CN105047898B - A kind of twin spherical lithium ion secondary battery lithium-rich anode material and preparation method thereof - Google Patents
A kind of twin spherical lithium ion secondary battery lithium-rich anode material and preparation method thereof Download PDFInfo
- Publication number
- CN105047898B CN105047898B CN201510305521.2A CN201510305521A CN105047898B CN 105047898 B CN105047898 B CN 105047898B CN 201510305521 A CN201510305521 A CN 201510305521A CN 105047898 B CN105047898 B CN 105047898B
- Authority
- CN
- China
- Prior art keywords
- lithium
- secondary battery
- lithium ion
- anode material
- ion secondary
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
Abstract
The invention belongs to technical field of lithium ion is and in particular to a kind of twin spherical lithium ion secondary battery lithium-rich anode material and preparation method thereof.Lithium ion secondary battery anode material Li of the present invention1.13Ni0.3Mn0.57O2, it is the size that linked by the ball symbiosis of about 1 μm of two diameters in 2 μm about of homogeneous twin spherical richness lithium material.The present invention adopts simple chemical precipitation, the method for mixed sintering, has prepared the lithium-rich anode material of twin spherical looks, and synthesis is simple, with low cost.Material has been carried out with electrochemical Characterization, the cycle performance of material be improved significantly, material Stability Analysis of Structures in constant current charge-discharge cyclic process, mean voltage decay is minimum.
Description
Technical field
The invention belongs to technical field of lithium ion and in particular to a kind of twin spherical lithium ion secondary battery richness lithium just
Pole material and preparation method thereof.
Background technology
Lithium ion battery because its energy density is high, self-discharge rate is little, have extended cycle life, memory-less effect etc. many excellent
Gesture, becomes the confession energy of main flow in portable.The performance of lithium ion battery is often by the property of its positive electrode
Can determine.
Stratified material cobalt acid lithium (LiCoO2) due to extensive the features such as running voltage is high, discharge and recharge is steady, electrical conductivity is high
Application is on portable devices.But because it is expensive, overcharge resistant ability is poor, have certain toxicity, it is difficult to give birth to
Produce motive-power battery.Commercial motive-power battery positive electrode is mainly LiFePO4 (LiFePO4), its abundant raw material, low cost,
But the capacity of ferric phosphate lithium cell is not high and electrical conductivity is poor.For reduces cost, improve specific capacity, in recent years, rich lithium is just
Pole material receives extensive attention.It has a higher specific discharge capacity, abundant raw material source, cheap.At present, Fu Li
Positive electrode still suffers from some problems, and coulombic efficiency is low first for it, capacity attenuation is fast, high rate performance is low in cyclic process etc.,
It is required for doing further improvement research, in cyclic process, the sharp-decay of mean voltage can lead to the reduction of energy density, very
Its commercial applications is also limit in big degree.
Content of the invention
It is an object of the invention to provide a kind of raw material is cheap, preparation process is simple, synthesize twin spherical looks and to material
The lithium ion secondary battery anode material Li that cyclical stability is greatly improved1.13Ni0.3Mn0.57O2Preparation method, its step
As follows：
1) by MnSO4·H2O and Na2CO3In molar ratio 1：After 1 weighs, it is dissolved in deionized water respectively, stirring 10～
20min, forms settled solution；Under stirring, to MnSO4The dehydrated alcohol of its volume 10～15% is poured in solution, with
After pour Na into2CO3Solution, continuously stirred 1～6h, after deionized water and dehydrated alcohol are centrifuged for several times respectively, vacuum at 50～80 DEG C
Dried 6～12h, obtains MnCO3Powder；
2) by gained MnCO3Powder processes 3 under the conditions of air, 400～500 DEG C (1～5 DEG C/min of programming rate)～
6h, obtains black MnO after being naturally down to room temperature2Pressed powder；
3) press Li1.13Ni0.3Mn0.57O2In chemical formula, Li, Ni, Mn stoichiometric proportion weighs LiOH H2O is (in order to compensate lithium
Volatilization under high temperature, somewhat excessive 2～5%), Ni (NO3)2·6H2Jointly it is dissolved in deionized water after O, add MnO2Powder, 40
Under the conditions of～80 DEG C, stirring is until be evaporated deionized water；
4) by step 3) product processes 6～18h under the conditions of 800～950 DEG C, thus obtaining lithium ion of the present invention
Secondary battery positive electrode material Li1.13Ni0.3Mn0.57O2.
A kind of lithium ion secondary battery anode material of the present invention, it is characterised in that being to be prepared by said method, obtains
To the size being linked by the ball symbiosis of about 1 μm of two diameters in 2 μm about of homogeneous twin spherical precursor material, and
Keep pattern and size in follow-up reaction well, prepare the rich lithium material of homogeneous twin spherical looks.
