CN108417830A - A kind of nickel lithium manganate cathode material and preparation method thereof - Google Patents
A kind of nickel lithium manganate cathode material and preparation method thereof Download PDFInfo
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- CN108417830A CN108417830A CN201810234855.9A CN201810234855A CN108417830A CN 108417830 A CN108417830 A CN 108417830A CN 201810234855 A CN201810234855 A CN 201810234855A CN 108417830 A CN108417830 A CN 108417830A
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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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- 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
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Abstract
The present invention provides a kind of nickel lithium manganate cathode materials, the micron bar assembled for nickel ion doped nano particle, the average grain diameter of the nickel ion doped nano particle is 150~250nm, and the average diameter of the micron bar is 1.5~2.5 μm, and the average length of the micron bar is 6~12 μm.The present invention provides a kind of graded structures of micron/nano assembling, that is the graded structure of nano particle and micron bar structure composite, nano particle is conducive to the quick embedded and abjection of lithium ion, structure based on micron bar structure, thermodynamic stability is excellent, and the two combines the specific capacity and cyclical stability for improving nickel lithium manganate cathode material.
Description
Technical field
The present invention relates to the technical field of anode material for lithium-ion batteries more particularly to a kind of nickel lithium manganate cathode material and
Preparation method.
Background technology
Fossil energy increasingly depleted exacerbates research of the mankind to traditional energy substitute products.Lithium ion battery (LIBs) is made
Having both energy density height for one kind, the novel energy having extended cycle life with environmental pollution outstanding advantages of small is set in mobile communication
Standby (such as mobile phone), electric vehicle and the various fields of hybrid electric vehicle possess broad prospect of application.Currently, commercialization positive electrode cobalt
Sour lithium (LiCoO2) since battery capacity is small, the defect of high rate performance and cyclical stability difference has been unable to meet the market demand.Tool
The positive electrode of standby high power capacity and high voltage, becomes the research and development direction for the following high performance lithium ion battery, answers
Also constantly expanded with market.
LiMn2O4 (LiMn2O4) it is to compare lithium cobaltate cathode material, mangaic acid with the positive electrode of three-dimensional lithium ion tunnel
Lithium has many advantages, such as that price is low, current potential is high, environmental-friendly and security performance is high.And nickel ion doped (LiNi0.5Mn1.5O4) it is used as manganese
A kind of nickel substitution product of sour lithium, the characteristics of not only inheriting LiMn2O4 high specific discharge capacity (theoretical specific capacity 147mAh/g),
It is also equipped with the high-voltage discharge platform of 4.7V, 15% or more is higher by than the 4V voltage platforms of LiMn2O4.
But when nickel ion doped is used as positive electrode, chemical property is again usually by pattern, granularity, pattern, knot
The different degrees of influence of the factors such as brilliant degree.The prior art by nickel ion doped nanosizing by improving nickel lithium manganate cathode material
Grain size is reduced to nano-scale by high rate performance, in favor of the quick conveying of lithium ion.However, due to the knot of nano-particle
Structure unstability, product thermodynamic stability can be caused to reduce can improve with interface, to make its specific capacity and cyclical stability
Decline.
Invention content
It is provided by the present invention the object of the present invention is to provide a kind of nickel lithium manganate cathode material and preparation method thereof
Nickel lithium manganate cathode material has height ratio capacity and excellent cyclical stability.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme：
The present invention provides a kind of nickel lithium manganate cathode materials, are the micron bar that nickel ion doped nano particle assembles,
The average grain diameter of the nickel ion doped nano particle is 150~250nm, and the average diameter of the micron bar is 1.5~2.5 μm,
The average length of the micron bar is 6~12 μm.
The present invention also provides a kind of preparation methods of the nickel lithium manganate cathode material described in above-mentioned technical proposal, including such as
Lower step：
(1) nickel nitrate, manganese nitrate and glycine are dissolved in the water, obtain raw material mixed liquor；
(2) strong base solution is added dropwise in the raw material mixed liquor, carries out hydro-thermal reaction, obtains nickel manganese presoma；
(3) it is calcined after mixing the nickel manganese presoma with lithium carbonate, obtains nickel lithium manganate cathode material.
