CN108832118A - MnO2The preparation method of intermediate and preparation method thereof and lithium-rich manganese-based anode material - Google Patents
MnO2The preparation method of intermediate and preparation method thereof and lithium-rich manganese-based anode material Download PDFInfo
- Publication number
- CN108832118A CN108832118A CN201810660336.9A CN201810660336A CN108832118A CN 108832118 A CN108832118 A CN 108832118A CN 201810660336 A CN201810660336 A CN 201810660336A CN 108832118 A CN108832118 A CN 108832118A
- Authority
- CN
- China
- Prior art keywords
- mno
- preparation
- lithium
- manganese
- anode material
- 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.)
- Pending
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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
-
- 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
- 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 present invention relates to Material Fields, in particular to a kind of MnO2The preparation method of intermediate and preparation method thereof and lithium-rich manganese-based anode material.By MnO2Intermediate and LiOHH2O, Ni (OH)2And Co3O4After mixing, the furnace cooling after 700-900 DEG C of calcining.By introducing polyvinylpyrrolidone (PVP) and ethylene glycol (EG), MnO is prepared in modification2Intermediate, and as manganese source, the lithium-rich manganese-based anode material with good crystallinity can be prepared further across solid phase reaction.Improvement prepares the chemical property that material shows to be obviously improved, due to uniform nanoscale primary particle can be by shorter Li+Transmission path significantly increases kinetics of diffusion, and cellular secondary structure can better adapt in cyclic process due to Li+The lattice distortion that deintercalation generates repeatedly, enhancing structure stability.
Description
Technical field
The present invention relates to Material Fields, in particular to a kind of MnO2Intermediate and preparation method thereof and rich lithium manganese
The preparation method of base anode material.
Background technique
Lithium ion battery is due to its high-energy density, good safety and longer service life, in mobile chemical-electrical
It is concerned in source.Lithium-rich manganese-based anode material, one of the anode material for lithium-ion batteries as great potential are considered as solid
Solution material Li [Lix/3Niα(1-x)Coβ(1-x)Mn2x/3+γ(1-x)]O2Or nanocomposite xLi2MnO3(1-x)LiMO2(M=Ni,
Co, Mn), can be provided under relatively high operating voltage higher specific capacity (>250mAh·g-1), and be concerned.
But due to following problems：Irreversible transition from layer structure to spinel structure causes long-term cyclic process to be discharged
The continuous decaying of platform；Lower lithium ion diffusion coefficient itself brings poor high rate performance etc., and practical application receives
Larger limitation.
Summary of the invention
The purpose of the present invention is to provide a kind of MnO2The preparation method of intermediate.
The purpose of the present invention is to provide a kind of MnO2Intermediate.
The purpose of the present invention is to provide a kind of preparation method of lithium-rich manganese-based anode material, can be improved it is lithium-rich manganese-based just
The chemical property of pole material.
To achieve the goals above, this hair, the technical solutions adopted are as follows for bright embodiment：
A kind of MnO2The preparation method of intermediate, includes the following steps：Include the following steps：It is added into manganese salt solution
It is stirred until homogeneous after PVP, obtains the first solution；Under agitation by ammonium bicarbonate soln or sodium carbonate liquor and the first solution
Hybrid reaction to milky white precipitate generates；Wherein, manganese salt solution is the mixed solution of manganate and alcohol and deionized water.
A kind of MnO2Intermediate, using such as above-mentioned MnO2The preparation method of intermediate is made.
A kind of preparation method of lithium-rich manganese-based anode material, by such as above-mentioned MnO2Intermediate and LiOHH2O, Ni
(OH)2And Co3O4(n in molar ratio(LiOH.H2O):n(MnO2):n(Ni(OH)2):n(Co3O4)=1.0-1.5:0.50-0.55:0.11-
0.15:After 0.12-0.14) mixing, the furnace cooling after 700-900 DEG C of calcining.
The beneficial effects of the invention are as follows：
A kind of MnO provided by the invention2The preparation method of intermediate, includes the following steps：PVP is added into manganese salt solution
After be stirred until homogeneous, obtain the first solution；Ammonium bicarbonate soln or sodium carbonate liquor are mixed under agitation with the first solution
Reaction to milky white precipitate is closed to generate；Wherein, manganese salt solution is the mixed solution of manganate and alcohol and deionized water.
A kind of MnO provided by the invention2Intermediate, using such as above-mentioned MnO2The preparation method of intermediate is made.
