CN103682303B - Lithium ion battery anode active material and preparation method thereof and lithium ion battery - Google Patents

Lithium ion battery anode active material and preparation method thereof and lithium ion battery Download PDF

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Publication number
CN103682303B
CN103682303B CN201310554493.9A CN201310554493A CN103682303B CN 103682303 B CN103682303 B CN 103682303B CN 201310554493 A CN201310554493 A CN 201310554493A CN 103682303 B CN103682303 B CN 103682303B
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lithium ion
ion battery
active material
mno
anode active
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CN103682303A (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
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—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
    • 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
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    • 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
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
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    • 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

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Abstract

The invention provides a kind of lithium ion battery anode active material, comprise manganese dioxide nano pipe.The invention provides a kind of preparation method of lithium ion battery anode active material, it comprises the following steps: potassium permanganate, hydrogen chloride and surfactant polyvinylpyrrolidone are mixed to form mixed liquor in water; And this mixed liquor is carried out hydro-thermal reaction in water heating kettle, reaction temperature is 120 DEG C ~ 180 DEG C, generates manganese dioxide nano pipe.The invention provides a kind of lithium ion battery, the negative active core-shell material of this lithium ion battery comprises manganese dioxide nano pipe.

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, researching and developing the graphite cathode material that novel height ratio capacity lithium ion battery negative material substitutes current commercial applications and seeming very urgent and necessary.
Since people's reported first transition metal oxide (TMOs such as Poizot in 2000, transitionmetaloxides) as since lithium ion battery negative material, transition metal oxide and other transistion metal compounds (TMX) 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, generates metal nanoparticle by displacement reaction, 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 storage device and excite wide spread interest.The oxide of manganese has numerous structures, and its electrochemical behavior is strongly depend on oxidation state, nanostructure and form.According to theory calculate, MnO, Mn 3o 4, Mn 2o 3, MnO 2theory storage lithium specific capacity be respectively 755,936,1018,1232mAh/g.Therefore MnO 2specific capacity the highest.Traditionally, MnO 2positive electrode as disposable lithium-battery in field of batteries widely uses, and the reversible capacity lower due to it 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 increased, but, MnO 2chemical property far away cannot be satisfactory, and reversible specific capacity is lower first, and what more cannot make us acceptance is cycle performance extreme difference, and repeatedly after circulation, capacity attenuation is rapid.Researcher is even had to suspect MnO 2whether there is electro-chemical activity, can secondary lithium battery be applied to.
Summary of the invention
In view of this, necessaryly provide a kind of lithium ion battery anode active material and preparation method thereof and lithium ion battery, 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 kind of 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 a mixed liquor in water; And this mixed liquor is carried out hydro-thermal reaction in water heating kettle, reaction temperature is 120 DEG C ~ 180 DEG C, generates manganese dioxide nano pipe.
A kind of 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 morphologies as negative active core-shell material, and reversible specific capacity is about 3 times of graphite, also not a halfpenny the worse compared with a lot of silicon-carbon cathode materials, and stable cycle performance, demonstrate good application prospect.
Accompanying drawing explanation
Fig. 1 is the negative active core-shell material MnO that the embodiment of the present invention adopts water heat transfer 2xRD figure.
Fig. 2 is the negative active core-shell material MnO that the embodiment of the present invention adopts water heat transfer 2sEM figure.
Fig. 3 is the negative active core-shell material MnO that the embodiment of the present invention adopts water heat transfer 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 pole active 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 the lithium ion battery anode active material constant current charge-discharge reversible specific capacity (i.e. charge specific capacity) after 80 times that circulates.
The embodiment of the present invention provides a kind of preparation method of lithium-ion negative pole active 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 hydro-thermal reaction by this mixed liquor in water heating kettle, and reaction temperature is 120 DEG C ~ 180 DEG C, 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 containing potassium permanganate, HCl and PVP.In this mixed liquor, the mol ratio of potassium permanganate and HCl can be add that Functionality, quality and appealing design elects the quality of potassium permanganate as 0.01% ~ 10% of 1:10 ~ 4:1, PVP, is more preferably 0.1% ~ 1%.In this mixed liquor, the concentration of potassium permanganate is preferably 0.01mol/L ~ 1mol/L.
In this step S2, this mixed liquor is put into hydrothermal reaction kettle, sealed by water heating kettle and be heated to 120 DEG C ~ 180 DEG C 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 dry in atmosphere, obtains MnO 2nanotube.This MnO 2nanotube is for obtain by this hydro-thermal reaction one-step synthesis.
In this hydro-thermal reaction, there is redox reaction in potassium permanganate and HCl, PVP guarantees to generate the MnO with nanotube pattern as surfactant 2.
Refer to Fig. 1, the black precipitate deionized water centrifuge washing prepared said method, to remove foreign ion, then carries out XRD test, with MnO after drying in atmosphere 2standard x RD figure be consistent, prove that synthetic product is MnO 2.Refer to Fig. 2, SEM test is carried out to above-mentioned product, can see that defining diameter is nano level hollow tubular structures, proves to obtain MnO 2nanotube.
The embodiment of the present invention provides a kind of lithium ion battery further, 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 the constant current charge-discharge reversible specific capacity after 80 times that circulates still can be greater than 800mAh/g.
Embodiment 1
By 1 mM of (mmol) KMnO 4with 4mmolHCl(concentrated hydrochloric acid) be dissolved in 45ml deionized water formation solution, add 4mgPVP, form mixed liquor.Then this mixed liquor is transferred in the water heating kettle inner bag of 65ml volume.Sealing water heating kettle is heated to 140 DEG C, 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 dry in atmosphere, obtains MnO 2nanotube.
By MnO 2nanotube makes 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 make 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/LLiPF 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 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 is up to 814mAh/g first, still can have the reversible specific capacity of 888mAh/g after 80 circulations.
Embodiment 2
By 1mmolKMnO 4with 10mmolHCl(concentrated hydrochloric acid) be dissolved in 45ml deionized water formation solution, add 1.6mgPVP, form mixed liquor.Then solution is transferred in the water heating kettle inner bag of 65ml volume.Sealing water heating kettle is heated to 120 DEG C, 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 dry in atmosphere, obtains MnO 2nanotube.
Embodiment 3
By 4mmolKMnO 4with 1mmolHCl(concentrated hydrochloric acid) be dissolved in 45mL deionized water formation solution, add 16mgPVP, form mixed liquor.Then this mixed liquor is transferred in the water heating kettle inner bag of 65ml volume.Sealing water heating kettle is heated to 180 DEG C, 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 dry in atmosphere, obtains MnO 2nanotube.
Embodiment 4
By 2mmolKMnO 4with 1mmolHCl(concentrated hydrochloric acid) be dissolved in 45ml deionized water formation solution, add 1mgPVP, form mixed liquor.Then this mixed liquor is transferred in the water heating kettle inner bag of 65ml volume.Sealing water heating kettle is heated to 160 DEG C, 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 dry in atmosphere, obtains MnO 2nanotube.
Embodiment 5
By 1mmolKMnO 4with 10mmolHCl(concentrated hydrochloric acid) be dissolved in 45ml deionized water formation solution, add 0.5mgPVP, form mixed liquor.Then this mixed liquor is transferred in the water heating kettle inner bag of 65ml volume.Sealing water heating kettle is heated to 140 DEG C, 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 dry in atmosphere, obtains MnO 2nanotube.
Embodiment 6
By 4mmolKMnO 4with 1mmolHCl(concentrated hydrochloric acid) be dissolved in 45ml deionized water formation solution, add 4mgPVP, form mixed liquor.Then this mixed liquor is transferred in the water heating kettle inner bag of 65ml volume.Sealing water heating kettle is heated to 140 DEG C, 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 dry in atmosphere, obtains MnO 2nanotube.
Manganese dioxide nano pipe preparation technology provided by the invention is simple, and reversible specific capacity is about 3 times of graphite, also not a halfpenny the worse compared with a lot of silicon-carbon cathode materials, and stable cycle performance, demonstrate good application prospect.
In addition, those skilled in the art also can do other changes in spirit of the present invention, and certainly, these changes done according to the present invention's spirit, all should be included within the present invention's scope required for protection.

Claims (2)

1. 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 mixed liquor in water, add that quality is the quality of potassium permanganate 0.01% ~ 10% of this polyvinylpyrrolidone; And
This mixed liquor is carried out hydro-thermal reaction in water heating kettle, and reaction temperature is 120 DEG C ~ 180 DEG C, and temperature retention time is 12 hours ~ 48 hours, generates manganese dioxide nano pipe.
2. the preparation method of lithium ion battery anode active material as claimed in claim 1, it is characterized in that, the mol ratio of this potassium permanganate and hydrogen chloride is 1:10 ~ 4:1.
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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PCT/CN2014/089740 WO2015067136A1 (en) 2013-11-11 2014-10-28 Active material for negative electrode of lithium ion battery and preparation method therefor, and lithium ion battery

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CN103682303B (en) * 2013-11-11 2016-03-02 江苏华东锂电技术研究院有限公司 Lithium ion battery anode active material and preparation method thereof 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
CN104167540A (en) * 2014-08-13 2014-11-26 江苏华东锂电技术研究院有限公司 Negative electrode active material and preparation method thereof and lithium ion battery
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
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
CN115064683B (en) * 2022-07-12 2024-04-26 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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