Preferably, the molar ratio of the nickel nitrate and glycine is 1:10~15.
Preferably, the strong base solution is the aqueous solution of sodium hydroxide and/or potassium hydroxide.
Preferably, in the strong base solution alkali a concentration of 5~8mol/L；The amount of the substance of the nickel nitrate and highly basic are molten
The ratio between volume of liquid is 1mmol:3~5mL.
Preferably, the temperature of the hydro-thermal reaction is 120~160 DEG C, and the time of the hydro-thermal reaction is 20~26h.
Preferably, the calcining includes the first calcining and the second calcining；The temperature of first calcining is 300~400 DEG C,
The time of first calcining is 2~3h；It is described second calcining temperature be 800~850 DEG C, it is described second calcining time be
6~8h.
Preferably, be warming up to the first calcining and be warming up to the second calcining required temperature heating rate independently be 100~
150℃/h。
Preferably, the molar ratio of the lithium atom in the lithium carbonate and nickel nitrate, manganese nitrate is 1.03~1.06:0.5:
1.5。
Preferably, it is mixed into ground and mixed in the step (4).
The present invention provides a kind of nickel lithium manganate cathode materials, are the micron bar that nickel ion doped nano particle assembles,
The average grain diameter of the nickel ion doped nano particle is 150~250nm, and the average diameter of the micron bar is 1.5~2.5 μm,
The average length of the micron bar is 6~12 μm.The present invention provides a kind of graded structures of micron-nanometer assembling, that is, receive
The graded structure of rice grain and micron bar structure composite, nano particle are conducive to the quick embedded and abjection of lithium ion, micron
Structure based on stick structure, thermodynamic stability is excellent, the two combine improve nickel lithium manganate cathode material specific capacity and
Cyclical stability.
The experimental results showed that nickel lithium manganate cathode material provided by the present invention is used to prepare lithium ion battery, test
Its chemical property, under the multiplying power of 1,2,5,10,15 and 20C, gained battery be able to offer 144,140,131,125,
The reversible discharge specific capacity of 118 and 112mAh/g, highest specific capacity is very close to theoretical specific capacity 147mAh/g；And in 1C multiplying powers
The specific capacity of lower cycle charge-discharge 200 times, battery is still stablized in 142mAh/g, and coulombic efficiency reaches 99.16%, has excellent
Cyclical stability and high rate performance.
Description of the drawings
Fig. 1 prepares the flow chart of nickel lithium manganate cathode material；
The scanning electron microscope (SEM) photograph of 1 gained nickel manganese presoma of Fig. 2 embodiments, wherein figure a is low power scanning electron microscope (SEM) photograph, figure b is height
Times scanning electron microscope (SEM) photograph；
The transmission electron microscope picture of 1 gained nickel manganese presoma of Fig. 3 embodiments；
The scanning electron microscope (SEM) photograph of 1 gained nickel lithium manganate cathode material of Fig. 4 embodiments, wherein figure a is low power scanning electron microscope (SEM) photograph, figure
B is high power scanning electron microscope (SEM) photograph；
The transmission electron microscope picture of 1 gained nickel lithium manganate cathode material of Fig. 5 embodiments；
The XRD diagram of 1 gained nickel lithium manganate cathode material of Fig. 6 embodiments；
The infrared spectrogram of 1 gained nickel lithium manganate cathode material of Fig. 7 embodiments；
The Raman spectrogram of 1 gained nickel lithium manganate cathode material of Fig. 8 embodiments；
The cyclic voltammetry curve for the lithium ion battery that Fig. 9 is prepared using 1 gained nickel lithium manganate cathode material of embodiment；
The ac impedance spectroscopy for the lithium ion battery that Figure 10 is prepared using 1 gained nickel lithium manganate cathode material of embodiment；
The charging and discharging curve for the lithium ion battery that Figure 11 is prepared using 1 gained nickel lithium manganate cathode material of embodiment；
The discharge-rate performance map for the lithium ion battery that Figure 12 is prepared using 1 gained nickel lithium manganate cathode material of embodiment；
The cyclical stability test for the lithium ion battery that Figure 13 is prepared using 1 gained nickel lithium manganate cathode material of embodiment
Figure.