The invention has the beneficial effects as follows：
(1) the rich lithium material Li preparing1.13Ni0.3Mn0.57O2For twin spherical looks, purity is high, reproducible.
(2) equipment that preparation uses is simple, does not have the use of expensive device, raw material is cheap and easy to get, with low cost.
(3) technique is very simple, and repeatability preferably, can be not only used for experimental implementation, is well suited for industrial large-scale production again.
(4) anode material for lithium-ion batteries of present invention preparation has particularly stable circulating ratio performance, mean voltage
Stable, there is no the phenomenon of the generally mean voltage rapid decay that richness lithium material is showed.
The present invention adopts simple chemical precipitation, the method for mixed sintering, has prepared the lithium-rich anode of twin spherical looks
Material, synthesis is simple, with low cost.Material has been carried out with electrochemical Characterization, the cycle performance of material be improved significantly, material
Stability Analysis of Structures in constant current charge-discharge cyclic process, mean voltage decay is minimum.
Brief description
For the technical scheme that is illustrated more clearly that in the present invention and its performance preparing material, correlation is given below
Diagram.
Fig. 1 is the MnCO of embodiment 1 preparation3Material and finally rich lithium material Li1.13Ni0.3Mn0.57O2Scanning electron microscope (SEM) photograph
(SEM).Figure (a) is MnCO under 2 μm of scales3Scanning electron microscope (SEM) photograph (SEM).Figure (b) is Li under 2 μm of scales1.13Ni0.3Mn0.57O2
Scanning electron microscope (SEM) photograph (SEM).From scanning electron microscopic picture it can be seen that the Li of final preparation1.13Ni0.3Mn0.57O2Twin spherical looks are protected
Hold preferably, size is more uniform, soilless sticking.
Fig. 2 is the Li of embodiment 1 preparation1.13Ni0.3Mn0.57O2X-ray diffraction (XRD) collection of illustrative plates of material.Spread out from x- ray
Penetrate (XRD) collection of illustrative plates can draw, X-ray diffraction (XRD) the collection of illustrative plates free from admixture peak of prepared material occurs, that is, prove preparation
Material be pure phase rich lithium material Li1.13Ni0.3Mn0.57O2.
Fig. 3 is the Li of embodiment 1 preparation1.13Ni0.3Mn0.57O2As anode material for lithium-ion batteries, lithium piece is as to electricity
Pole, the cycle performance figure of the half-cell of making.It can be seen that under the electric current density of 40m A/g, the putting first of material
Electric specific capacity is 212.4mAh/g, and after 50 times circulate, specific discharge capacity still can reach 208.6mAh/g, and discharge specific volume
Amount conservation rate is 98.2%, and therefrom illustrative material has extraordinary cyclical stability.
Fig. 4 is the Li of embodiment 1 preparation1.13Ni0.3Mn0.57O2As positive electrode, lithium piece as to electrode, the half of making
The battery perseverance under 40mA/g, 100mA/g, 200mA/g, 500mA/g, 1A/g, 2A/g, 100mA/g difference electric current density respectively
Current test high rate performance figure.It can be seen that material each electric current density test under stable circulation, and 1A/g with
And under the high current of 2A/g, the specific capacity of material still can reach 127mAh/g and 87mAh/g respectively it was demonstrated that material has relatively
Outstanding high rate performance.
Fig. 5 is the Li of embodiment 1 preparation1.13Ni0.3Mn0.57O2Positive electrode under 40mA/g electric current density, constant current cycle
The variation diagram of 50 mean voltage.The mean voltage of material changes very little in cyclic process as we can see from the figure, follows for 50 times
Only decayed after ring 0.058V, and for the battery compared to the rich lithium material assembling of usual method preparation, the stability of battery is non-
Chang Youyi.
Fig. 6 is the Li of embodiment 1 preparation1.13Ni0.3Mn0.57O2Positive electrode under 40mA/g electric current density, constant current cycle
The variation diagram of the differential curve (dQ/dV curve) to voltage for the specific capacity during 50 times, the discharge process of battery made.
Respectively the differential to voltage for the specific capacity is done to the discharge process of the 1st, 2,10,20,30,40,50 times.Can see from curve chart
The peak shape of curve is particularly stable, does not almost have what change, characterizes in whole cyclic process, the cathode material structure frame of battery
Frame is very stable, and this cycle performance stable with measured battery matches.
Specific embodiment
Embodiment 1：
In molar ratio 1：1 weighing MnSO4·H2O (0.507g) and Na2CO3(0.3179g) it is dissolved in 70mL deionization respectively
Water, stirring 20min so that medicine is fully dissolved, formed settled solution, backward MnSO47mL dehydrated alcohol is poured successively in solution
And Na2CO3Solution, stirs 3h, deionized water and dehydrated alcohol centrifuge washing 3 times, vacuum drying treatment 8h at 60 DEG C respectively, obtains
To MnCO3Powder；By MnCO3Powder is transferred to Muffle furnace (2 DEG C/min of programming rate) under air conditionses, 400 DEG C of process 5h,
Obtain the MnO of about 0.25g2Pressed powder.
