CN105206824B - A kind of preparation method of height ratio capacity lithium-rich anode material - Google Patents

A kind of preparation method of height ratio capacity lithium-rich anode material Download PDF

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CN105206824B
CN105206824B CN201510688092.1A CN201510688092A CN105206824B CN 105206824 B CN105206824 B CN 105206824B CN 201510688092 A CN201510688092 A CN 201510688092A CN 105206824 B CN105206824 B CN 105206824B
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lithium
anode material
rich anode
reaction kettle
preparation
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CN105206824A (en
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洪振生
谢超冰
曾悦峰
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Fujian Normal University
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Fujian Normal University
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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
    • 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
    • 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)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention belongs to the preparation fields of anode material for lithium-ion batteries, and in particular to a kind of preparation method of height ratio capacity lithium-rich anode material.Using hydro-thermal method one-step synthesis lithium-rich anode material, following steps are specifically included：1）Manganese acetate, nickel acetate, cobalt acetate are put into inner liner of reaction kettle, add in deionized water, stirring makes each dissolution of raw material, under 40 70 DEG C of water-bath, adds in lithium hydroxide solution, stirs 10 20 minutes, adds the reaction of 3 8mL hydrogen peroxide；2）After inner liner of reaction kettle is sealed, it is put into reaction kettle；When 180 200 DEG C of reactions 12 48 are small, then sample is obtained after centrifuge washing is dried, gained sample again through 400 600 DEG C of annealing 26 it is small when, lithium-rich anode material is made.According to said method material obtained has preferable cyclical stability, and with very high coulombic efficiency for the first time（More than 90%）.

Description

A kind of preparation method of height ratio capacity lithium-rich anode material
Technical field
The invention belongs to the preparation fields of anode material for lithium-ion batteries, and in particular to a kind of height ratio capacity lithium-rich anode material The preparation method of material.
Background technology
Lithium ion battery has high voltage, high power capacity and the remarkable advantages such as has extended cycle life and be widely used in mobile electricity The fields such as sub- equipment, national defense industry, electric vehicle.Due to the energy and the needs of environmental protection, electric vehicle has become current new Industry of greatest concern in energy field.Thus, developing high performance lithium-ion-power cell has become most popular in recent years One of research field.Lithium-rich positive electrode xLi2MnO3·(1-x)LiMO2（M=Co, Mn, Ni etc.；0~1）, because with higher Specific capacity, excellent high-temperature behavior, abundant raw material, good nontoxic, good cycling stability and security the advantages that, become near The positive electrode of the relatively broad concern of people over year.The manganese reserves very abundant in China, can be significantly using lithium-rich anode material The cost of current commercial Li-ion battery is reduced, makes it possible to the device as portable electronic product energy resource supply and traffic One energy storage device of instrument.The synthesis of lithium-rich positive electrode has many methods, there is coprecipitation, sol-gal process, spray Mist seasoning, solid phase method, ion-exchange etc..But these methods operate all relative complex.
And rich lithium material has the characteristics that capacity is high, operating voltage window is high, high temperature stability performance is preferable, for electrolysis Liquid it is more demanding；But it also has the shortcomings that high rate performance is poor, cyclical stability is poor simultaneously, during as positive electrode, Specific discharge capacity under general low current density can reach 300mAh/g or so.But the coulombic efficiency for the first time of material is relatively low, no Reversible capacity loss is larger.
The content of the invention
It is an object of the invention to be directed to existing rich lithium material, cycle efficieny is relatively low for the first time, and preparation method is not complicated, easily-controllable The deficiencies of processed, provides a kind of preparation method of height ratio capacity lithium-rich anode material.The present invention passes through hydro-thermal method one-step synthesis richness lithium Material enormously simplifies operating procedure, while the coulombic efficiency for the first time of obtained material also greatly improves.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of preparation method of height ratio capacity lithium-rich anode material, using hydro-thermal method one-step synthesis lithium-rich anode material, tool Body comprises the following steps：
1）0.6-0.735g manganese acetates, 0.2-0.249g nickel acetates, 0.2-0.249g cobalt acetates is weighed to be put into reaction kettle In lining, 10-15mL deionized waters are added in, stirring makes each dissolution of raw material, under 40-70 DEG C of water-bath, adds in 50-55mL concentration It for the lithium hydroxide solution of 2-2.5moL/L, stirs 10-20 minutes, adds the reaction of 3-8mL hydrogen peroxide；
2）After inner liner of reaction kettle is sealed, it is put into reaction kettle；It is washed when 180-200 DEG C of reaction 12-48 is small, then through centrifugation Wash it is dry after obtain sample, gained sample again through 400-600 DEG C of annealing 2-6 it is small when, lithium-rich anode material is made.
According to the application of height ratio capacity lithium-rich anode material made from above-mentioned preparation method, specially in lithium ion battery just Application in the material of pole；Lithium battery assembles：75-85 in mass ratio:10-15:5-10 weighs lithium-rich anode material, carbon black, gathers partially Vinyl fluoride after mixed grinding, is evenly coated in 0.25 cm2Aluminium flake on do anode, cathode is lithium metal, and electrolyte is 1M LiPF6 EC+EMC (EC/ EMC=1/1 v/v) solution.
Battery assembling carries out in the glove box of argon atmosphere（The content of water and oxygen is below 0.5 ppm）.
The beneficial effects of the present invention are：
1）The present invention uses the hydro-thermal method one-step synthesis rich lithium material of high-purity high-crystallinity, enormously simplifies operation step Suddenly, it is easy to operate, at low cost, purity is high, has excellent performance, be conducive to industrialized production；
2）It is high by rich lithium material, specific discharge capacity made from this method；It is 30 mA g in current density-1When, electric discharge Specific capacity is up to 370mAhg-1, 400 mA g of high current-1When specific capacity reach 140 mAhg-1；And material have preferably follow Ring stability, and prepared material has very high coulombic efficiency for the first time（More than 90%）.
Description of the drawings
Fig. 1 is the XRD diagram of sample made from hydro-thermal and the lithium-rich anode material after being further heat-treated；
Fig. 2 is the scanning electron microscope (SEM) photograph of lithium-rich anode material（SEM）；
Fig. 3 is charging and discharging curve figure of the lithium-rich anode material under different current densities；
Fig. 4 is lithium-rich anode material in 200 mA g of current density-1Under cycle performance figure.
Specific embodiment
The present invention is further illustrated the present invention with the following example, but protection scope of the present invention is not limited to following reality Apply example.
Embodiment 1
A kind of preparation method of height ratio capacity lithium-rich anode material, using hydro-thermal method one-step synthesis lithium-rich anode material, tool Body comprises the following steps：
1）0.6g manganese acetates, 0.249g nickel acetates, 0.2g cobalt acetates is weighed to be put into inner liner of reaction kettle, add in 13mL go from Sub- water, stirring makes each dissolution of raw material, under 60 DEG C of water-bath, adds in the lithium hydroxide solution that 52mL concentration is 2moL/L, stirring 15 minutes, add the reaction of 5mL hydrogen peroxide；
2）After inner liner of reaction kettle is sealed, it is put into reaction kettle；It is dried when 190 DEG C of reactions 24 are small, then through centrifuge washing After obtain sample, gained sample again through 500 DEG C of annealing 4 it is small when, lithium-rich anode material is made.
According to the application of height ratio capacity lithium-rich anode material made from above-mentioned preparation method, specially in lithium ion battery just Application in the material of pole；Lithium battery assembles：In mass ratio 80:12:8 weigh lithium-rich anode material, carbon black, Kynoar, mix After closing grinding, 0.25 cm is evenly coated in2Aluminium flake on do anode, cathode is lithium metal, and electrolyte is 1M LiPF6EC+EMC (EC/ EMC=1/1 v/v) solution.
Battery assembling carries out in the glove box of argon atmosphere（The content of water and oxygen is below 0.5 ppm）.
Fig. 1 is the XRD of sample made from hydro-thermal and the lithium-rich anode material after being further heat-treated, can be from figure Find out that XRD is not much different, illustrate that we can synthesize the lithium-rich anode material of high-crystallinity by one step hydro thermal method.To material It carries out analysis of chemical elements and obtains lithium-rich anode material chemical formula as Li1.12 Ni0.14Mn0.52Co0.16O2.Fig. 2 is lithium-rich anode material The scanning electron microscope (SEM) photograph of material（SEM）, as can be seen from the figure scantling be about 30 nm-60 nm, particle size is smaller, and have There is good uniformity.Fig. 3 is charging and discharging curve of the lithium-rich anode material under different current densities, is 30 in current density mA g-1When, specific discharge capacity is up to 370mAhg-1, 400 mA g of high current-1When specific capacity reach 140 mAhg-1.Fig. 4 is Lithium-rich anode material is in 200 mA g of current density-1Under cycle performance figure, by 100 times cycle specific capacities can reach 180mAhg-1, it can be seen that material has preferable cyclical stability, and prepared material is imitated with very high coulomb for the first time Rate（More than 90%）.
Embodiment 2
A kind of preparation method of height ratio capacity lithium-rich anode material, using hydro-thermal method one-step synthesis lithium-rich anode material, tool Body comprises the following steps：
1）It weighs 0.735g manganese acetates, 0.249g nickel acetates, 0.249g cobalt acetates to be put into inner liner of reaction kettle, adds in 15mL Deionized water, stirring makes each dissolution of raw material, and under 70 DEG C of water-bath, it is molten to add in the lithium hydroxide that 55mL concentration is 2.5moL/L Liquid stirs 10 minutes, adds the reaction of 8mL hydrogen peroxide；
2）After inner liner of reaction kettle is sealed, it is put into reaction kettle；It is dried when 180 DEG C of reactions 48 are small, then through centrifuge washing After obtain sample, gained sample again through 400 DEG C of annealing 6 it is small when, lithium-rich anode material is made.
According to the application of height ratio capacity lithium-rich anode material made from above-mentioned preparation method, specially in lithium ion battery just Application in the material of pole；Lithium battery assembles：In mass ratio 85:10:10 weigh lithium-rich anode material, carbon black, Kynoar, mix After closing grinding, 0.25 cm is evenly coated in2Aluminium flake on do anode, cathode is lithium metal, and electrolyte is 1M LiPF6EC+EMC (EC/ EMC=1/1 v/v) solution.
Battery assembling carries out in the glove box of argon atmosphere（The content of water and oxygen is below 0.5 ppm）.
Embodiment 3
A kind of preparation method of height ratio capacity lithium-rich anode material, using hydro-thermal method one-step synthesis lithium-rich anode material, tool Body comprises the following steps：
1）It weighs 0.65g manganese acetates, 0.22g nickel acetates, 0.22g cobalt acetates to be put into inner liner of reaction kettle, adds in 10mL and go Ionized water, stirring makes each dissolution of raw material, under 40 DEG C of water-bath, adds in the lithium hydroxide solution that 50mL concentration is 2moL/L, stirs It mixes 20 minutes, adds the reaction of 3mL hydrogen peroxide；
2）After inner liner of reaction kettle is sealed, it is put into reaction kettle；It is dried when 200 DEG C of reactions 12 are small, then through centrifuge washing After obtain sample, gained sample again through 600 DEG C of annealing 2 it is small when, lithium-rich anode material is made.
According to the application of height ratio capacity lithium-rich anode material made from above-mentioned preparation method, specially in lithium ion battery just Application in the material of pole；Lithium battery assembles：In mass ratio 75:15:5 weigh lithium-rich anode material, carbon black, Kynoar, mix After closing grinding, 0.25 cm is evenly coated in2Aluminium flake on do anode, cathode is lithium metal, and electrolyte is 1M LiPF6EC+EMC (EC/ EMC=1/1 v/v) solution.
Battery assembling carries out in the glove box of argon atmosphere（The content of water and oxygen is below 0.5 ppm）.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with Modification should all belong to the covering scope of the present invention.

Claims (2)

1. a kind of preparation method of height ratio capacity lithium-rich anode material, it is characterised in that：Using hydro-thermal method one-step synthesis richness lithium just Pole material, specifically includes following steps：
1) 0.6-0.735g manganese acetates, 0.2-0.249g nickel acetates, 0.2-0.249g cobalt acetates is weighed to be put into inner liner of reaction kettle, 10-15mL deionized waters are added in, stirring makes each dissolution of raw material, and under 40-70 DEG C of water-bath, it is 2- to add in 50-55mL concentration The lithium hydroxide solution of 2.5moL/L stirs 10-20 minutes, adds the reaction of 3-8mL hydrogen peroxide；
2) after inner liner of reaction kettle is sealed, it is put into reaction kettle；It is done when 180-200 DEG C of reaction 12-48 is small, then through centrifuge washing Obtain sample after dry, gained sample again through 400-600 DEG C of annealing 2-6 it is small when, lithium-rich anode material is made.
2. the application of height ratio capacity lithium-rich anode material made from preparation method according to claim 1, it is characterised in that： Application in anode material for lithium-ion batteries, in mass ratio 75-85:10-15:5-10 weighs lithium-rich anode material, carbon black, gathers Vinylidene after mixed grinding, is evenly coated in 0.25cm2Aluminium flake on do anode, cathode is lithium metal, and electrolyte is 1M LiPF6EC+EMC solution.
CN201510688092.1A 2015-10-23 2015-10-23 A kind of preparation method of height ratio capacity lithium-rich anode material Expired - Fee Related CN105206824B (en)

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CN107256962B (en) * 2017-06-19 2019-08-23 上海纳米技术及应用国家工程研究中心有限公司 A kind of the tertiary cathode material nickel cobalt aluminium and preparation method and application of aluminium foil growth in situ
CN108376778A (en) * 2018-02-27 2018-08-07 天津丹兴科技有限责任公司 The method that solvent-thermal method prepares high-performance lithium-rich anode material

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CN1277321C (en) * 2004-10-20 2006-09-27 天津化工研究设计院 Method of prepn, of positive electrode laminated cell lithium manganate of lithium ion
CN103311532B (en) * 2013-05-24 2015-01-21 天津大学 Preparation method of lithium-enriched anode material with nano-grade lamellar-spinel composite structure
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