Specific implementation mode
The present invention provides a kind of nickel lithium manganate cathode materials, are the micron bar that nickel ion doped nano particle assembles,
The average grain diameter of the nickel ion doped nano particle is 150~250nm, and the average diameter of the micron bar is 1.5~2.5 μm,
The average length of the micron bar is 6~12 μm.
In the present invention, the average grain diameter of the nickel ion doped nano particle be 150~250nm, preferably 170~
230nm, more preferably 190~210nm.
In the present invention, the average diameter of the micron bar be 1.5~2.5 μm, preferably 1.7~2.3 μm, more preferably
1.9~2.1 μm.
In the present invention, the average length of the micron bar is 6~12 μm, preferably 7~10 μm, more preferably 7.5~9
μm。
The present invention also provides a kind of preparation methods of the nickel lithium manganate cathode material described in above-mentioned technical proposal, including such as
Lower step：
(1) nickel nitrate, manganese nitrate and glycine are dissolved in the water, obtain raw material mixed liquor；
(2) strong base solution is added dropwise in the raw material mixed liquor, carries out hydro-thermal reaction, obtains nickel manganese presoma；
(3) it is calcined after mixing the nickel manganese presoma with lithium carbonate, obtains nickel lithium manganate cathode material.
The flow chart of preparation method provided by the present invention is as shown in Figure 1.Strong base solution is added dropwise in raw material mixed liquor,
Glycine and metal ion Ni2+And Mn2+Chelation occurs, forms stable chelate, through hydro-thermal reaction, obtains surface light
Sliding rodlike nickel manganese presoma；Lithium carbonate and nickel manganese presoma are uniformly mixed, then through calcining, lithiation, release occurs
Go out carbon dioxide gas (as shown in the grey shading part in the left side in Fig. 1), while impurity decomposes, and is stablized and pure
Nickel lithium manganate cathode material, gained nickel lithium manganate cathode material be graded structure micron bar, i.e., by nano particle assemble and
At micron bar (structural representation in such as Fig. 1).
Nickel nitrate, manganese nitrate and glycine are dissolved in the water by the present invention, obtain raw material mixed liquor.
In the present invention, the molar ratio of the nickel nitrate and manganese nitrate is 1:3.
In the present invention, the molar ratio of the nickel nitrate and glycine is preferably 1:10~15, more preferably 1:12~13.
In the present invention, the glycine can chelate unstable Ni as chelating agent when follow-up strong base solution is added2+And Mn2 +, stable chelate is formed, heavy metal ion is avoided to form hydroxide precipitation, is follow-up water to form stable suspension
The uniformity of thermal response and the crystallinity of product provide guarantee, avoid the aggregation and overlapping of product.
After obtaining raw material mixed liquor, strong base solution is added dropwise in the raw material mixed liquor by the present invention, obtains suspension.
In the present invention, strong base solution is added into raw material mixed liquor by the way of dropwise addition, Ni can be reduced2+With
Mn2+The precipitation reaction rate occurred with alkali, is combined with the chelation of glycine and ultimately forms stable suspension.
In the present invention, the strong base solution is preferably the aqueous solution of sodium hydroxide and/or potassium hydroxide；Work as strong base solution
For the two mixture when, the present invention is not particularly limited the ratio of sodium hydroxide and potassium hydroxide, can be arbitrary proportion.
In the present invention, the concentration of alkali is preferably 5~8mol/L in the strong base solution, more preferably 6~7mol/L.
In the present invention, the ratio between the amount of the substance of the nickel nitrate and the volume of strong base solution are preferably 1mmol:3~
5mL, more preferably 1mmol:3.5~4.5mL.
In the present invention, the speed of the dropwise addition is preferably 2~4s/ drops.
In the present invention, during dropwise addition, the raw material mixed liquor is preferably stirring；The rotating speed of the stirring is preferred
For 900~1100rpm, more preferably 950~1050rpm.
After being added dropwise to complete, the present invention preferably continues to maintain 0.5~2h of stirring, obtains suspension.