In order to synthesize final rich lithium material, we weigh 0.16g MnO2Powder, and stoichiometrically weigh
LiOH·H2O (excessive 5%, 0.1607g) and Ni (NO3)2·6H2O (0.2817g) is mixed with gained powder in deionized water,
After stirring is evaporated deionized water, move into Muffle furnace, under the conditions of 850 DEG C, process 12h, both obtain Li1.13Ni0.3Mn0.57O2Electrode material,
About 0.28g.
Weigh 0.075g richness lithium material Li1.13Ni0.3Mn0.57O2, conductive auxiliary agent (super P is conductive black), binding agent
(PVDF is Kynoar) is according to mass ratio 7.5：1.5：1 mixing, gained slurry is coated on aluminium foil, 120 DEG C of vacuum dryings
Afterwards, it is cut into the square positive plate of length of side 8mm.Make negative pole from lithium piece, conventional lithium-ion battery electrolytes elected as by electrolyte,
I.e. 1mol/L lithium hexafluoro phosphate (LiPF6)/ethylene carbonate (EC)：Dimethyl carbonate (DMC)：Ethyl methyl carbonate (EMC) mixed
Close liquid=1：1：8 (volume ratios), are assembled into 2032 type button cells, and do corresponding electro-chemical test.The circulating battery of preparation
Performance curve is as shown in figure 3, electric current density is 40mA/g it can be seen that the cycle performance of battery is very good.High rate performance figure is such as
Shown in Fig. 4, electric current density is 40mA/g, 100mA/g, 200mA/g, 500mA/g, 1A/g, 2A/g, 100mA/g, shows that battery has
There is preferably high rate performance., as shown in figure 5, battery discharge mean voltage is stable, decay is less for mean voltage situation.Battery is done
, as shown in fig. 6, peak shape varies less, battery is stable for the differential curve of specific capacity and voltage.
Claims (4)
1. a kind of twin spherical lithium ion secondary battery lithium-rich anode material Li1.13Ni0.3Mn0.57O2Preparation method, its step
As follows：
1) by MnSO4·H2O and Na2CO3In molar ratio 1：After 1 weighs, it is dissolved in deionized water respectively, stirs 10～20min, formed
Settled solution；Under stirring, to MnSO4Pour the dehydrated alcohol of its volume 10～15% in solution into, be then poured into Na2CO3
Solution, continuously stirred 1～6h, after deionized water and dehydrated alcohol are centrifuged for several times respectively, vacuum drying treatment 6 at 50～80 DEG C～
12h, obtains MnCO3Powder；
2) by gained MnCO3Powder processes 3～6h under the conditions of air, 400～500 DEG C, obtains black after being naturally down to room temperature
MnO2Pressed powder；
3) weigh LiOH H2O、Ni(NO3)2·6H2Jointly it is dissolved in deionized water after O, add step 2) MnO for preparing2Powder
End, LiOH H2O、Ni(NO3)2·6H2O、MnO2Consumption between three kinds of materials meets Li1.13Ni0.3Mn0.57O2Li in chemical formula,
The stoichiometric proportion of Ni, Mn, under the conditions of 40～80 DEG C, stirring is until be evaporated deionized water；
4) by step 3) product processes 6～18h under the conditions of 800～950 DEG C, thus obtaining twin spherical lithium ion secondary battery
Lithium-rich anode material Li1.13Ni0.3Mn0.57O2.
2. a kind of twin spherical lithium ion secondary battery lithium-rich anode material Li as claimed in claim 11.13Ni0.3Mn0.57O2
Preparation method it is characterised in that：Step 2) 1～5 DEG C/min of programming rate.
3. a kind of twin spherical lithium ion secondary battery lithium-rich anode material Li as claimed in claim 11.13Ni0.3Mn0.57O2
Preparation method it is characterised in that：Step 3) in, LiOH H2O excessive 2～5%.
