CN104064765A - Novel graphene coated lithium nickelate battery cathode material and preparation method thereof - Google Patents

Novel graphene coated lithium nickelate battery cathode material and preparation method thereof Download PDF

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Publication number
CN104064765A
CN104064765A CN201410271810.0A CN201410271810A CN104064765A CN 104064765 A CN104064765 A CN 104064765A CN 201410271810 A CN201410271810 A CN 201410271810A CN 104064765 A CN104064765 A CN 104064765A
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Prior art keywords
lithium nickelate
coated lithium
positive electrode
add
graphite alkene
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CN201410271810.0A
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Chinese (zh)
Inventor
孙琦
李岩
孙慧英
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QINGDAO QIANYUN HIGH-TECH NEW MATERIAL Co Ltd
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QINGDAO QIANYUN HIGH-TECH NEW MATERIAL Co Ltd
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Priority to CN201410271810.0A priority Critical patent/CN104064765A/en
Publication of CN104064765A publication Critical patent/CN104064765A/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
    • H01M4/52—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
    • 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
    • H01M4/58—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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a novel graphene coated lithium nickelate battery cathode material and a preparation method thereof. The novel graphene coated lithium nickelate battery cathode material is prepared from the following components in parts by weight: 30 parts of graphene oxide, 100 parts of active material, 15 parts of functional material, 20 parts of conductive material and 20 parts of binding material, wherein the functional material is 60% lithium iron nitrate solution; the cathode material is lithium nickelate; the conductive agent is flake graphite. The defect of failure of lithium ion batteries caused by self-discharge of protection boards is overcome by adopting the novel graphene coated lithium nickelate battery cathode material, thus improving self-discharge of the whole battery pack, achieving the aim of prolonging the lithium battery storage time and ensuring that the lithium batteries can be stored for a longer time under the condition that users do not charge the electric appliances after using the electric appliances.

Description

Lithium nickelate electricity positive electrode that a kind of novel graphite alkene is coated and preparation method thereof
Technical field
The present invention relates to coated lithium nickelate electricity positive electrode of a kind of novel graphite alkene and preparation method thereof.
Background technology
Lithium ion battery is since commercialization, and lithium ion battery positive electrode used is mostly lithium nickelate, lithium nickelate or ternary material etc., and its component is mainly that active material adds conductive agent adding additives again, and described active material is lithium nickelate, lithium nickelate or ternary etc.; It is active material that negative material adopts graphite mostly, then adds some conductive agents and binding agent; Its advantage is that capacity is higher, have extended cycle life, but nickel resources is deficient, expensive and have toxicity, therefore seeks the important research direction that excellent honest and clean, the dependable performance of price, eco-friendly positive electrode become lithium ion battery.Spinel-type positive electrode and ternary material layered oxide that the lithium nickelate of take is representative in the past decade obtain broad research, still due to its defect existing separately, have restricted their development prospect.In addition, the system that positive and negative pole material forms has a common feature to discharge the later stage exactly, and especially, when electric discharge finishes, voltage drop is very fast, and namely, in this voltage range the inside, the capacity of lithium ion battery 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 coated lithium nickelate electricity positive electrode of a kind of novel graphite alkene and preparation method thereof is provided.
For solving the problems of the technologies described above, the coated lithium nickelate of this novel graphite alkene electricity positive electrode by weight, by following component according to shown in ratio be prepared from, graphene oxide 30, active material 100, functional material 15, electric conducting material 20, binding material 20.
As optimization, the ferric nitrate lithium solution that described functional material is 60%.
As optimization, described positive electrode is lithium nickelate.
As optimization, described conductive agent is crystalline flake graphite.
The coated lithium nickelate electricity method for preparing anode material of this novel graphite alkene 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 1 h left and right lower than 20 ℃, then temperature to 32 ~ 38 ℃ reaction 2 h that raise, slowly drip quantitative deionized water, stir, when system temperature declines, add hydrogen peroxide cessation reaction, filter, wash, be dried; Add in the process of thermal agitation, add a certain amount of finely dispersed carbon nano-tube ethylene glycol slurries, then continue to stir 2 h; Make graphene oxide;
(2) graphene oxide being dispersed in to volume ratio is in the water of 3:1 and the mixed solvent of acetone, water or chloroform, and ultrasonic or stirring, disperses it completely equably;
(3) by the adding in mixed solution of active material, functional material, electric conducting material, binding material, again ultrasonic or stir, add or do not add dopant acid, it is acid that whole mixed solution system is, and its pH value is between 2 ~ 4;
(4), under ice-water bath and inert atmosphere protection, add ammonium persulfate aqueous solution or FeCl 3chloroformic solution, stirring reaction 24h under constant temperature, then by product centrifugation, washing, the vacuum drying chamber of putting into 60 ℃ is dried, and is ground to powder.
The coated lithium nickelate of a kind of novel graphite alkene of the present invention electricity method for preparing anode material method is simple; with low cost; overcome lithium ion battery and because of baffle self discharge, caused the defect of inefficacy; thereby improve the self discharge of whole battery pack; realize to extend the object of lithium battery resting period, guarantee that user uses electrical appliance and can store the longer time in the situation of not charging.
Embodiment
The coated lithium nickelate of this novel graphite alkene electricity positive electrode by weight, by following component according to shown in ratio be prepared from, graphene oxide 30, active material 100, functional material 15, electric conducting material 20, binding material 20.Described functional material is 60% ferric nitrate lithium solution.Described positive electrode is lithium nickelate.Described conductive agent is crystalline flake graphite
The coated lithium nickelate electricity method for preparing anode material of this novel graphite alkene 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 1 h left and right lower than 20 ℃, then temperature to 32 ~ 38 ℃ reaction 2 h that raise, slowly drip quantitative deionized water, stir, when system temperature declines, add hydrogen peroxide cessation reaction, filter, wash, be dried; Add in the process of thermal agitation, add a certain amount of finely dispersed carbon nano-tube ethylene glycol slurries, then continue to stir 2 h; Make graphene oxide;
(2) graphene oxide being dispersed in to volume ratio is in the water of 3:1 and the mixed solvent of acetone, water or chloroform, and ultrasonic or stirring, disperses it completely equably;
(3) by the adding in mixed solution of active material, functional material, electric conducting material, binding material, again ultrasonic or stir, add or do not add dopant acid, it is acid that whole mixed solution system is, and its pH value is between 2 ~ 4;
(4), under ice-water bath and inert atmosphere protection, add ammonium persulfate aqueous solution or FeCl 3chloroformic solution, stirring reaction 24h under constant temperature, then by product centrifugation, washing, the vacuum drying chamber of putting into 60 ℃ is dried, and is ground to powder.
The present invention includes but be not limited to above-mentioned execution mode, any product that meets the description of these claims, within all falling into protection scope of the present invention.

