CN107768664A - A kind of lithium-rich manganese-based anode material of molybdenum doping and preparation method thereof - Google Patents
A kind of lithium-rich manganese-based anode material of molybdenum doping and preparation method thereof Download PDFInfo
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- CN107768664A CN107768664A CN201710992179.7A CN201710992179A CN107768664A CN 107768664 A CN107768664 A CN 107768664A CN 201710992179 A CN201710992179 A CN 201710992179A CN 107768664 A CN107768664 A CN 107768664A
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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
- H01M4/50—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
- 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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- 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 provides a kind of lithium-rich manganese-based anode material of molybdenum doping, has chemical formula shown in Formulas I：Li1.2Mn0.54‑xMoxCo0.13Ni0.13O2Formulas I；Wherein, 0.05≤x≤0.1.The present invention is substituted with metal cation Mo to the manganese ion in the lithium-rich manganese base material of stratiform, realize to the bulk phase-doped of stratiform lithium-rich manganese base material, the lithium-rich manganese-based anode material Stability Analysis of Structures of molybdenum doping in the present invention, can voltage attenuation and capacity attenuation in cyclic process processed.Present invention also offers a kind of preparation method of the lithium-rich manganese-based anode material of molybdenum doping, the present invention is prepared using sol-gal process, obtained stratiform lithium-rich manganese-based anode material structural stability, so as to improve cycle performance and suppress pressure drop caused by cyclic process.
Description
Technical field
The invention belongs to technical field of lithium-ion battery, more particularly to a kind of lithium-rich manganese-based anode material of molybdenum doping
And preparation method thereof.
Background technology
With social development, facing mankind two large problems are environmental pollution and energy crisis.Human social development be unable to do without
The non-renewable energy resources such as coal, oil, natural gas, but these resources always have one day and are depleted.In being so that human development
New energy technology and form with development, the service efficiency of the energy is improved, such as, solar energy, geothermal energy and wind energy etc..But this
There is region and discontinuity in a little new energy technologies, limit its use.Therefore, it is necessary to develop corresponding energy storage device,
The sustainable supply energy can really be realized to reach the energy use demand of the mankind.
Lithium ion battery occurs bringing hope to new energy sustainable utilization, because it has output cell voltage, energy
Density is high, memory-less effect, has extended cycle life, and self discharge is small, many-sided advantage such as has a safety feature.Lithium ion battery is included just
Pole material, electrolyte, barrier film and negative material.Positive electrode is straight as one of lithium ion battery critical material, its performance quality
Connect the quality for being related to battery performance.Compared with negative material, the specific capacity of positive electrode is than relatively low, such as stratiform LiCoO2
And ternary material, spinel structure LiMn2O4With olivine-type structure LiFePO4Specific capacity Deng positive electrode be all
Below 200mAh/g, it is serious to hinder lithium ion battery to obtain high-energy-density, hinder it further to develop.However, stratiform richness lithium
Material, which has, exceedes 250mAh/g capacity, and cheap, environment-friendly, raw material sources enrich, suitable large-scale industry
Production.Regrettably there is poor high rate performance in stratiform richness lithium material, and producing voltage in poor cycle performance and cyclic process declines
Subtract, seriously hinder it further to develop.
The content of the invention
It is an object of the invention to provide a kind of lithium-rich manganese-based anode material of molybdenum doping and preparation method thereof, in the present invention
The lithium-rich manganese-based anode material Stability Analysis of Structures of molybdenum doping, good cycle and can effectively suppress to press caused by cyclic process
Drop.
The present invention provides a kind of lithium-rich manganese-based anode material of molybdenum doping, has chemical formula shown in Formulas I：
Li1.2Mn0.54-xMoxCo0.13Ni0.13O2Formulas I；
Wherein, 0.05≤x≤0.5.
The present invention provides a kind of preparation method of the lithium-rich manganese-based anode material of molybdenum doping, comprises the following steps：
A) lithium source, nickel source, cobalt source and manganese source are dissolved in the water according to the mol ratio in Formulas I chemical formula, obtain mixing gold
Belong to salting liquid；
B organic acid and molybdenum source) are added into the step A successively) in mixed salt solution in, obtain mixed solution；
C) be evaporated the step B) in mixed solution in moisture, obtain gelatinous mass, the gelatinous mass carried out
Dry, obtain intermediate；
D) by the step C) in intermediate sintered 5~8 hours at 450~600 DEG C, then at 750~950 DEG C
Insulation 10~24 hours, obtains the lithium-rich manganese-based anode material with the molybdenum doping of Formulas I chemical formula；
Li1.2Mn0.54-xMoxCo0.13Ni0.13O2Formulas I；
Wherein, 0.05≤x≤0.5.
