CN104009219B - A kind of porous foam shape manganese based solid solution positive electrode and preparation method thereof - Google Patents
A kind of porous foam shape manganese based solid solution positive electrode and preparation method thereof Download PDFInfo
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- CN104009219B CN104009219B CN201310679958.3A CN201310679958A CN104009219B CN 104009219 B CN104009219 B CN 104009219B CN 201310679958 A CN201310679958 A CN 201310679958A CN 104009219 B CN104009219 B CN 104009219B
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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
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The present invention relates to a kind of porous foam shape solid solution cathode material and preparation method thereof.Pore forming method is pyrolyzed particular by high-molecular compound, the lithium salts of certain stoichiometric proportion, manganese salt, nickel salt, cobalt salt are configured to the aqueous solution first, then high-molecular compound is added in mixing salt solution, then precipitating reagent is added, dried at a certain temperature after reaction completely, it is to obtain porous foam shape manganese based solid solution that certain time is then sintered under high temperature air atmosphere.Solid solution obtained by the present invention has the three-dimensional structure of porous foam shape, on the one hand improves the contact area of electrode material and electrolyte, is advantageous to the diffusion of lithium ion, so as to improve power density energy density.On the other hand the change of tension force in cyclic process can also be adjusted, improves its cyclical stability.
Description
Technical field
The present invention relates to novel energy resource material technology field, and in particular to a kind of porous foam shape manganese based solid solution positive electrode
And preparation method thereof.
Background technology
Since the nineties in last century, lithium ion battery in the very big share of portable electronic product market share, and by
Step is applied on electric automobile and hybrid-electric car.Traditional anode material of lithium battery LiCoO2Because of price
Height, security is low and toxicity is big, is restricted the more massive application of lithium ion battery.Spinelle LiMn2O4And olivine
LiFePO4Because the features such as abundant Mn, Fe reserves, hypotoxicity and security, has attracted the interest of expert, but LiMn2O4's
Low capacity and LiFePO4Low-voltage cause them that there is relatively low energy density.
Lithium-rich manganese-based layed solid-solution material xLi2MnO3·(1-x)LiMO2 The reason of (at least one of M=Ni, Co, Mn)
By specific capacity more than 300 mAh/g, 200 mAh/g can be actually more than using capacity, operating voltage is high, it is considered to be the next generation is most
Promising anode material of lithium battery.
Porous material has substantial amounts of application in lithium ion cell positive and negative material, shows good electrochemistry
Matter.This loose structure, the contact area of electrode material and electrolyte is on the one hand improved, be advantageous to the diffusion of lithium ion, from
And improve power density energy density.On the other hand the change of tension force in cyclic process can also be adjusted, it is steady to improve its circulation
It is qualitative.For lithium-rich manganese-based layed solid-solution material, cycle performance begins to fail after first lap, and this is due to companion
With O in body phase lattice2-Abjection, Li+Can occur can not reverse back it is embedding, so as to which the change of lattice arrangement can be caused, in material table
Face produces micro-crack or amorphous material.And porous material can play a part of a buffering and regulation, thus can subtract
The structure change of small material.
The content of the invention
The purpose of the present invention is just being to provide a kind of porous foam shape manganese based solid solution positive electrode and preparation method thereof, can be with
The contact area of electrode material and electrolyte is improved, is advantageous to the diffusion of lithium ion, so as to improve power density energy density,
The change of tension force in cyclic process can also be adjusted simultaneously, improve its cyclical stability.
In order to solve the above technical problems, the technical solution used in the present invention is：A kind of porous foam shape manganese based solid solution
Positive electrode and preparation method thereof is the salt-mixture that lithium acetate, manganese acetate, nickel acetate, cobalt acetate are configured by certain stoichiometric proportion
Solution；The high-molecular compound pore creating material of certain mass percent is added in above-mentioned mixing salt solution, carries out ultrasonic disperse
Uniformly；The precipitating reagent of stoichiometric proportion identical with metal salt is added gradually in said mixture；By thing mixed above one
Determine to dry at temperature；By above-mentioned dried object pulverize it is last under high temperature air atmosphere sinter certain time obtain porous bubble
Foam shape manganese based solid solution.
The total concentration of above-mentioned mixing salt solution is 1-5 mol/L.
Above-mentioned high-molecular compound pore creating material includes polyvinylpyrrolidone（PVP）, polyvinyl alcohol（PVA）, polyethylene glycol
（PEG）And phenolic resin, mass fraction are 10% -50%.
Above-mentioned precipitating reagent is oxalic acid or carbonic acid.
Above-mentioned drying temperature is 80-150 °C.