In the present invention, the time for continuing to stirring is preferably 1~1.5h.
After obtaining suspension, the suspension is carried out hydro-thermal reaction by the present invention, obtains nickel manganese presoma.As shown in Figure 1,
After hydro-thermal reaction, rodlike nickel manganese presoma is obtained.
In the present invention, the temperature of the hydro-thermal reaction is preferably 120~160 DEG C, more preferably 130~150 DEG C, optimal
It is selected as 135~145 DEG C；The time of the hydro-thermal reaction is preferably 20~26h, more preferably 22~for 24 hours.In the present invention, water
In thermal process reactor, water promotes as solvent and pressure transmission medium by the nickel manganese Metal ion and hydroxide of complexing of glycin
Sodium solution reacts, and crystal is gradually nucleated, grows and crystallizes precipitation along one-dimensional square, ultimately forms the nickel manganese of one-dimensional rod-like structure
Presoma.
After completing hydro-thermal reaction, the present invention preferably post-processes the product of the hydro-thermal reaction, obtains nickel manganese forerunner
Body.
In the present invention, the post-processing preferably includes successively cooling, is filtered, washed and dried.
The present invention is not particularly limited the rate of the cooling, can be cooled to room temperature the product of the hydro-thermal reaction
.
In the present invention, the filtering is preferably centrifugal filtration；The rotating speed of the centrifugal filtration is preferably 6000~
8000rpm, more preferably 6500~7500rpm；The time of the centrifugation is preferably 5~8min, more preferably 6~7min.
In the present invention, by the way that the product of hydro-thermal reaction to be filtered, solid product is obtained.
In the present invention, the washing is preferably distilled water with detergent；The number of the washing is preferably 2~4 times.
In the present invention, the washing can remove the impurity such as nitrate ion.
The present invention is not particularly limited the mode of the washing, using the mode of washing of this field routine.At this
In inventive embodiments, the mode of the washing preferably uses distilled water centrifuge washing, is particularly preferred as using 50mL centrifuge tubes,
Distillation water consumption independently is 25-35mL every time, and each centrifugation time independently is 5~7 minutes, and the rotating speed centrifuged every time is independent
Ground is 6500~7500rpm.
The present invention is not particularly limited the mode of the drying, can obtain the product of constant weight.Of the invention real
It applies in example, the drying is preferably forced air drying；The temperature of the drying is preferably 70~100 DEG C, more preferably 80~90 DEG C；
The time of the drying is preferably 10~15h, more preferably 12~13h.
After obtaining nickel manganese presoma, the present invention calcines after mixing the nickel manganese presoma with lithium carbonate, obtains nickel
Manganate cathode material for lithium.In the present invention, nickel manganese presoma is mixed with lithium carbonate, obtains uniform mixture (such as Fig. 1 institutes
Show), the rodlike nickel ion doped (as shown in Figure 1) that lithiation generates nano particle assembling then occurs by calcining.
In the present invention, the lithium atom in the lithium carbonate and nickel nitrate, manganese nitrate molar ratio be preferably 1.03~
1.06:0.5:1.5, more preferably 1.04~1.05:0.5:1.5.
In the present invention, the lithium carbonate is preferably powdered lithium carbonate.The present invention does not have the grain size of the lithium carbonate
Particular determination, commercially available lithium carbonate powder.
In the present invention, the mixing is preferably ground and mixed；The time of the ground and mixed is preferably 15~30min,
More preferably 20~25min.In the present invention, before the ground and mixed can ensure that lithium carbonate powder is homogeneously dispersed in nickel manganese
It drives in body.
In the present invention, the calcining preferably includes the first calcining and the second calcining；The temperature of first calcining is preferred
It is 300~400 DEG C, more preferably 330~360 DEG C；The time of first calcining is preferably 2~3h, more preferably 2.3~
2.7h；The temperature of second calcining is preferably 800~850 DEG C, more preferably 820~830 DEG C；The time of second calcining
Preferably 6~8h, more preferably 6.5~7.5h.