The preparation method of a kind of lithium-rich manganese-based anode material provided by the invention, by such as above-mentioned MnO2Intermediate with
LiOH·H2O, Ni (OH)2And Co3O4(n in molar ratio(LiOH.H2O):n(MnO2):n(Ni(OH)2): n(Co3O4)=1.0-1.5:0.50-
0.55:0.11-0.15:After 0.12-0.14) mixing, the furnace cooling after 700-900 DEG C of calcining.By introducing polyvinyl pyrrole
MnO is prepared in alkanone (PVP) and ethylene glycol (EG), modification2Intermediate, and as manganese source, it can further across solid phase reaction
The lithium-rich manganese-based anode material with good crystallinity is prepared.The addition of PVP and EG will not change lithium-rich manganese base material
Crystal structure, there are obvious porous structures for the second particle of resulting materials, and are distributed with narrower primary particle size.Improvement preparation
Material shows the chemical property being obviously improved, due to uniform nanoscale primary particle can be by shorter Li+
Transmission path significantly increases kinetics of diffusion, and cellular secondary structure can better adapt in cyclic process due to Li+It takes off repeatedly
The lattice distortion of embedding generation, enhancing structure stability.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is T-MnO2The XRD diffracting spectrum of sample；
Fig. 2 is the XRD diffracting spectrum of T-LNCM sample；
Fig. 3 is O-MnO2SEM figure；
Fig. 4 is T-MnO2SEM figure；
The SEM that Fig. 5 is O-LNCM schemes；
The SEM that Fig. 6 is T-LNCM schemes；
Fig. 7 is the first charge-discharge curve of O-LNCM/T-LNCM；
Fig. 8 is the high rate performance figure of O-LNCM/T-LNCM；
The different multiplying that Fig. 9 is O-LNCM/T-LNCM normalizes capacity retention ratio；
Figure 10 is O-LNCM/T-LNCM sample 0.5C circulation life diagram；
Figure 11 is T-LNCM different multiplying cycle life figure；
Figure 12 is differential capacity (dQ/dV) curve graph of O-LNCM/T-LNCM sample；
Figure 13 is the cyclic voltammetry curve figure of O-LNCM；
Figure 14 is the cyclic voltammetry curve figure of T-LNCM；
Figure 15 is the EIS curve that the present invention applies the lithium-rich manganese-based anode material that example provides；
Figure 16 is the fitting of the Zre and ω -1/2 for the low frequency region that the present invention applies the lithium-rich manganese-based anode material that example provides
Linear relationship chart.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
In the description of the present invention, it should be noted that term " first ", " second " etc. are only used for distinguishing description, without
It can be interpreted as indication or suggestion relative importance.
Below to the MnO of the embodiment of the present invention2The preparation of intermediate and preparation method thereof and lithium-rich manganese-based anode material
Method is specifically described.
A kind of MnO provided in an embodiment of the present invention2The preparation method of intermediate, including：
S1, it is stirred until homogeneous after PVP is added into manganese salt solution, obtains the first solution.
Further, manganese salt solution is the mixed solution of manganate and alcohol and deionized water.
Specifically, manganate is dissolved in the mixed solution of deionized water and alcohol.
It should be noted that being according to specific when in the above-mentioned mixed solution that manganate is dissolved in deionized water and alcohol
Solubility of the manganate in deionized water and alcoholic solution selected.
When above-mentioned manganate being dissolved in the mixed solution of deionized water and alcohol, it shall be guaranteed that solute can be completely molten
Solution is in a solvent.
Further, any one of manganate in manganese nitrate, manganese acetate or manganese sulfate.
Above-mentioned manganese nitrate, manganese acetate or manganese sulfate can be dissolved in the mixed solution of deionized water and alcohol.
Further, any one of above-mentioned alcohol in ethylene glycol, glycerine or polyethylene glycol.
Further, when PVP being added into the above-mentioned manganese salt solution prepared, the quality of manganate is PVP mass
4-6 times.
Further, it is also stirred after above-mentioned PVP being added in manganese salt solution, stirs to get the first solution.
Specifically, in the present embodiment, above-mentioned stirring, by the way of magnetic agitation.Optionally, it stirs two hours,
So that PVP is evenly dispersed into manganese salt solution.
S2, by ammonium bicarbonate soln or sodium carbonate liquor and the first solution under agitation hybrid reaction to milky
Precipitating generates.
Specifically, ammonium bicarbonate soln is that ammonium bicarbonate solubility is made in deionized water.Sodium carbonate liquor is by carbon
Sour sodium dissolution is made in deionized water.
It should be understood that the quality of above-mentioned ammonium hydrogen carbonate is true according to the solubility selection of ammonium hydrogen carbonate in deionized water
It is real.The quality of above-mentioned sodium carbonate is certain according to the solubility selection of sodium carbonate in deionized water.
Further, in the present embodiment, by ammonium bicarbonate soln or sodium carbonate liquor and the first solution in stirring bar
Under part mixing be by ammonium bicarbonate soln or sodium carbonate liquor under conditions of continuously stirring, be added in the first solution.
First solution and ammonium bicarbonate soln or sodium carbonate liquor produce milky white precipitate after sufficiently reacting.