Above-mentioned sintering temperature is 800-1000 °C, roasting time 5-10h, and heating rate is 3-10 °C/min.
Advantages of the present invention：The present invention is prepared for porous foam shape solid solution using high-molecular compound pyrolysis pore forming method
Positive electrode, the contact area of electrode material and electrolyte is on the one hand improved, be advantageous to the diffusion of lithium ion, so as to improve
Power density energy density.On the other hand the change of tension force in cyclic process can also be adjusted, improves its cyclical stability.
Brief description of the drawings
Fig. 1 is the solid solution Li of PVP pore-creating of the present invention1.2(Mn0.4Ni0.25Co0.15)O2Low power SEM figure；
Fig. 2 is the solid solution Li of PVP pore-creating of the present invention1.2(Mn0.4Ni0.25Co0.15)O2High power SEM figure；
Fig. 3 is the solid solution Li of the present invention with PVP pore-creating and non-pore-creating1.2(Mn0.4Ni0.25Co0.15)O2In 0.05C,
Voltage window is that the recursive nature under 2.0V -4.8V compares.
Embodiment
Embodiment 1
With the solid solution Li of PVP pore-creating1.2(Mn0.4Ni0.25Co0.15)O2Preparation process
（1）Stoichiometrically 1.2：0.4：0.25：0.15 proportional arrangement 400ml concentration is 2 mol/L's
LiCH3CO2、Mn(CH3CO2)2、Ni(CH3CO2)2、Co(CH3CO2)2Salting liquid.
（2）By the PVP that mass fraction is 20%（Mw=10000）It is added in above-mentioned mixing salt solution, ultrasonic disperse is uniform.
（3）By the H that 400ml concentration is 1 mol/L2C2O4It is added gradually in said mixture.
（4）Above material is dried under 120 °C after reacting 3h.
（5）Above-mentioned dried object is pulverized and last obtains porous foam shape manganese base in 800 °C of air atmosphere sintering 5h
Solid solution.
Embodiment 2
With the solid solution Li of PVA pore-creating1.2(Mn0.4Ni0.25Co0.15)O2Preparation process
（1）Stoichiometrically 1.2：0.4：0.25：0.15 proportional arrangement 400ml concentration is 2 mol/L's
LiCH3CO2、Mn(CH3CO2)2、Ni(CH3CO2)2、Co(CH3CO2)2Salting liquid.
（2）By the PVA that mass fraction is 30%（Mw=15000）It is added in above-mentioned mixing salt solution, ultrasonic disperse is uniform.
（3）By the H that 400ml concentration is 1 mol/L2C2O4It is added gradually in said mixture.
（4）Above material is dried under 120 °C after reacting 3h.
（5）The above-mentioned dried object last sintering 5h under 800 °C of high temperature air atmosphere that pulverizes is obtained into porous foam
Shape manganese based solid solution.
Embodiment 3
The solid solution Li of phenolic resin pore-creating1.2(Mn0.4Ni0.25Co0.15)O2Preparation process
（1）Stoichiometrically 1.2：0.4：0.25：0.15 proportional arrangement 400ml concentration is 2 mol/L's
LiCH3CO2、Mn(CH3CO2)2、Ni(CH3CO2)2、Co(CH3CO2)2Salting liquid.
（2）The formaldehyde that mass fraction is 10% is added in above-mentioned mixing salt solution, ultrasonic disperse is uniform.
（3）By 0.4mol H2C2O4With the resorcinol of the amount of certain material（Formaldehyde：Resorcinol=1.5：1）It is dissolved in
In 400ml water, then it is added gradually in said mixture.
（4）By the present 80 °C of reactions 5h of thing mixed above, it is then transferred under 120 °C and dries.
（5）Above-mentioned dried object is pulverized and last obtains porous foam shape in 850 °C of high temperature air atmosphere sintering 10h
Manganese based solid solution.
Embodiment 4（Comparative example）
The solid solution Li of common Co deposited synthesis1.2(Mn0.4Ni0.25Co0.15)O2Preparation process
（1）Stoichiometrically 1.2：0.4：0.25：0.15 proportional arrangement 400ml concentration is 2 mol/L's
LiCH3CO2、Mn(CH3CO2)2、Ni(CH3CO2)2、Co(CH3CO2)2Salting liquid.
（2）By the H that 400ml concentration is 1 mol/L2C2O4It is added gradually in said mixture.
（3）Above material is dried under 120 °C after reacting 3h.
（4）The above-mentioned dried object last sintering 5h under 800 °C of air atmosphere that pulverizes is obtained into porous foam shape manganese
Based solid solution.
Fig. 1 is the solid solution Li of PVP pore-creating of the present invention1.2(Mn0.4Ni0.25Co0.15)O2Low power SEM figure.By low power
For photo we can observe that the material is in integrally porous pumiceous texture, pore size distribution is uniform.Fig. 2 is PVP of the present invention
The solid solution Li of pore-creating1.2(Mn0.4Ni0.25Co0.15)O2High power SEM figure.By high power photo we can observe that aperture it is big
It is small in 100-500nm or so, reunite each other between particle, form three-dimensional netted structure, be advantageous to the conduction of electronics.
Fig. 3 is the solid solution Li of the present invention with PVP pore-creating and non-pore-creating1.2(Mn0.4Ni0.25Co0.15)O2In 0.05C,
Voltage window is that the recursive nature under 2.0V -4.8V compares.By that can confirm that the structure of porous foam shape can be obvious in figure
The specific capacitance of solid solution can also be improved simultaneously by improving the cyclical stability of solid solution.
The present invention is prepared for porous foam shape solid solution cathode material, a side using high-molecular compound pyrolysis pore forming method
Face improves the contact area of electrode material and electrolyte, is advantageous to the diffusion of lithium ion, so as to improve power density energy
Density.On the other hand the change of tension force in cyclic process can also be adjusted, improves its cyclical stability.
Certainly, it is limitation of the present invention that described above, which is not, and the present invention is also not limited to the example above, the art
Those of ordinary skill, in the essential scope of the present invention, the variations, modifications, additions or substitutions made, should all belong to the present invention
Protection domain.
Claims (1)
- A kind of 1. preparation method of porous foam shape manganese based solid solution positive electrode, it is characterised in that：A kind of porous foam The preparation method of shape manganese based solid solution positive electrode is stoichiometrically 1.2:0.4:0.25:0.15 proportional arrangement 400mL Concentration is 2mol/L lithium acetate, manganese acetate, nickel acetate, the mixing salt solution of cobalt acetate；It is 10% -50% by mass fraction High-molecular compound pore creating material is added in above-mentioned mixing salt solution, and it is uniform to carry out ultrasonic disperse；It is 1mol/L by 400mL concentration Precipitating reagent be added gradually in said mixture；Thing mixed above is dried at 80-150 DEG C；Will be above-mentioned dried mixed Compound pulverize it is last 5-10h is sintered under high temperature air atmosphere, that is, obtain porous foam shape manganese based solid solution；The high-molecular compound pore creating material includes polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyethylene glycol (PEG) Or phenolic resin；Described sintering temperature is 800-1000 DEG C, and heating rate is 3-10 DEG C/min；The precipitating reagent is oxalic acid or carbonic acid.
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| CN104466101A (en) * | 2014-12-29 | 2015-03-25 | 华南师范大学 | High-capacity lithium ion battery anode material 0.5Li2MnO3*0.5LiMn1/3Ni1/3Co1/3O2 and preparation method thereof |
| CN105110314B (en) * | 2015-07-28 | 2017-03-08 | 大连理工大学 | A kind of synthetic method of the nitrogen-doped nanometer foamy carbon of embedded metal oxide Hollow Nanoparticles |
| CN106784632B (en) * | 2016-12-21 | 2020-04-17 | 桑顿新能源科技有限公司 | Method for synthesizing high-interface-stability cathode material |
| CN107946090B (en) * | 2017-11-20 | 2019-07-02 | 宝鸡文理学院 | A kind of high capacity cobalt ions intercalation porous manganese dioxide electrode material and preparation method thereof |
| CN108039481A (en) * | 2017-12-25 | 2018-05-15 | 湖北环天高科新能源有限公司 | A kind of fluorine-containing power battery positive electrode |
| CN108054375A (en) * | 2017-12-25 | 2018-05-18 | 湖北环天高科新能源有限公司 | A kind of power battery positive electrode |
| CN108039480A (en) * | 2017-12-25 | 2018-05-15 | 湖北环天高科新能源有限公司 | Power battery positive electrode |
| CN109786695B (en) * | 2018-12-29 | 2022-01-28 | 合肥融捷能源材料有限公司 | High-rate lithium nickel cobalt manganese oxide positive electrode material and preparation method thereof |
| CN112320848A (en) * | 2020-11-12 | 2021-02-05 | 齐鲁工业大学 | Preparation method of vanadium trioxide porous particles |
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Denomination of invention: Porous foamed manganese-based solid solution anode material and preparation method thereof Effective date of registration: 20200629 Granted publication date: 20171212 Pledgee: China Construction Bank Corporation Qingdao Zhongshan Road sub branch Pledgor: QINGDAO QIANYUN HIGH-TECH NEW MATERIAL Co.,Ltd. Registration number: Y2020370010025 |