In the present invention, stable basal body structure, while effectively control can be obtained by the first calcining of lower temperature
Mn3+Content, can improve electrode material electric conductivity and Jahn-Teller effect caused by structure collapses；It is warming up to second
After calcination temperature, lithiation occurs, releases carbon dioxide gas (as shown in the grey shading part in the left side in Fig. 1),
Impurity decomposes simultaneously, is stablized and pure nickel lithium manganate cathode material, gained nickel lithium manganate cathode material are that graduation is tied
The micron bar of structure, i.e., the micron bar (structural representation in such as Fig. 1) assembled by nano particle.
In the present invention, the heating rate for being warming up to the first calcining and being warming up to the second calcining required temperature is preferably 100
~150 DEG C/h, more preferably 120~130 DEG C/h.
Rodlike nickel lithium manganate cathode material provided by the present invention forms lithium ion cell positive after being mixed with carbon black, can have
Effect shortens the diffusion length of lithium ion, and keeps rock-steady structure (as shown in the grey shading part on the right side in Fig. 1).
Nickel lithium manganate cathode material provided by the invention and preparation method thereof is carried out specifically with reference to embodiment
It is bright, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
(1) by 2mmol Ni (NO3)2·6H2O、6mmol Mn(NO3)2·6H2O and 26.7mmol glycine is dissolved in
In 50mL deionized waters, raw material mixed liquor is obtained；
(2) under stirring, the sodium hydroxide solution of a concentration of 5mol/L of 10mL is added dropwise in raw material mixed liquor, institute
It is 10 minutes to state time for adding；After being added dropwise to complete, continues to stir 30min, obtain suspension；
(3) suspension being transferred in hydrothermal reaction kettle and carries out hydro-thermal reaction, the temperature of hydro-thermal reaction is 140 DEG C,
The time of hydro-thermal reaction is for 24 hours；After completing hydro-thermal reaction, after reaction kettle is cooled to room temperature, by centrifuging, precipitated
Object；It is washed with distilled water sediment 3 times, using 50mL centrifuge tubes, centrifuge washing is carried out at rotating speed 7500rpm, wash every time
With 25~35mL of water；By the sediment after washing in 80 DEG C of dry 12h, nickel manganese presoma is obtained；
(4) lithium carbonate and nickel manganese presoma is uniform by ground and mixed, the time of the grinding is 10~15min, institute
The molar ratio for stating lithium and nickel, manganese in lithium carbonate is 1.05:05:1.5；Gained mixture is placed in Muffle furnace, is warming up to 300
DEG C, the first calcining 2h is carried out, then heats to 850 DEG C, the second calcining 6h is carried out, obtains nickel lithium manganate cathode material；The liter
Temperature independently is 150 DEG C/h to 300 DEG C with the heating rate for being warming up to 850 DEG C.
Table is carried out to the surface topography of nickel manganese presoma obtained by the present embodiment step (3) using low power and high power scanning electron microscope
Sign, as shown in Fig. 2, Fig. 2 a are low power SEM figures, Fig. 2 b are high power SEM figures, as seen from Figure 2 before nickel manganese obtained by the present embodiment
Drive body is size uniform, and the average length of the smooth one-dimensional micron stick in surface, micron bar is 10 μm, average diameter 800nm.
Nickel manganese presoma obtained by the present embodiment step (3) is characterized using transmission electron microscope, gained TEM figures are such as Fig. 3 institutes
Show, nickel manganese presoma is uniform club shaped structure as seen from Figure 3, is matched with the SEM figures of Fig. 2.
It is characterized using the pattern of nickel lithium manganate cathode material obtained by scanning electron microscope the present embodiment, the results are shown in Figure 4,
Gained nickel lithium manganate cathode material remains as one-dimensional rod-like structure as shown in Figure 4, and average length is 8 μm, and average diameter is 2 μm.
Fig. 4 a are low power scanning electron microscope (SEM) photograph, and Fig. 4 b are high power scanning electron microscope (SEM) photograph, can be seen that the nickel ion doped of club shaped structure just by Fig. 4 b
Pole material is made of the particle that average diameter is 200nm, for the graded structure of micron-nanometer assembling.
Nickel lithium manganate cathode material obtained by the present embodiment is characterized using transmission electron microscope, the results are shown in Figure 5.By scheming
5 can be clearly seen that club shaped structure is assembled by nano particle, consistent with the structure that Fig. 4 b are shown；In addition, may be used also by Fig. 5
To see in micron bar there is also gap, illustrate that micron bar has porous structure.
Nickel ion doped obtained by the present embodiment is subjected to X-ray diffraction test, the results are shown in Figure 6, the feature of gained XRD diagram
Peak and standard PDF cards No.80-2162 (nickel ion doped LiNi0.5Mn1.5O4Standard card) it is completely corresponding, and occur without miscellaneous peak,
Illustrate that nickel ion doped obtained by the present embodiment is pure nickel ion doped LiNi0.5Mn1.5O4。
Nickel ion doped obtained by the present embodiment is subjected to the test of infrared and Raman spectrum, as a result as shown in Figure 7 and Figure 8.Fig. 7 and
Characteristic peak in Fig. 8 illustrates to contain a certain amount of Mn in product3+, while also illustrating that Fd3m phases are nickel lithium manganate cathode material
Main phase.The infrared spectrum of Fig. 7 is in 472,497,559,588 and 623cm-1The characteristic peak that place occurs, the Raman spectrum 398 of Fig. 8,
493 and 632cm-1The characteristic peak that place occurs all points to the Fd3m phases of product, and in Raman spectrum 588-623cm-1Region does not have
Occur being directed toward P43The swarming of 32 phases is as a result, further confirmed LiNi0.5Mn1.5O4In main phase be Fd3m phases.
Electrochemical property test：By nickel lithium manganate cathode material obtained by the present embodiment and conductive black, binder (PVDF)
It is 7 according to mass ratio:2:1 ratio is configured to uniform anode sizing agent, is coated on aluminium foil, after dry and tabletting, institute
The load capacity for obtaining circular electric pole piece is 2~3mg/cm2；The aluminium foil for being coated with anode sizing agent cuts into disk as anode；
By it is described anode successively with diaphragm, lithium anode and electrolyte (i.e. 1mol/LLiPF6Solution, the solvent of the solution
By ethylene carbonate (EC) and dimethyl carbonate (DMC) with 1:1 volume ratio mixes) it forms into lithium ion battery, and survey
Try the chemical property of lithium ion battery.
Fig. 9 be lithium ion battery in the case where 0.1mV/s sweeps speed, the cyclic voltammetry curve in the sections 3.3V~5.0V, oxidation
Reduction peak is corresponding with the voltage platform in Figure 11 charging and discharging curves.Two groups of redox peaks are observed that in figure in total,
Swarming near 4.7V corresponds to Ni2+/Ni3+And Ni3+/Ni4+The redox reaction in two stages；Weak peak near 4.0V corresponds to
Mn3+/Mn4+Redox reaction, the small figure in Fig. 9 is the partial enlarged view of the process, it can be seen that figure line is faint to be risen
Volt, illustrates a small amount of Mn3+Presence.In cyclic process three times, only there are slight change, main redox peaks in CV curves
Can be observed, and figure line is almost along same track, illustrate micron-nanometer package assembly in cyclic process compared with
Good stability.
Figure 10 is the ac impedance spectroscopy of lithium ion battery, is measured in the frequency range of 10mHz~100kHz at room temperature,
As seen from the figure, there is subtle rising in the resistance of lithium ion battery after 5 circle of cycle, hereafter with the increase of the cycle number of turns,
The resistance of battery remains unchanged substantially, illustrates that nickel lithium manganate cathode material provided by the present invention has excellent stable circulation
Property.
Figure 11 is the charging and discharging curve of lithium ion battery, as seen from the figure, the charge specific capacity under 0.1,1,2 and 5C multiplying powers
Respectively 181,156,145 and 138mAh/g, corresponding specific discharge capacity are respectively 158,150,141 and 135mAh/g.More than
Data are obtained in first time charge and discharge cycles under different multiplying, it can be seen that actual specific capacity close to theoretical specific capacity；And
And in low range first time discharge process, the charging and discharging capacity of material even can be only slight beyond theoretical value, although the
During secondary charge and discharge cycles, specific discharge capacity falls back to theoretical value rapidly hereinafter, the result remains able to illustrate material
Possess preferable specific capacity.
Figure 12 is that the discharge-rate performance map of lithium ion battery is followed under 1,2,5,15 and 20C multiplying powers successively as seen from the figure
Ring 5 times, lithium ion battery can provide the reversible specific capacity of 144,140,131,125,118 and 112mAh/g；When electric current is restored to
When 1C multiplying powers, specific capacity can be restored to 143mAh/g substantially, close to initial value, illustrate using positive electrode obtained by the present embodiment
The lithium ion battery of preparation has excellent high rate performance.
Figure 13 is the cyclical stability test chart of lithium ion battery, and as seen from the figure, lithium ion battery recycles under 1C multiplying powers
After 200 times, specific discharge capacity is stablized in 142mAh/g, and coulombic efficiency reaches 99.16%, illustrates using anode obtained by the present embodiment
The cyclical stability of the lithium ion battery of material preparation is excellent.
Embodiment 2
(1) by 2mmol Ni (NO3)2·6H2O、6mmol Mn(NO3)2·6H2O and 20mmol glycine is dissolved in 50mL
In deionized water, raw material mixed liquor is obtained；
(2) under stirring, the sodium hydroxide solution of a concentration of 5mol/L of 10mL is added dropwise in raw material mixed liquor, institute
It is 10min to state time for adding；After being added dropwise to complete, continues to stir 30min, obtain suspension；
(3) suspension being transferred in hydrothermal reaction kettle and carries out hydro-thermal reaction, the temperature of hydro-thermal reaction is 140 DEG C,
The time of hydro-thermal reaction is for 24 hours；After completing hydro-thermal reaction, after reaction kettle is cooled to room temperature, by centrifuging, precipitated
Object；It is washed with distilled water sediment 3 times, using 50mL centrifuge tubes, centrifuge washing is carried out at rotating speed 7500rpm, wash every time
With 25~35mL of water；By the sediment after washing in 80 DEG C of dry 12h, nickel manganese presoma is obtained；
(4) lithium carbonate and nickel manganese presoma is uniform by ground and mixed, the time of the grinding is 10~15min, institute
The molar ratio for stating lithium and nickel, manganese in lithium carbonate is 1.05:05:1.5；Gained mixture is placed in Muffle furnace, is warming up to 300
DEG C, the first calcining 2h is carried out, then heats to 850 DEG C, the second calcining 6h is carried out, obtains nickel lithium manganate cathode material；The liter
Temperature independently is 150 DEG C/h to 300 DEG C with the heating rate for being warming up to 850 DEG C.
Table is carried out to the surface topography of nickel manganese presoma obtained by the present embodiment step (3) using low power and high power scanning electron microscope
Sign, as a result similar to Fig. 2, the average length of nickel manganese presoma obtained by the present embodiment is 11 μm, average diameter 900nm.
It is characterized using the pattern of nickel lithium manganate cathode material obtained by scanning electron microscope the present embodiment, it is as a result similar to Fig. 4,
The average length of gained nickel lithium manganate cathode material is 9 μm, and average diameter is 2.4 μm, the nickel ion doped anode material of club shaped structure
Material is made of the particle that average diameter is 240nm.
Nickel lithium manganate cathode material obtained by the present embodiment is characterized using transmission electron microscope, is as a result similar to Fig. 5, it is rodlike
Structure is assembled by nano particle, and micron bar has porous structure.
Nickel ion doped obtained by the present embodiment is subjected to X-ray diffraction test, Fig. 6 is as a result similar to, illustrates the present embodiment institute
It is pure nickel ion doped LiNi to obtain nickel ion doped0.5Mn1.5O4。
Nickel ion doped obtained by the present embodiment is subjected to the test of infrared and Raman spectrum, is as a result similar to Fig. 7 and Fig. 8.
