有限公司 Active material for negative electrode of lithium ion battery and preparation method therefor, and lithium ion battery
CN104183822A (en) * 2014-08-13 2014-12-03 江苏华东锂电技术研究院有限公司 Negative active material, preparation method of negative active material, and lithium ion battery
WO2016023399A1 (en) * 2014-08-13 2016-02-18 江苏华东锂电技术研究院有限公司 Negative electrode active material, preparation method therefor, and lithium-ion battery
WO2016023398A1 (en) * 2014-08-13 2016-02-18 江苏华东锂电技术研究院有限公司 Negative electrode active material, preparation method therefor, and lithium-ion battery
CN104261479A (en) * 2014-09-28 2015-01-07 上海第二工业大学 Metal-doped nano manganese dioxide electrode material and preparation method thereof
CN104261479B (en) * 2014-09-28 2017-03-08 上海第二工业大学 A kind of metal doping nano manganese bioxide electrode material and preparation method thereof
CN106992291A (en) * 2017-04-19 2017-07-28 扬州大学 Manganese dioxide modification core shell structure-hollow microporous carbon ball coats the preparation method of nanometer sulfur molecule
CN109768262A (en) * 2019-01-25 2019-05-17 天津理工大学 A kind of cadmium modified manganese dioxide positive electrode and its preparation method and application
CN109768262B (en) * 2019-01-25 2021-12-24 天津理工大学 Cadmium modified manganese dioxide positive electrode material and preparation method and application thereof
CN115064683A (en) * 2022-07-12 2022-09-16 中国人民解放军空军工程大学 Manganese oxide composite electrode material, preparation method thereof and application thereof in preparation of lithium ion battery cathode material

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