Preferably, the lithium source is lithium hydroxide, the one or more in lithium carbonate and lithium acetate；
Nickel source is nickel nitrate, the one or more in nickel sulfate and nickel acetate；
Cobalt source is cobalt nitrate, the one or more in cobaltous sulfate and cobalt acetate；
Manganese source is manganese nitrate, the one or more in manganese sulfate and manganese acetate.
Preferably, the concentration of the mixed salt solution is 0.1~3mol/L.
Preferably, the organic acid is the one or more in citric acid, tartaric acid and glycine；
The mol ratio of the organic acid and all transition metal ions in mixed solution is (1~3)：1.
Preferably, the molybdenum source is the one or more in sodium molybdate, molybdenum acid ammonia and potassium molybdate.
Preferably, the step C) in the temperature that is evaporated be 80~120 DEG C；
The step C) in time for being evaporated be 10~15 hours.
Preferably, the step C) in dry temperature be 100~150 DEG C；
The step C) in dry time be 10~15 hours.
Preferably, the step C) in sintering detailed process be：
By the step B) in intermediate rise to 450~600 DEG C from room temperature with 1~5 DEG C/min speed, sintering 5~8
Hour；Then 750~900 DEG C are being risen to 1~5 DEG C/min speed, is being incubated 10~24 hours, obtains with Formulas I chemical formula
Molybdenum doping lithium-rich manganese-based anode material.
The invention provides a kind of lithium-rich manganese-based anode material of molybdenum doping, has chemical formula shown in Formulas I：Li1.2Mn0.54- xMoxCo0.13Ni0.13O2Formulas I；Wherein, 0.05≤x≤0.5.Lithium-rich manganese base material of the present invention with metal cation Mo to stratiform
In manganese ion substituted, realize to the bulk phase-doped of stratiform lithium-rich manganese base material, the rich lithium manganese of the molybdenum doping in the present invention
Base anode material Stability Analysis of Structures, can voltage attenuation and capacity attenuation in cyclic process processed.
Present invention also offers a kind of preparation method of the lithium-rich manganese-based anode material of molybdenum doping, the present invention is coagulated using colloidal sol
Prepared by glue method, obtained stratiform lithium-rich manganese-based anode material structural stability, so as to improve cycle performance and suppress cyclic process
Caused pressure drop.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
The embodiment of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis
The accompanying drawing of offer obtains other accompanying drawings.
Fig. 1 is that the modified layered lithium-rich manganese-based anode material of molybdenum doping and pure phase stratiform are lithium-rich manganese-based in the embodiment of the present invention 1
The XRD of positive electrode；
Fig. 2 is molybdenum (Mo) doping vario-property stratiform lithium-rich manganese-based anode material in the embodiment of the present invention 1
(Li1.2Mn0.49Mo0.05Co0.13Ni0.13O2) SEM figure；
Fig. 3 is the SEM figures of pure phase stratiform lithium-rich manganese-based anode material in the embodiment of the present invention 1；
Fig. 4 is the laminate lithium-rich manganese-based anode material of the embodiment of the present invention 1 through the cyclic curve before and after molybdenum doping；
Fig. 5 is with experiment made of molybdenum (Mo) doping vario-property stratiform lithium-rich manganese-based anode material in the embodiment of the present invention 1
Charging and discharging curve of the battery in 100 circle cyclic processes；
Fig. 6 is that experimental cell made of pure phase stratiform lithium-rich manganese-based anode material circulates in 100 circles in the embodiment of the present invention 1
During charging and discharging curve.
Embodiment
The invention provides a kind of lithium-rich manganese-based anode material of molybdenum doping, has chemical formula shown in Formulas I：
Li1.2Mn0.54-xMoxCo0.13Ni0.13O2Formulas I；
Wherein, 0.05≤x≤0.5.
In the present invention, the x can be 0.05,0.1,0.25,0.3 or 0.5.The positive pole material with Formulas I structure
Expect for the bulk phase-doped stratiform lithium-rich manganese-based anode material of molybdenum.