Further, milky white precipitate is filtered, after washing, drying.
Specifically, in the present embodiment, drying above-mentioned milky white precipitate is done in vacuum drying box at 80 degrees Celsius
Dry 12 hours.
It should be noted that above-mentioned specific drying time and temperature can be according to the specific ingredients of milky white precipitate
It is specifically chosen.
Further, also to milky white precipitate in 380-420 DEG C of progress heat after being dried to above-mentioned milky white precipitate
Processing.
Specifically, in the present embodiment, above-mentioned milky white precipitate is dried is that sample is placed in air gas
In atmosphere, it is heat-treated.Optionally, 5 hours are handled when being heat-treated to above-mentioned milky white precipitate.
Some embodiments of the present invention also provide a kind of MnO2Intermediate.This MnO2Intermediate is using above-mentioned
MnO2The preparation method of intermediate is made.
Some embodiments of the present invention also provide a kind of preparation method of lithium-rich manganese-based anode material, including following step
Suddenly：
By MnO obtained above2Intermediate and LiOHH2O, Ni (OH)2And Co3O4(n in molar ratio(LiOH.H2O):
n(MnO2):n(Ni(OH)2):n(Co3O4)=1.0-1.5:0.50-0.55:0.11-0.15:After 0.12-0.14) mixing, in 700-900
DEG C calcining after furnace cooling.
Further, to MnO2Intermediate and LiOHH2O, Ni (OH)2And Co3O4It is also ground before calcining.
Specifically, in the present embodiment, by above-mentioned MnO2Intermediate and LiOHH2O, Ni (OH)2And Co3O4Mixing
After object grinds 1.5-3 hours in the ball mill, it is dried in vacuo 10-15 hours.
It should be understood that above-mentioned by MnO2Intermediate and LiOHH2O, Ni (OH)2And Co3O4Mixture grind in the ball mill
When grinding rate can be selected according to the actual situation.Optionally, by above-mentioned MnO2Intermediate and LiOHH2O, Ni
(OH)2And Co3O4Mixture in the ball mill with 200rpm ball milling 2 hours.
Further, by above-mentioned MnO2Intermediate and LiOHH2O, Ni (OH)2And Co3O4Mixture ground in ball mill
After mill 450-550 DEG C pre-burning 4-6 hours.Then it is warming up to 700-900 DEG C of calcining 10-15 hours again, then cools to the furnace
Room temperature to get arrive lithium-rich manganese-based anode material.
Feature and performance of the invention are described in further detail with reference to embodiments：
Embodiment 1
A kind of lithium-rich manganese-based anode material provided in this embodiment is obtained in this way：
1)MnO2Intermediate preparation
2.704g manganese sulfate is dissolved in 80mL deionized water and 20mL ethylene glycol mixed solution, then 0.5g PVP is added
The mixed system magnetic agitation 2 hours, is labeled as solution a；2.530g NH4HCO3It is dissolved in 30mL deionized water, is continuously stirred
Under the conditions of, it is slowly added in solution a, obtains milky white precipitate.Filtering precipitate, after washed, in 80 DEG C of vacuum drying ovens
Middle drying 12 hours, then by gained sample in air atmosphere, 400 DEG C are heat-treated 5 hours to prepare MnO2, it is denoted as T-
MnO2。
2) prepared by lithium-rich manganese-based anode material
By 1) middle gained MnO2With LiOHH2O, Ni (OH)2And Co3O4(n in molar ratio(LiOH.H2O): n(MnO2):
n(Ni(OH)2):n(Co3O4)=1.2:0.54:0.13:0.13) it after mixing, is ground 2 hours in 200rpm ball mill, then 120
DEG C vacuum drying 12 hours, later by mixture at 500 DEG C after pre-burning 5 hours, be warming up to 800 DEG C and calcine 12 hours, then with
Furnace is cooled to room temperature to get to lithium-rich manganese base material, is denoted as T-LNCM.
Embodiment 2
A kind of lithium-rich manganese-based anode material provided in this embodiment is obtained in this way：
1)MnO2Intermediate preparation
4g manganese acetate is dissolved in 100mL deionized water and 30mL glycerine mixed solution, then the mixing is added in 1g PVP
System magnetic agitation 2 hours, is labeled as solution a；5g sodium carbonate is dissolved in 60mL deionized water, will under continuous stirring condition
It is slowly added in solution a, obtains milky white precipitate.Filtering precipitate, after washed, dry 12 is small in 80 DEG C of vacuum drying ovens
When, then by gained sample in air atmosphere, 380 DEG C are heat-treated 5 hours to prepare MnO2, it is denoted as T-MnO2。
2) prepared by lithium-rich manganese-based anode material
By 1) middle gained MnO2With LiOHH2O, Ni (OH)2And Co3O4(n in molar ratio(LiOH.H2O): n(MnO2):
n(Ni(OH)2):n(Co3O4)=1.2:0.54:0.13:0.13) it after mixing, grinds 1.5 hours in 200rpm ball mill, then exists
120 DEG C are dried in vacuo 12 hours, later by mixture at 450 DEG C after pre-burning 5 hours, are warming up to 700 DEG C and calcine 10 hours, then
Room temperature is cooled to the furnace to get to lithium-rich manganese base material, is denoted as T-LNCM.