Claims (5)

1. the coated lithium nickelate electricity positive electrode of a novel graphite alkene, it is characterized in that: by weight, the coated lithium nickelate of this novel graphite alkene electricity positive electrode by following component according to shown in ratio be prepared from, graphene oxide 30, active material 100, functional material 15, electric conducting material 20, binding material 20.
2. the coated lithium nickelate electricity positive electrode of novel graphite alkene according to claim 1, is characterized in that: the ferric nitrate lithium solution that described functional material is 60%.
3. the coated lithium nickelate electricity positive electrode of novel graphite alkene according to claim 1, is characterized in that: described positive electrode is lithium nickelate.
4. the coated lithium nickelate electricity positive electrode of novel graphite alkene according to claim 1, is characterized in that: described conductive agent is crystalline flake graphite.
5. the coated lithium nickelate electricity method for preparing anode material of a novel graphite alkene, it is characterized in that: the coated lithium nickelate electricity positive electrode of described novel graphite alkene is the coated lithium nickelate electricity positive electrode of the arbitrary described novel graphite alkene of claim 1 ~ 4, and 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 1 h left and right lower than 20 ℃, then temperature to 32 ~ 38 ℃ reaction 2 h that raise, slowly drip quantitative deionized water, stir, when system temperature declines, add hydrogen peroxide cessation reaction, filter, wash, be dried; Add in the process of thermal agitation, add a certain amount of finely dispersed carbon nano-tube ethylene glycol slurries, then continue to stir 2 h; Make graphene oxide;
(2) graphene oxide being dispersed in to volume ratio is in the water of 3:1 and the mixed solvent of acetone, water or chloroform, and ultrasonic or stirring, disperses it completely equably;
(3) by the adding in mixed solution of active material, functional material, electric conducting material, binding material, again ultrasonic or stir, add or do not add dopant acid, it is acid that whole mixed solution system is, and its pH value is between 2 ~ 4;
(4), under ice-water bath and inert atmosphere protection, add ammonium persulfate aqueous solution or FeCl 3chloroformic solution, stirring reaction 24h under constant temperature, then by product centrifugation, washing, the vacuum drying chamber of putting into 60 ℃ is dried, and is ground to powder.
CN201410271810.0A 2014-06-18 2014-06-18 Novel graphene coated lithium nickelate battery cathode material and preparation method thereof Pending CN104064765A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410271810.0A CN104064765A (en) 2014-06-18 2014-06-18 Novel graphene coated lithium nickelate battery cathode material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410271810.0A CN104064765A (en) 2014-06-18 2014-06-18 Novel graphene coated lithium nickelate battery cathode material and preparation method thereof

Publications (1)

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CN104064765A true CN104064765A (en) 2014-09-24

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