Present invention also offers a kind of preparation method of the lithium-rich manganese-based anode material of molybdenum doping, comprise the following steps：
A) lithium source, nickel source, cobalt source and manganese source are dissolved in the water according to the mol ratio in Formulas I chemical formula, obtain mixing gold
Belong to salting liquid；
B organic acid and molybdenum source) are added into the step A successively) in mixed salt solution in, obtain mixed solution；
C) be evaporated the step B) in mixed solution in moisture, obtain gelatinous mass, the gelatinous mass carried out
Dry, obtain intermediate；
D) by the step C) in intermediate sintered 5~8 hours at 450~600 DEG C, then at 750~950 DEG C
Insulation 10~24 hours, obtains the lithium-rich manganese-based anode material with the molybdenum doping of Formulas I chemical formula；
Li1.2Mn0.54-xMoxCo0.13Ni0.13O2Formulas I；
Wherein, 0.05≤x≤0.5.
The present invention is preferably by lithium source, manganese source, cobalt source and nickel source according to the mol ratio (i.e. 1.2 in Formulas I chemical formula:0.54:
0.13:0.13) it is dissolved in respectively in deionized water, then respective solution is mixed again, obtains mixed salt solution.In the present invention
In, the lithium source is lithium hydroxide, the one or more in lithium carbonate and lithium acetate；Nickel source is nickel nitrate, nickel sulfate and acetic acid
One or more in nickel；Cobalt source is cobalt nitrate, the one or more in cobaltous sulfate and cobalt acetate；Manganese source is manganese nitrate, sulfuric acid
One or more in manganese and manganese acetate.In the mixed salt solution concentration of all metal ions be preferably 0.1~
3mol/L, more preferably 0.5~2.5mol/L, most preferably 1~2mol/L.Wherein, the concentration of the solution of lithium source is preferably 0.1
~3mol/L, more preferably 0.5~2.5mol/L, most preferably 1~2mol/L；The concentration of the solution of manganese source is preferably 0.1~
3mol/L, more preferably 0.5~2.5mol/L, most preferably 1~2mol/L；The concentration of the solution of cobalt source is preferably 0.1~
3mol/L, more preferably 0.5~2.5mol/L, most preferably 1~2mol/L；The concentration of the solution of nickel source is preferably 0.1~
3mol/L, more preferably 0.5~2.5mol/L, most preferably 1~2mol/L.
The present invention preferably first adds organic acid in above-mentioned mixed salt solution, then according still further to chemical formula shown in Formulas I
In mol ratio molybdenum source is added thereto, be stirred 1~2 hour, obtain mixed solution.The organic acid is preferably lemon
One or more in acid, tartaric acid and glycine；The organic acid and whole transition metal in the mixed salt solution
Mol ratio be preferably (1~3)：1, more preferably 2:1.The molybdenum source is preferably one in sodium molybdate, molybdenum acid ammonia and potassium molybdate
Kind is a variety of.
In the present invention, the temperature being evaporated is preferably 80~120 DEG C, more preferably 90~110 DEG C, is most preferably
100℃；The time being evaporated is preferably 10~15 hours, more preferably 11~14 hours, most preferably 12~13 hours.This
Invention preferably carries out above-mentioned be evaporated under agitation.After deionized water is all evaporated, gelatinous mass is obtained.
Then above-mentioned gelatinous mass is dried, the temperature of the drying is preferably 100~150 DEG C, more preferably 110
~140 DEG C, most preferably 120~130 DEG C；The time of the drying is preferably 10~15 hours, more preferably 11~14 hours,
Most preferably 12~13 hours.After obtaining dried object, the present invention is carried out ball mill grinding, obtains intermediate.
Above-mentioned intermediate is sintered by the present invention, and the detailed process of the sintering is：
By the step B) in intermediate rise to 450~600 DEG C from room temperature with 1~5 DEG C/min speed, be preferably
500~550 DEG C, sinter 5~8 hours, preferably 6~7 hours；Then 750~900 are being risen to 1~5 DEG C/min speed
DEG C, preferably 800~850 DEG C, 10~24 hours are incubated, preferably 12~20 hours, through natural cooling after sintering, is had
The lithium-rich manganese-based anode material of the molybdenum doping of Formulas I chemical formula.