4. a kind of twin spherical lithium ion secondary battery lithium-rich anode material Li1.13Ni0.3Mn0.57O2It is characterised in that：It is right
1～3 any one method of requirement prepares.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510305521.2A CN105047898B (en) | 2015-06-05 | 2015-06-05 | A kind of twin spherical lithium ion secondary battery lithium-rich anode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510305521.2A CN105047898B (en) | 2015-06-05 | 2015-06-05 | A kind of twin spherical lithium ion secondary battery lithium-rich anode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105047898A CN105047898A (en) | 2015-11-11 |
| CN105047898B true CN105047898B (en) | 2017-03-01 |
Family
ID=54454276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510305521.2A Expired - Fee Related CN105047898B (en) | 2015-06-05 | 2015-06-05 | A kind of twin spherical lithium ion secondary battery lithium-rich anode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105047898B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021037678A1 (en) * | 2019-08-28 | 2021-03-04 | Basf Se | Particulate material, method for its manufacture and use |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2566473B (en) | 2017-09-14 | 2020-03-04 | Dyson Technology Ltd | Magnesium salts |
| GB2566472B (en) | 2017-09-14 | 2020-03-04 | Dyson Technology Ltd | Magnesium salts |
| GB2569390A (en) | 2017-12-18 | 2019-06-19 | Dyson Technology Ltd | Compound |
| GB2569388B (en) | 2017-12-18 | 2022-02-02 | Dyson Technology Ltd | Compound |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102832386B (en) * | 2012-08-31 | 2014-09-24 | 华南师范大学 | Preparation method of long-life layered lithium-rich material Li[Li0.13Ni0.30Mn0.57]O2 |
| CN103474650B (en) * | 2013-10-11 | 2015-06-17 | 哈尔滨工业大学 | Method for preparing hollow high voltage nickel manganese acid lithium anode material |
| CN104157844B (en) * | 2014-08-19 | 2016-03-16 | 哈尔滨工业大学 | High-rate lithium-rich manganese-based anode material of a kind of nano-micro structure and preparation method thereof |
-
2015
- 2015-06-05 CN CN201510305521.2A patent/CN105047898B/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021037678A1 (en) * | 2019-08-28 | 2021-03-04 | Basf Se | Particulate material, method for its manufacture and use |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105047898A (en) | 2015-11-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102790217B (en) | Carbon cladded ferriferrous oxide negative electrode material of lithium ion battery and preparation method thereof | |
| CN110474044A (en) | A kind of high-performance water system Zinc ion battery positive electrode and the preparation method and application thereof | |
| CN103280574A (en) | Lithium-enriched ternary anode material of power lithium-ion battery and preparation method of lithium-enriched ternary anode material | |
| CN107331853B (en) | Graphene composite multilayer porous spherical lithium manganate electrode material and lithium ion battery prepared from same | |
| CN105047898B (en) | A kind of twin spherical lithium ion secondary battery lithium-rich anode material and preparation method thereof | |
| CN107492643A (en) | A kind of titanium phosphate lithium coats LiNi1/3Co1/3Mn1/3O2Positive electrode and preparation method thereof | |
| CN108807886A (en) | Double-coating anode material for lithium-ion batteries LiNi0.6Co0.2Mn0.2O2And preparation method thereof | |
| CN107834050A (en) | A kind of lithium-enriched cathodic material of lithium ion battery and its improved method | |
| CN110429268A (en) | A kind of modified boron doping lithium-rich manganese-based anode material and the preparation method and application thereof | |
| CN104037412B (en) | The preparation method of high performance lithium ion secondary battery negative material multilevel hierarchy nano-hollow ball | |
| CN106207130A (en) | A kind of lithium battery nickelic positive electrode of surface modification and preparation method thereof | |
| CN111162256A (en) | Mixed polyanion type sodium ion battery positive electrode material and preparation thereof | |
| CN107902633A (en) | A kind of selenizing pyrite material and its battery of preparation | |
| CN106784677A (en) | A kind of preparation of lithium-enriched cathodic material of lithium ion battery and improved method | |
| CN108975297A (en) | The method that the crystallization water by removing nanoscale iron phosphate prepares high performance lithium iron phosphate positive material | |
| CN102931383A (en) | Preparation method of composite anode material of lithium-ion power battery | |
| CN108054350A (en) | Lithium-sulfur battery composite cathode material and preparation method thereof | |
| CN103441238A (en) | Mg-doped Li-rich anode material and preparation method for same | |
| CN110707294A (en) | Lithium-philic heteroatom and metal oxide co-doped three-dimensional fiber framework lithium battery cathode and preparation method thereof | |
| CN102903918A (en) | Preparation method for manganese phosphate lithium nanosheet | |
| CN103413935A (en) | Mo-doped lithium-rich positive electrode material and preparation method thereof | |
| CN105006563A (en) | Preparation method for lithium ion battery anode active material Li2ZnTi3O8 | |
| CN107195884A (en) | A kind of lithium metasilicate doped graphene lithium ion battery negative material and preparation method thereof | |
| CN107256962B (en) | A kind of the tertiary cathode material nickel cobalt aluminium and preparation method and application of aluminium foil growth in situ | |
| CN110336026A (en) | The preparation method and water system sodium-ion battery of water system sodium-ion battery positive material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170301 Termination date: 20180605 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |