CN105609728A - Modified graphene-doped lithium nickelate battery cathode material and preparation method thereof - Google Patents

Modified graphene-doped lithium nickelate battery cathode material and preparation method thereof Download PDF

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Publication number
CN105609728A
CN105609728A CN201511025478.0A CN201511025478A CN105609728A CN 105609728 A CN105609728 A CN 105609728A CN 201511025478 A CN201511025478 A CN 201511025478A CN 105609728 A CN105609728 A CN 105609728A
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lithium nickelate
modified graphene
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parts
graphene
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姜殿凯
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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
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a modified graphene-doped lithium nickelate battery cathode material and a preparation method thereof. The modified graphene-doped lithium nickelate battery cathode material is prepared from the following components in parts by weight: 30 parts of graphene oxide, 60 parts of lithium nickelate, 25 parts of 45% lithium iron nitrate solution, 3 parts of flake graphite and 3 parts of binding material. The modified graphene-doped lithium nickelate battery cathode material overcomes the defect of failure of lithium ion batteries caused by self-discharge of protection boards, so that self-discharge of the whole battery pack is improved, the aim of prolonging the storage time of lithium batteries is achieved, and the lithium batteries can be stored for a longer time under the condition that users do not charge electric appliances after using the electric appliances.

Description

Lithium nickelate electricity positive electrode that a kind of modified graphene is coated and preparation method thereof
Technical field
The present invention relates to coated lithium nickelate electricity positive electrode of a kind of modified graphene and preparation method thereof.
Background technology
Lithium ion battery is since commercialization, and lithium ion battery positive electrode used is mostly lithium nickelate, nickelAcid lithium or ternary material etc., its component is mainly that active material adds conductive agent adding additives again, described active materialMaterial is lithium nickelate, lithium nickelate or ternary etc.; It is active material that negative material adopts graphite mostly, then adds oneA little conductive agents and binding agent; Its advantage is that capacity is higher, has extended cycle life, but nickel resources scarcity, priceExpensive and there is toxicity, therefore seek excellent honest and clean, the dependable performance of price, eco-friendly positive electrode becomes lithiumThe important research direction of ion battery. Spinel-type positive electrode taking lithium nickelate as representative and ternary material layerShape oxide in the past decade obtains broad research, but because its defect existing has separately restricted themDevelopment prospect. In addition, the system of positive and negative pole material composition has a common feature to discharge the later stage exactly, outstandingIt is that voltage drop is very fast in the time that electric discharge finishes, namely at this voltage range the inside, lithium-ion electricThe capacity in pond has not almost had.
Summary of the invention
The technical problem to be solved in the present invention is the above-mentioned defect that how to overcome prior art, and a kind of modification is providedLithium nickelate electricity positive electrode of graphene coated and preparation method thereof.
For solving the problems of the technologies described above, the coated lithium nickelate of this modified graphene electricity positive electrode by weightMeter, by following component according to shown in ratio be prepared from, graphene oxide 30, lithium nickelate 60,45% nitreAcid iron lithium solution 25, crystalline flake graphite 3, binding material 3.
The coated lithium nickelate electricity method for preparing anode material of this modified graphene comprises the following steps:
(1) get graphite and sodium nitrate, with mass ratio 2:1 ratio, be placed in the concentrated sulfuric acid of a certain amount of ice bath,Under stirring, add 3 times to the nickelic sour potassium of described graphite quality, mix, control temperature and stir lower than 20 DEG CMix 1h left and right, temperature to the 32～38 DEG C reaction 2h that then raises, slowly drips quantitative deionized water, fully stirsMix evenly, in the time that system temperature declines, add hydrogen peroxide cessation reaction, filter, wash, be dried; Heating is stirredIn the process of mixing, add a certain amount of finely dispersed CNT ethylene glycol slurries, then continue to stir 2h;Make graphene oxide;
(2) graphene oxide being dispersed in to volume ratio is the water of 3:1 and the mixed solvent of acetone, water or chloroformIn, ultrasonic or stirring, disperses it completely equably;
(3) by the adding in mixed solution of active material, functional material, conductive material, binding material,Ultrasonic or stirring, adds or does not add dopant acid again, and it is acid that whole mixed solution system is, its pH valueBetween 2～4;
(4), under ice-water bath and inert atmosphere protection, add ammonium persulfate aqueous solution or FeCl3Chloroform moltenLiquid, stirring reaction 24h under constant temperature, then by product centrifugation, washing, puts into the vacuum of 60 DEG CIn drying box, dry, be ground to powder.
The coated lithium nickelate of a kind of modified graphene of the present invention electricity method for preparing anode material method is simple, costCheap, overcome lithium ion battery and caused the defect of inefficacy because of baffle self discharge, thereby improved wholeThe self discharge of battery pack, realizes and extends the object of lithium battery resting period, ensure that user uses electrical appliance andIn the situation of not charging, can store the longer time.
Detailed description of the invention
The coated lithium nickelate of this modified graphene electricity positive electrode by weight, by following component according to shown inRatio is prepared from, graphene oxide 30, lithium nickelate 60,45% ferric nitrate lithium solution 25, crystalline flake graphite3, binding material 3.
The coated lithium nickelate electricity method for preparing anode material of this modified graphene comprises the following steps:
(1) get graphite and sodium nitrate, with mass ratio 2:1 ratio, be placed in the concentrated sulfuric acid of a certain amount of ice bath,Under stirring, add 3 times to the nickelic sour potassium of described graphite quality, mix, control temperature and stir lower than 20 DEG CMix 1h left and right, temperature to the 32～38 DEG C reaction 2h that then raises, slowly drips quantitative deionized water, fully stirsMix evenly, in the time that system temperature declines, add hydrogen peroxide cessation reaction, filter, wash, be dried; Heating is stirredIn the process of mixing, add a certain amount of finely dispersed CNT ethylene glycol slurries, then continue to stir 2h;Make graphene oxide;
(2) graphene oxide being dispersed in to volume ratio is the water of 3:1 and the mixed solvent of acetone, water or chloroformIn, ultrasonic or stirring, disperses it completely equably;
(3) by the adding in mixed solution of active material, functional material, conductive material, binding material,Ultrasonic or stirring, adds or does not add dopant acid again, and it is acid that whole mixed solution system is, its pH valueBetween 2～4;
(4), under ice-water bath and inert atmosphere protection, add ammonium persulfate aqueous solution or FeCl3Chloroform moltenLiquid, stirring reaction 24h under constant temperature, then by product centrifugation, washing, puts into the vacuum of 60 DEG CIn drying box, dry, be ground to powder.
The present invention includes but be not limited to above-mentioned embodiment, any product that meets the description of these claims,Within all falling into protection scope of the present invention.

Claims (2)

1. the coated lithium nickelate electricity positive electrode of modified graphene, is characterized in that: by weight,The coated lithium nickelate of this modified graphene electricity positive electrode by following component according to shown in ratio be prepared from, oxygenFunctionalized graphene 30, lithium nickelate 60,45% ferric nitrate lithium solution 25, crystalline flake graphite 3, binding material 3.
2. the coated lithium nickelate electricity method for preparing anode material of modified graphene, is characterized in that: described inThe coated lithium nickelate electricity positive electrode of modified graphene is that modified graphene claimed in claim 1 is coatedLithium nickelate electricity positive electrode, its preparation method comprises the following steps:
(1) get graphite and sodium nitrate, with mass ratio 2:1 ratio, be placed in the concentrated sulfuric acid of a certain amount of ice bath,Under stirring, add 3 times to the nickelic sour potassium of described graphite quality, mix, control temperature and stir lower than 20 DEG CMix 1h left and right, temperature to the 32～38 DEG C reaction 2h that then raises, slowly drips quantitative deionized water, fully stirsMix evenly, in the time that system temperature declines, add hydrogen peroxide cessation reaction, filter, wash, be dried; Heating is stirredIn the process of mixing, add a certain amount of finely dispersed CNT ethylene glycol slurries, then continue to stir 2h;Make graphene oxide;
(2) graphene oxide being dispersed in to volume ratio is the water of 3:1 and the mixed solvent of acetone, water or chloroformIn, ultrasonic or stirring, disperses it completely equably;
(3) by the adding in mixed solution of active material, functional material, conductive material, binding material,Ultrasonic or stirring, adds or does not add dopant acid again, and it is acid that whole mixed solution system is, its pH valueBetween 2～4;
(4), under ice-water bath and inert atmosphere protection, add ammonium persulfate aqueous solution or FeCl3Chloroform moltenLiquid, stirring reaction 24h under constant temperature, then by product centrifugation, washing, puts into the vacuum of 60 DEG CIn drying box, dry, be ground to powder.
CN201511025478.0A 2015-12-30 2015-12-30 Modified graphene-doped lithium nickelate battery cathode material and preparation method thereof Pending CN105609728A (en)

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CN201511025478.0A CN105609728A (en) 2015-12-30 2015-12-30 Modified graphene-doped lithium nickelate battery cathode material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201511025478.0A CN105609728A (en) 2015-12-30 2015-12-30 Modified graphene-doped lithium nickelate battery cathode material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN105609728A true CN105609728A (en) 2016-05-25

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Application publication date: 20160525