The invention provides a kind of lithium-rich manganese-based anode material of molybdenum doping, has chemical formula shown in Formulas I：Li1.2Mn0.54- xMoxCo0.13Ni0.13O2Formulas I；Wherein, 0.05≤x≤0.5.Lithium-rich manganese base material of the present invention with metal cation Mo to stratiform
In manganese ion substituted, realize to the bulk phase-doped of stratiform lithium-rich manganese base material, the rich lithium manganese of the molybdenum doping in the present invention
Base anode material Stability Analysis of Structures, can voltage attenuation and capacity attenuation in cyclic process processed.
Present invention also offers a kind of preparation method of the lithium-rich manganese-based anode material of molybdenum doping, the present invention is coagulated using colloidal sol
Prepared by glue method, obtained stratiform lithium-rich manganese-based anode material structural stability, so as to improve cycle performance and suppress cyclic process
Caused pressure drop.
In order to further illustrate the present invention, with reference to embodiments to a kind of the lithium-rich manganese-based of molybdenum doping provided by the invention
Positive electrode and preparation method thereof is described in detail, but can not be understood as limiting the scope of the present invention.
Embodiment 1
It is 1.2 according to mol ratio shown in stratiform lithium-rich manganese-based anode material chemical formula:0.54:0.13:0.13 weighs one
Quantitative lithium salts, nickel salt, bore salt and manganese salt dissolving in deionized water, be configured to the aqueous solution that concentration is 0.1mol/L, and will
Above solution is mixed.
It is 1 according to all transition metal ions in mixed solution and organic acid mol ratio:Citric acid is added to by 1 amount
State in mixed solution.
Ammonium molybdate is added in above-mentioned mixed solution according to the amount that molybdenum doping amount is x=0.05, is stirred 1h.
The mixed solution of above-mentioned acquisition stirs 10h at 80 DEG C, until deionized water is all evaporated, obtains gelatinous mass,
Then it is put into drying box after 100 DEG C of dry 10h, takes out dried object and carry out ball mill crushing.
Broken powder body material is finally raised to 450 DEG C of sintering 8h in air atmosphere with 1 DEG C/min from 25 DEG C, then existed again
750 DEG C of insulation 24h are raised to 1 DEG C/min in air atmosphere, room temperature is naturally cooled to and obtains molybdenum (Mo) doping vario-property stratiform richness lithium
Manganese-based anode material (Li1.2Mn0.49Mo0.05Co0.13Ni0.13O2)。
To molybdenum (Mo) doping vario-property stratiform lithium-rich manganese-based anode material of the gained of embodiment 1
(Li1.2Mn0.49Mo0.05Co0.13Ni0.13O2) divide with the pure phase stratiform lithium-rich manganese-based anode material progress XRD obtained by embodiment 1
Analysis and sem analysis.As shown in Figures 1 to 3, Fig. 1 is the modified layered lithium-rich manganese-based anode material of (A) molybdenum doping in the embodiment of the present invention 1
The XRD of material and (B) pure phase stratiform lithium-rich manganese-based anode material.As known to XRD, stratiform richness lithium manganese after molybdenum (Mo) doping vario-property
Base anode material is consistent with stratiform richness lithium material diffraction maximum before modified, and it is lithium-rich manganese-based just to illustrate that molybdenum (Mo) doping does not change stratiform
Pole material phase structure.Fig. 2 is molybdenum (Mo) doping vario-property stratiform lithium-rich manganese-based anode material in the embodiment of the present invention 1
(Li1.2Mn0.49Mo0.05Co0.13Ni0.13O2) SEM figure, Fig. 3 be the embodiment of the present invention 1 in pure phase stratiform lithium-rich manganese-based anode material
The SEM figures of material.Contrasted from Fig. 2 and Fig. 3, after molybdenum (Mo) doping, the microstructure of material does not change.
By embodiment 1 according to 8：1：1 ratio is by the molybdenum prepared (Mo) doping vario-property stratiform lithium-rich manganese-based anode material
(Li1.2Mn0.49Mo0.05Co0.13Ni0.13O2), conductive black SuperP, binding agent PVDF add N- methyl arsenic pyrrolidones stirred
Mixing is mixed, then the slurry of gained is dried 12 hours at 120 DEG C coated on aluminium foil and obtains positive plate.Full of argon gas
Battery assembling is carried out in glove box, negative pole is metal lithium sheet, and barrier film is polypropylene, LiPF6For electrolyte.Gained is implemented into battery
Charge-discharge test is carried out in the case where multiplying power is 1C multiplying powers, the cyclic curve of gained is as shown in Figure 4.Fig. 4 is the middle level of the embodiment of the present invention 1
Shape lithium-rich manganese-based anode material is through the cyclic curve before and after molybdenum doping.