Embodiment 3
A kind of lithium-rich manganese-based anode material provided in this embodiment is obtained in this way：
1)MnO2Intermediate preparation
6.6g manganese nitrate is dissolved in 120mL deionized water and 40mL ethylene glycol mixed solution, then 1.1 g PVP are added should
Mixed system magnetic agitation 2 hours, is labeled as solution a；2.5g NH4HCO3It is dissolved in 30mL deionized water, continuous stirring condition
Under, it is slowly added in solution a, obtains milky white precipitate.Filtering precipitate after washed, is done in 80 DEG C of vacuum drying ovens
Dry 12 hours, then by gained sample in air atmosphere, 400 DEG C were heat-treated 5 hours to prepare MnO2, it is denoted as T-MnO2。
2) prepared by lithium-rich manganese-based anode material
By 1) middle gained MnO2With LiOHH2O, Ni (OH)2And Co3O4(n in molar ratio(LiOH.H2O): n(MnO2):
n(Ni(OH)2):n(Co3O4)=1.5:0.55:0.15:0.14) it after mixing, is ground 2 hours in 200rpm ball mill, then 120
DEG C vacuum drying 12 hours, later by mixture at 500 DEG C after pre-burning 5 hours, be warming up to 800 DEG C and calcine 12 hours, then with
Furnace is cooled to room temperature to get to lithium-rich manganese base material, is denoted as T-LNCM.
Embodiment 4
A kind of lithium-rich manganese-based anode material provided in this embodiment is obtained in this way：
1)MnO2Intermediate preparation
5.4g manganese sulfate is dissolved in 160mL deionized water and 40mL ethylene glycol mixed solution, then 2.7g PVP is added should
Mixed system magnetic agitation 2 hours, is labeled as solution a；2.530g NH4HCO3It is dissolved in 30mL deionized water, continuously stirs item
Under part, it is slowly added in solution a, obtains milky white precipitate.Filtering precipitate, after washed, in 80 DEG C of vacuum drying ovens
12 hours dry, then by gained sample in air atmosphere, 400 DEG C are heat-treated 5 hours to prepare MnO2, it is denoted as T-MnO2。
2) prepared by lithium-rich manganese-based anode material
By 1) middle gained MnO2With LiOHH2O, Ni (OH)2And Co3O4(n in molar ratio(LiOH.H2O): n(MnO2):
n(Ni(OH)2):n(Co3O4)=1.3:0.52:0.14:0.13) it after mixing, grinds 2.5 hours in 210rpm ball mill, then exists
125 DEG C are dried in vacuo 12 hours, later by mixture at 500 DEG C after pre-burning 5 hours, are warming up to 800 DEG C and calcine 12 hours, then
Room temperature is cooled to the furnace to get to lithium-rich manganese base material, is denoted as T-LNCM.
Comparative example：
Common commercially available MnO2Lithium-rich manganese-based anode material obtained, is denoted as O-MnO2。
Select the common MnO of purchase2(Chengdu Ke Long chemical reagent factory), is counted as：O-MnO2.Preparation method and embodiment 1-4
The method of step 2) lithium-rich manganese-based anode material preparation is identical.Chemical reagent used is AR pure.
Experimental example：
1, the lithium-rich manganese-based anode material provided the embodiment 1-4 lithium-rich manganese-based anode material provided and comparative example is adopted
Appearance structure is carried out to sample with X-ray diffractometer and carries out phenetic analysis.The result is shown in Figure 1-Fig. 2.
Fig. 1 is T-MnO2The XRD diffracting spectrum of sample；Fig. 2 is the XRD diffracting spectrum of T-LNCM sample.For T-MnO2
Crystal structure, diffraction maximum and tetragonal crystal system MnO2Normal data match, illustrate by precipitating and heat treatment process, at
Function has prepared required MnO2Material.And T-LNCM sample except the weak diffraction maximum between 20o-25o be superlattice structure feature with
Outside, remaining all diffraction maximum can be with α-NaFeO2Structure is corresponding, in addition to this two classes peak, does not observe other impurities phase,
Illustrate resulting materials purity with higher.(006)/(012), (018)/(110) significantly division peak show its well-crystallized
Layer structure.By calculating, the I of T-LNCM sample(003)/I(104)Diffraction peak intensity ratio is 1.47, and it is lower to illustrate that material has
Cationic mixing degree further proves to be based on MnO2The organic matter auxiliary preparation lithium-rich manganese base material crystal of intermediate possesses well
Crystallinity and the degree of order.
2, the lithium-rich manganese-based anode material provided the embodiment 1-4 lithium-rich manganese-based anode material provided and comparative example is adopted
Appearance structure is carried out to sample with field emission scanning electron microscope and carries out phenetic analysis.As a result see Fig. 3-Fig. 6.
Fig. 3-Fig. 6 is respectively O-MnO2、T-MnO2, O-LNCM and T-LNCM SEM figure.O-MnO2Assembled by primary particle
At not of uniform size, the random second particle of pattern, average grain diameter is about 480nm；And obtained by precipitating and heat treatment process
T-MnO2Microscopic appearance be uniform micron ball, about 5 μm of average diameter, results of grain size analysis is shown, average grain diameter is about
357nm, and compare O-MnO2With narrower particle diameter distribution.Boundary between O-LNCM primary particle is not obvious and reunites
Seriously, grain size distribution is within the scope of one biggish (about 250nm~1um)；A crystallite dimension ratio of T-LNCM
It is more uniform, 300nm or so is concentrated on, the reunion between particle is less, and (Fig. 6 wire is shown it is observed that apparent hole exists
Out).It can thus be seen that the difference of manganese source pattern, produces the pattern of lithium-rich manganese-based anode material and significantly affects.
3, the lithium-rich manganese-based anode material that the embodiment 1-4 lithium-rich manganese-based anode material provided and comparative example are provided
Electrochemistry can be carried out test.As a result see Fig. 7-Fig. 8.
Sample assembly is subjected to electrochemical property test at R2032 button cell, concrete operations are as follows：By 85wt.%'s
Sample is prepared, the acetylene black of 10wt.% and the PVDF bonding agent of 5wt.% are put and be sufficiently mixed in the agate mortar, then by the slurry
Material, which is coated on aluminium foil, prepares electrode slice, and standing and drying is finally punched into the positive disk that diameter is 14mm.By electrode slice 150
DEG C vacuum drying 12 hours after carry out button cell assembling.Using the LiPF of 1.0mol/L6(VEC:VDMC=1:It 1) is electrolysis
Liquid, Celgard 2400 are diaphragm, and metal lithium sheet is cathode, are being free of H2O and O2The argon atmosphere gloves of (being lower than 0.1ppm)
Battery assembly is carried out in case.Button cell constant current charge-discharge is carried out using new prestige CT-3008 type full-automatic battery controlled testing instrument
It tests (voltage range 2.0-4.8V).Cyclic voltammetric (Cyclic is carried out using the CHI660E of Shanghai Chen Hua company production
Voltammetry, CV) it tests, voltage range range 2.0-5V sweeps fast 0.2mV/s.Electrochemical impedance is carried out using CHI660E
Compose (Electrochemical Impedance Spectroscopy, EIS) test, amplitude 5mV, frequency 105~10- 2Hz。
Fig. 7-Fig. 9 is respectively first charge-discharge curve, high rate performance figure and the different multiplying normalization of O-LNCM/T-LNCM
Capacity retention ratio.As seen from Figure 7, for charging process, it can be seen that two significantly correspond to the area of different electrochemical reactions
Domain.The charging slope below 4.5V corresponds to stratified material and typically takes off lithium reaction：Lithium ion is from LiMO2Middle abjection, along with
Ni2+/Co3+The process aoxidized to high-valence state, Li2MnO3It is electrochemicaUy inert in this voltage range；Occur when 4.5V voltage special
It levies charging platform and corresponds to Li2MnO3The activation process of component.O-LNCM sample specific discharge capacity is 222 mAhg-1, can not
Inverse specific capacity loss is 69mAhg-1, corresponding to 76.3% coulombic efficiency；T-LNCM sample specific discharge capacity is
283mAh·g-1, irreversible specific capacity loss is 48mAhg-1, corresponding to 85.5% coulombic efficiency.Reversible discharge specific capacity
Related with the homogenization of T-LNCM sample primary particle with the raising of coulombic efficiency supposition, particle diameter distribution more evenly is conducive to
The transmission of lithium ion reduces the activation polarization of lithium ion deintercalation process, improves efficiency for charge-discharge.Multi-hole secondary structure provides
Additional storage Li+Active site, further increase reversible specific capacity.
Figure 10 is O-LNCM/T-LNCM sample 0.5C circulation life diagram；Figure 11 is that T-LNCM different multiplying recycles the longevity
Life figure；Figure 12 is differential capacity (dQ/dV) curve graph of O-LNCM/T-LNCM sample.All material is in advance in 2-4.8V electricity
Pressure is with 25mAg-1Low current density under 3 periods of charge and discharge to ensure sufficiently to activate.As shown in Figure 10, O-LNCM sample follows
Specific capacity after ring 50 weeks is 160mAhg-1, to recycle initial capacity (180mAhg-1) 88.9%, T-LNCM cycles samples
Specific capacity after 50 weeks is 205mAhg-1, to recycle initial capacity (226 mAhg-1) 90.7%.As can be seen that compared to O-
LNCM sample while T-LNCM sample shows higher specific discharge capacity, also possesses higher circulation volume conservation rate.And scheme
11 further compared cyclical stability of the T-LNCM sample at 0.5C, 1C and 2C multiplying power, and the increase of current density is not
Have and the capacity retention ratio generation of material is significantly affected, even if capacitance loss rate is also only 11.2%, relatively under 2C high magnification
Stable average discharge volt also indicates that T-LNCM sample equally has good structural stability even if compared under high magnification.
As shown in Figure 12, all curves can show the reduction process of transition metal ions, carefully comparison discovery, near 3.75V
Peak corresponds to Co4+And Ni4+Reduction, current potential hardly follows the increase of cycle-index and moves, and only intensity is subtracted
It is small, structurally, due to combine bond energy difference, the transition process of different transition metal is simultaneously uneven, cause part from
Son is assembled or is thickened in the material, and electro-chemical activity is lost during iterative cycles, and the stabilization of reduction potential is attributable to
The homogenization of primary particle is conducive to reduce the activation polarization of lithium ion deintercalation, stabilizes Co4+And Ni4+Equilibrium potential,
Improve the electrochemical reversibility of its oxidation-reduction pair.While the reduction peak peak intensity of 3.2V or so Mn weakens, spike potential by
Step is negative to move, and in addition to activation polarization process, main cause is tetrahedron of the metal ion from TM layers of octahedral sites to Li layer
The migration in site, the transformation corresponding to material from layer structure to spinel structure.Although this phase transition process belongs to rich lithium manganese material
Intrinsic structure feature is expected, but for T-LNCM sample, even if the reduction potential of Mn is still at 2C high rate cyclic 50 times
Higher than 3V, show that its irreversible phase transition course is suppressed significantly.Generally speaking, T-LNCM sample possesses the more of uniform grading distribution
Pore structure not only improves electrochemical process invertibity by the good contact provided between electrolyte and internal particle, together
Even if when at higher current densities, be still adapted to Li+Quick deintercalation and diffusion, and keep stratiform structural stability, have
Effect alleviates the voltage attenuation as caused by stratiform to spinel structure transformation during circulation.
The respectively cyclic voltammetry curve figure of O-LNCM and T-LNCM of Figure 13,14.In first week CV curve, the oxygen of 4.0V
Change peak and corresponds to Ni2+/Ni4+And Co3+/Co4+Oxidation, and second sharp oxidation peak near 4.7V is attributed to
Li2MnO3Li in component2The net abjection of O component, and the oxidation peak is almost vanished from sight in subsequent circulation, also demonstrates this
Really irreversible oxidation process.In addition, three cathode peaks correspond respectively to the reduction of Co, Ni and Mn.And second and third week bent
Line close to being overlapped, illustrates except Li2MnO3Outside activation of component, remaining reaction is reversible.Although the CV curve peak of two kinds of samples
Shape is similar, but the week activation peak head of T-LNCM sample and the responsive current density at subsequent reversible oxidation peak are all larger than O-LNCM
Sample shows that the material is more fully activated during initial charge and reversibly takes part in subsequent reactions, provides more
High specific discharge capacity, this is consistent with the test result in Fig. 7-9.
Figure 15 and Figure 16 is respectively the EIS curve of resulting materials and the Z of low frequency regionreAnd ω-1/2Fit linear relationship
Figure.Circulation carries out after recycling with 50 times for the first time under 0.5C multiplying power respectively for the test of EIS, charges to sample before test
4.5V.EIS fitting map and equivalent-circuit model, EIS matched curve and real axis are shown in Figure 15 in the intersection point generation of high frequency region
The Ohmic resistance (Rs) of table lithium-ion battery systems, the lithium ion mobility resistance on the semicircle and SEI film of high-frequency range
(Rsf) related, the charge transfer resistance (R occurred on the semicircle and solid/electrolyte interface of intermediate frequency rangect) related, in low frequency
In range, line of collimation is attributed to Li in volume electrode+The Warburg impedance of diffusion.Slope of a curve in Figure 16 can be used to come
Calculate Warburg coefficient (σω), according to equation:DLi +=R2T2/2n4 F4A2C2σω 2(R:Ideal gas constant；T:Absolute temperature；
n:The electron number (being 1 for the reaction) of per molecule during charge/discharge；F:Faraday constant；C:Li in electrode+Concentration；A:
Electrode surface area), the electrochemical diffusion coefficient of lithium ion can be calculated, fitting impedance parameter is listed in table 1.As seen from the table, no matter
After recycling or recycling for the first time for 50 times, T-LNCM sample all has lower R compared with O-LNCM samplesfAnd RctValue and compared with
High DLi +.Specifically, T-LNCM sample recycle for the first time in lower RsfValue shows that evengranular microstructure inhibits
The growth of SEI film reduces the consumption in the forming process of SEI to Li, to obtain the Initial Coulombic for being higher than O-LNCM sample
Efficiency.And T-LNCM sample porous structure feature is conducive to the reduction of Charge-transfer resistance and the quick diffusion of lithium ion, assigns
The more excellent chemical property of material, it is consistent with aforementioned high rate performance and cycle performance test result that EIS analyzes result.