A and B is the cyclic curve of molybdenum (Mo) doping vario-property and pure stratiform richness lithium material made from embodiment 1 respectively in Fig. 4.
From Fig. 4 A, the stratiform richness lithium material first discharge specific capacity of molybdenum (Mo) doping vario-property as made from embodiment 1 is
183.2mAh/g, capability retention reaches 98.3% after 100 circulations, but pure stratiform richness lithium material follows by 100 times
Capability retention only has 45% after ring.By being contrasted between Fig. 5 and Fig. 6 it can be seen that molybdenum (Mo) doping can effectively suppress to circulate
During voltage attenuation.From result above, using material circulation stability can be effectively improved after molybdenum (Mo) doping vario-property,
And stabilizing material structure suppresses voltage attenuation.
Embodiment 2
According to mol ratio shown in stratiform lithium-rich manganese-based anode material chemical formula weigh a certain amount of lithium salts, nickel salt, bore salt and
Manganese salt, which dissolves, in deionized water, is configured to the aqueous solution of the concentration for 1.5mol/L, and above solution is mixed.
It is 1 according to all transition metal ions in mixed solution and organic acid mol ratio：Tartaric acid is added to by 1.5 amount
In above-mentioned mixed solution.
Sodium molybdate is added in above-mentioned mixed solution according to the amount that molybdenum doping amount is x=0.1, is stirred 1.5h.
The mixed solution of above-mentioned acquisition stirs 12h at 90 DEG C, until deionized water is all evaporated, obtains gelatinous mass,
Then it is put into drying box after 120 DEG C of dry 11h, takes out dried object and carry out ball mill crushing.
Broken powder body material is finally raised to 500 DEG C of sintering 6h in air atmosphere with 2 DEG C/min from 25 DEG C, then existed again
800 DEG C of insulation 12h are raised to 2 DEG C/min in air atmosphere, room temperature is naturally cooled to and obtains molybdenum (Mo) doping vario-property stratiform richness lithium
Manganese-based anode material (Li1.2Mn0.44Mo0.1Co0.13Ni0.13O2)。
Chemical property analysis is carried out to molybdenum (Mo) the doping vario-property stratiform lithium-rich manganese-based anode material of the gained of embodiment 2：
Weigh 0.8g molybdenums (Mo) doping vario-property stratiform lithium-rich manganese-based anode material (Li1.2Mn0.44Mo0.1Co0.13Ni0.13O2), 0.05g second
Acetylene black and 0.05gPVDF, 0.4g NMP dispersion mixings are added, gained slurry is coated on aluminium foil, in anaerobism glove box after drying
In using metal lithium sheet as to electrode, be assembled into CR2025 button cells.At 25 DEG C, 1C multiplying powers are carried out 100 times between 2-4.8V
Charge and discharge cycles are tested, the results showed that molybdenum (Mo) doping vario-property stratiform lithium-rich manganese-based anode material (Li1.2Mn0.54- xMoxCo0.13Ni0.13O2) there is high specific capacity, stable circulation, and can effectively suppress material structure change generation voltage and decline
Subtract, show excellent electrochemical performance.
Embodiment 3
According to mol ratio shown in stratiform lithium-rich manganese-based anode material chemical formula weigh a certain amount of lithium salts, nickel salt, bore salt and
Manganese salt, which dissolves, in deionized water, is configured to the aqueous solution of the concentration for 1.5mol/L, and above solution is mixed.
It is 1 according to all transition metal ions in mixed solution and organic acid mol ratio：Glycine is added to by 2 amount
State in mixed solution.
Molybdic acid sodium source is added in above-mentioned mixed solution according to the amount that molybdenum doping amount is x=0.25, is stirred 1.5h.
The mixed solution of above-mentioned acquisition stirs 13h at 100 DEG C, until deionized water is all evaporated, obtains gelatinous mass,
Then it is put into drying box after 125 DEG C of dry 13h, takes out dried object and carry out ball mill crushing.
Broken powder body material is finally raised to 525 DEG C of sintering 5-8h, Ran Houzai in air atmosphere with 3 DEG C/min from 25 DEG C
850 DEG C of insulation 17h are raised to 3 DEG C/min in air atmosphere, room temperature is naturally cooled to and obtains molybdenum (Mo) doping vario-property stratiform richness
Lithium manganese-based anode material (Li1.2Mn0.29Mo0.25Co0.13Ni0.13O2)。
Chemical property analysis is carried out to molybdenum (Mo) the doping vario-property stratiform lithium-rich manganese-based anode material of the gained of embodiment 3：
Weigh 0.8g molybdenums (Mo) doping vario-property stratiform lithium-rich manganese-based anode material (Li1.2Mn0.29Mo0.25Co0.13Ni0.13O2), 0.05g second
Acetylene black and 0.05gPVDF, 0.4g NMP dispersion mixings are added, gained slurry is coated on aluminium foil, in anaerobism glove box after drying
In using metal lithium sheet as to electrode, be assembled into CR2025 button cells.At 25 DEG C, 1C multiplying powers are carried out 100 times between 2-4.8V
Charge and discharge cycles are tested, the results showed that molybdenum (Mo) doping vario-property stratiform lithium-rich manganese-based anode material has high specific capacity, circulation
It is stable, and can effectively suppress material structure change and produce voltage attenuation, show excellent electrochemical performance.
Embodiment 4
According to mol ratio shown in stratiform lithium-rich manganese-based anode material chemical formula weigh a certain amount of lithium salts, nickel salt, bore salt and
Manganese salt, which dissolves, in deionized water, is configured to the aqueous solution of the concentration for 2mol/L, and above solution is mixed.
It is 1 according to all transition metal ions in mixed solution and organic acid mol ratio：Citric acid is added to by 1.3 amount
In above-mentioned mixed solution.
Ammonium molybdate is added in above-mentioned mixed solution according to the amount that molybdenum doping amount is x=0.3, is stirred 1.2h.
The mixed solution of above-mentioned acquisition stirs 14h at 110 DEG C, until deionized water is all evaporated, obtains gelatinous mass,
Then it is put into drying box after 140 DEG C of dry 11h, takes out dried object and carry out ball mill crushing.
Broken powder body material is finally raised to 500 DEG C of sintering 7h in air atmosphere with 4 DEG C/min from 25 DEG C, then existed again
900 DEG C of insulation 15h are raised to 4 DEG C/min in air atmosphere, room temperature is naturally cooled to and obtains molybdenum (Mo) doping vario-property stratiform richness lithium
Manganese-based anode material (Li1.2Mn0.24Mo0.3Co0.13Ni0.13O2)。
Chemical property analysis is carried out to the modified layered lithium-rich manganese-based anode material of molybdenum doping of the gained of embodiment 4：Weigh
0.8g molybdenums (Mo) doping vario-property stratiform lithium-rich manganese-based anode material (Li1.2Mn0.24Mo0.3Co0.13Ni0.13O2), 0.05g acetylene blacks
And 0.05gPVDF, add 0.4g NMP dispersion mixings, gained slurry coated on aluminium foil, after drying in anaerobism glove box with
Metal lithium sheet is to electrode, is assembled into CR2025 button cells.At 25 DEG C, 1C multiplying powers carry out 100 charge and discharges between 2-4.8V
Electric loop test, the results showed that the stratiform lithium-rich manganese-based anode material of molybdenum (Mo) doping has a high specific capacity, stable circulation, and
And can effectively suppress material structure change and produce voltage attenuation, show excellent electrochemical performance.
Embodiment 5
According to mol ratio shown in stratiform lithium-rich manganese-based anode material chemical formula weigh a certain amount of lithium salts, nickel salt, bore salt and
Manganese salt, which dissolves, in deionized water, is configured to the aqueous solution of the concentration for 3mol/L, and above solution is mixed.
It is 1 according to all transition metal ions in mixed solution and organic acid mol ratio：Tartaric acid is added to by 3 amount
State in mixed solution.
Ammonium molybdate is added in above-mentioned mixed solution according to the amount that molybdenum doping amount is x=0.5, is stirred 2h.
The mixed solution of above-mentioned acquisition stirs 15h at 120 DEG C, until deionized water is all evaporated, obtains gelatinous mass,
Then it is put into drying box after 150 DEG C of dry 10h, takes out dried object and carry out ball mill crushing.