The EIS fitting data of 1 resulting materials of table
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of MnO2The preparation method of intermediate, which is characterized in that include the following steps：
It is stirred until homogeneous after PVP is added into manganese salt solution, obtains the first solution；
By ammonium bicarbonate soln or sodium carbonate liquor, hybrid reaction to milky is sunk under agitation with first solution
It forms sediment and generates；
Wherein, the manganese salt solution is the mixed solution of manganate and alcohol and deionized water.
2. MnO as described in claim 12The preparation method of intermediate, which is characterized in that
Any one of the manganate in manganese nitrate, manganese acetate or manganese sulfate.
3. MnO as described in claim 12The preparation method of intermediate, which is characterized in that
Any one of the alcohol in ethylene glycol, glycerine or polyethylene glycol.
4. MnO as described in any one of claims 1-32The preparation method of intermediate, which is characterized in that
Also the milky white precipitate is heat-treated at 380-420 DEG C.
5. MnO as claimed in claim 42The preparation method of intermediate, which is characterized in that
It is also dried before being heat-treated to the milky white precipitate at 380-420 DEG C.
6. MnO as claimed in claim 42The preparation method of intermediate, which is characterized in that
The quality of the manganate is 4-6 times of the quality of the PVP.
7. a kind of MnO2Intermediate, which is characterized in that use MnO as claimed in any one of claims 1 to 62The preparation of intermediate
Method is made.
8. a kind of preparation method of lithium-rich manganese-based anode material, which is characterized in that include the following steps：
By MnO as claimed in claim 72Intermediate and LiOHH2O, Ni (OH)2And Co3O4(n in molar ratio(LiOH.H2O):
n(MnO2):n(Ni(OH)2):n(Co3O4)=1.0-1.5:0.50-0.55:0.11-0.15:After 0.12-0.14) mixing, in 700-900
DEG C calcining after furnace cooling.
9. the preparation method of lithium-rich manganese-based anode material as claimed in claim 8, which is characterized in that
To the MnO2Intermediate and the LiOHH2O, the Ni (OH)2With the Co3O4It is also ground before calcining.
10. the preparation method of lithium-rich manganese-based anode material as claimed in claim 8, which is characterized in that
700-900 DEG C calcining before also 450-550 DEG C pre-burning 4-6 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810660336.9A CN108832118A (en) | 2018-06-25 | 2018-06-25 | MnO2The preparation method of intermediate and preparation method thereof and lithium-rich manganese-based anode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810660336.9A CN108832118A (en) | 2018-06-25 | 2018-06-25 | MnO2The preparation method of intermediate and preparation method thereof and lithium-rich manganese-based anode material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108832118A true CN108832118A (en) | 2018-11-16 |
Family
ID=64137659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810660336.9A Pending CN108832118A (en) | 2018-06-25 | 2018-06-25 | MnO2The preparation method of intermediate and preparation method thereof and lithium-rich manganese-based anode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108832118A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111362317A (en) * | 2020-02-24 | 2020-07-03 | 西南交通大学 | LiNi0.6Co0.2Mn0.2O2Preparation method of (1) |
| CN113433464A (en) * | 2021-06-28 | 2021-09-24 | 中国科学院电工研究所 | High-order model parameter identification method and system suitable for lithium-rich manganese-based battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103811190A (en) * | 2014-01-16 | 2014-05-21 | 天津大学 | Antimony-doped tin dioxide coated porous manganese dioxide composite electrode material and preparation |
| CN106564967A (en) * | 2016-10-31 | 2017-04-19 | 安泰科技股份有限公司 | Lithium-rich manganese-based cathode material precursor, cathode material and preparation method thereof |
| CN108054371A (en) * | 2017-12-21 | 2018-05-18 | 哈尔滨工业大学 | A kind of high-tap density, high magnification and long-life lithium-rich manganese-based anode material and preparation method thereof |
| CN108172803A (en) * | 2017-12-30 | 2018-06-15 | 国联汽车动力电池研究院有限责任公司 | Cladded type richness lithium material that a kind of surface is modified and preparation method thereof and lithium ion battery |
-
2018
- 2018-06-25 CN CN201810660336.9A patent/CN108832118A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103811190A (en) * | 2014-01-16 | 2014-05-21 | 天津大学 | Antimony-doped tin dioxide coated porous manganese dioxide composite electrode material and preparation |
| CN106564967A (en) * | 2016-10-31 | 2017-04-19 | 安泰科技股份有限公司 | Lithium-rich manganese-based cathode material precursor, cathode material and preparation method thereof |
| CN108054371A (en) * | 2017-12-21 | 2018-05-18 | 哈尔滨工业大学 | A kind of high-tap density, high magnification and long-life lithium-rich manganese-based anode material and preparation method thereof |
| CN108172803A (en) * | 2017-12-30 | 2018-06-15 | 国联汽车动力电池研究院有限责任公司 | Cladded type richness lithium material that a kind of surface is modified and preparation method thereof and lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| XINGDE XIANG等: ""Preparation and characterization of size-uniform Li[Li0.131Ni0.304Mn0.565] O2 particles as cathode materials for high energy lithium ion battery"", 《JOURNAL OF POWER SOURCES》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111362317A (en) * | 2020-02-24 | 2020-07-03 | 西南交通大学 | LiNi0.6Co0.2Mn0.2O2Preparation method of (1) |
| CN111362317B (en) * | 2020-02-24 | 2021-02-02 | 西南交通大学 | LiNi0.6Co0.2Mn0.2O2Preparation method of (1) |
| CN113433464A (en) * | 2021-06-28 | 2021-09-24 | 中国科学院电工研究所 | High-order model parameter identification method and system suitable for lithium-rich manganese-based battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | The role of yttrium content in improving electrochemical performance of layered lithium-rich cathode materials for Li-ion batteries | |
| CN103441265B (en) | Rich lithium composite positive pole of a kind of codope and preparation method thereof | |
| CN106340638B (en) | A kind of high-rate lithium-rich manganese-based anode material of double layer hollow structure and preparation method thereof | |
| CN107910529A (en) | A kind of ternary cathode material of lithium ion battery of manganese Base Metal organic frame compound cladding and preparation method thereof | |
| CN107591519A (en) | Modified lithium nickel cobalt manganese positive electrode material and preparation method thereof | |
| CN107215900A (en) | A kind of method in lithium-rich manganese-based anode material oberbau spinel structure | |
| CN104485452A (en) | High-temperature type lithium manganate anode material for power lithium ion battery and preparation method of high-temperature type lithium manganate anode material | |
| CN106784790B (en) | A kind of preparation method of nickle cobalt lithium manganate tertiary cathode material | |
| CN106784655A (en) | A kind of coating modification method for improving lithium-rich manganese-based anode material performance | |
| Liang et al. | Synthesis and characterization of LiNi0. 6CoxMn0. 4-xO2 (x= 0.05, 0.1, 0.15, 0.2, 0.25 and 0.3) with high-electrochemical performance for lithium-ion batteries | |
| CN114005978B (en) | Cobalt-free cathode material and preparation method and application thereof | |
| CN105552360A (en) | Modified lithium nickel cobalt manganese oxide cathode material and preparation method thereof | |
| CN106450217A (en) | Modification method of lithium nickelate, cobaltate and manganate ternary material | |
| CN109301207A (en) | A kind of surface layer doping Ce3+And surface layer coats CeO2NCM tertiary cathode material and preparation method thereof | |
| CN111106331A (en) | Layered-spinel phase composite positive electrode material and preparation method thereof | |
| Gao et al. | Synthesis and electrochemical performance of long lifespan Li-rich Li1+ x (Ni0. 37Mn0. 63) 1− xO2 cathode materials for lithium-ion batteries | |
| CN105870438A (en) | Lithium secondary battery lithium-rich cathode composite and preparation method thereof | |
| CN109560265A (en) | A kind of effective method for coating for inhibiting lithium-rich manganese-based anode material oxygen to be lost | |
| CN105470454A (en) | Modified lithium ion battery positive electrode material and preparation method therefor | |
| CN106711439A (en) | Preparation method of Mg and Ti composite doped lithium-rich manganese based positive electrode material | |
| CN109786734A (en) | A kind of preparation method of the nickelic positive electrode of lithium secondary battery | |
| CN109713260A (en) | A kind of method of modifying of Phosphate coating lithium-rich manganese-based anode material | |
| Jiang et al. | A design strategy of large grain lithium-rich layered oxides for lithium-ion batteries cathode | |
| CN103311540A (en) | Lithium ion battery anode material and preparation method thereof | |
| Huang et al. | Effect of sintering temperature on the electrochemical performance of Li-rich Mn-basfed cathode material Li1. 2Mn0. 54Ni0. 13Co0. 13O2 by co-precipitation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181116 |