Broken powder body material is finally raised to 600 DEG C of sintering 5h in air atmosphere with 5 DEG C/min from 25 DEG C, then existed again
950 DEG C of insulation 10h are raised to 5 DEG C/min in air atmosphere, room temperature is naturally cooled to and obtains molybdenum (Mo) doping vario-property stratiform richness lithium
Manganese-based anode material (Li1.2Mn0.04Mo0.5Co0.13Ni0.13O2)。
Chemical property analysis is carried out to molybdenum (Mo) the doping vario-property stratiform lithium-rich manganese-based anode material of the gained of embodiment 5：
Weigh 0.8g molybdenums (Mo) doping vario-property stratiform lithium-rich manganese-based anode material (Li1.2Mn0.04Mo0.5Co0.13Ni0.13O2), 0.05g second
Acetylene black and 0.05gPVDF, 0.4g NMP dispersion mixings are added, gained slurry is coated on aluminium foil, in anaerobism glove box after drying
In using metal lithium sheet as to electrode, be assembled into CR2025 button cells.At 25 DEG C, 1C multiplying powers are carried out 100 times between 2-4.8V
Charge and discharge cycles are tested, the results showed that the stratiform lithium-rich manganese-based anode material of molybdenum (Mo) doping has high specific capacity, and circulation is surely
It is fixed, and can effectively suppress material structure change and produce voltage attenuation, show excellent electrochemical performance.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of lithium-rich manganese-based anode material of molybdenum doping, there is chemical formula shown in Formulas I：
Li1.2Mn0.54-xMoxCo0.13Ni0.13O2Formulas I；
Wherein, 0.05≤x≤0.5.
2. a kind of preparation method of the lithium-rich manganese-based anode material of molybdenum doping, comprises the following steps：
A) lithium source, nickel source, cobalt source and manganese source are dissolved in the water according to the mol ratio in Formulas I chemical formula, obtain mixed metal salt
Solution；
B organic acid and molybdenum source) are added into the step A successively) in mixed salt solution in, obtain mixed solution；
C) be evaporated the step B) in mixed solution in moisture, obtain gelatinous mass, the gelatinous mass be dried,
Obtain intermediate；
D) by the step C) in intermediate sintered 5~8 hours at 450~600 DEG C, be then incubated at 750~950 DEG C
10~24 hours, obtain the lithium-rich manganese-based anode material with the molybdenum doping of Formulas I chemical formula；
Li1.2Mn0.54-xMoxCo0.13Ni0.13O2Formulas I；
Wherein, 0.05≤x≤0.5.
3. preparation method according to claim 2, it is characterised in that the lithium source is lithium hydroxide, lithium carbonate and acetic acid
One or more in lithium；
Nickel source is nickel nitrate, the one or more in nickel sulfate and nickel acetate；
Cobalt source is cobalt nitrate, the one or more in cobaltous sulfate and cobalt acetate；
Manganese source is manganese nitrate, the one or more in manganese sulfate and manganese acetate.
4. preparation method according to claim 2, it is characterised in that the concentration of the mixed salt solution be 0.1~
3mol/L。
5. preparation method according to claim 2, it is characterised in that the organic acid is citric acid, tartaric acid and sweet ammonia
One or more in acid；
The mol ratio of the organic acid and all transition metal ions in mixed solution is (1~3)：1.
6. preparation method according to claim 2, it is characterised in that the molybdenum source is sodium molybdate, molybdenum acid ammonia and potassium molybdate
In one or more.
7. preparation method according to claim 2, it is characterised in that the step C) in the temperature that is evaporated be 80~120
℃；
The step C) in time for being evaporated be 10~15 hours.
8. preparation method according to claim 2, it is characterised in that the step C) in dry temperature be 100~150
℃；
The step C) in dry time be 10~15 hours.
9. preparation method according to claim 2, it is characterised in that the step C) in sintering detailed process be：
By the step B) in intermediate rise to 450~600 DEG C from room temperature with 1~5 DEG C/min speed, sintering 5~8 is small
When；Then 750~900 DEG C are being risen to 1~5 DEG C/min speed, is being incubated 10~24 hours, obtains that there is Formulas I chemical formula
The lithium-rich manganese-based anode material of molybdenum doping.
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| PCT/CN2017/116377 WO2019080310A1 (en) | 2017-10-23 | 2017-12-15 | Molybdenum-doped lithium-rich manganese-based cathode material and preparation method therefor |
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