Nickel lithium manganate cathode material obtained by the present embodiment is assembled according to electrochemical property test method described in embodiment 1
For lithium ion battery, its chemical property is tested, each performance is similar to Example 1.Lithium ion battery is following obtained by wherein
After ring 5 encloses, the resistance of battery is basically unchanged with excellent cyclical stability；Successively 5 are recycled under 1,2,5,15 and 20C multiplying powers
Secondary, lithium ion battery can provide the reversible specific capacity of 140,139,125,123,111 and 105mAh/g, when electric current is restored to 1C times
When rate, specific capacity can be restored to 137mAh/g substantially, close to initial value, illustrate to prepare using positive electrode obtained by the present embodiment
Lithium ion battery have excellent high rate performance；After lithium ion battery recycles 200 times under 1C multiplying powers, specific discharge capacity is stablized
In 138mAh/g, coulombic efficiency reaches 98.78%, illustrates using the lithium ion battery that obtained by the present embodiment prepared by positive electrode
Cyclical stability is excellent.
Embodiment 3
(1) by 2mmol Ni (NO3)2·6H2O、6mmol Mn(NO3)2·6H2O and 30mmol glycine is dissolved in 50mL
In deionized water, raw material mixed liquor is obtained；
(2) under stirring, the sodium hydroxide solution of a concentration of 5mol/L of 10mL is added dropwise in raw material mixed liquor, institute
It is 10min to state time for adding；After being added dropwise to complete, continues to stir 30min, obtain suspension；
(3) suspension being transferred in hydrothermal reaction kettle and carries out hydro-thermal reaction, the temperature of hydro-thermal reaction is 140 DEG C,
The time of hydro-thermal reaction is for 24 hours；After completing hydro-thermal reaction, after reaction kettle is cooled to room temperature, by centrifuging, precipitated
Object；It is washed with distilled water sediment 3 times, using 50mL centrifuge tubes, centrifuge washing is carried out at rotating speed 7500rpm, wash every time
With 25~35mL of water；By the sediment after washing in 80 DEG C of dry 12h, nickel manganese presoma is obtained；
(4) lithium carbonate and nickel manganese presoma is uniform by ground and mixed, the time of the grinding is 10~15min, institute
The molar ratio for stating lithium and nickel, manganese in lithium carbonate is 1.05:05:1.5；Gained mixture is placed in Muffle furnace, is warming up to 300
DEG C, the first calcining 2h is carried out, then heats to 850 DEG C, the second calcining 6h is carried out, obtains nickel lithium manganate cathode material；The liter
Temperature independently is 150 DEG C/h to 300 DEG C with the heating rate for being warming up to 850 DEG C.
Table is carried out to the surface topography of nickel manganese presoma obtained by the present embodiment step (3) using low power and high power scanning electron microscope
Sign, as a result similar to Fig. 2, the average length of nickel manganese presoma obtained by the present embodiment is 9 μm, average diameter 700nm.
It is characterized using the pattern of nickel lithium manganate cathode material obtained by scanning electron microscope the present embodiment, it is as a result similar to Fig. 4,
The average length of gained nickel lithium manganate cathode material is 6 μm, and average diameter is 1.5 μm, the nickel ion doped anode material of club shaped structure
Material is made of the particle that average diameter is 150nm.
Nickel lithium manganate cathode material obtained by the present embodiment is characterized using transmission electron microscope, is as a result similar to Fig. 5, it is rodlike
Structure is assembled by nano particle, and micron bar has porous structure.
Nickel ion doped obtained by the present embodiment is subjected to X-ray diffraction test, Fig. 6 is as a result similar to, illustrates the present embodiment institute
It is pure nickel ion doped LiNi to obtain nickel ion doped0.5Mn1.5O4。
Nickel ion doped obtained by the present embodiment is subjected to the test of infrared and Raman spectrum, is as a result similar to Fig. 7 and Fig. 8.
Nickel lithium manganate cathode material obtained by the present embodiment is assembled according to electrochemical property test method described in embodiment 1
For lithium ion battery, its chemical property is tested, each performance is similar to Example 1.Lithium ion battery is following obtained by wherein
After ring 5 encloses, the resistance of battery is basically unchanged with excellent cyclical stability；Successively 5 are recycled under 1,2,5,15 and 20C multiplying powers
Secondary, lithium ion battery can provide the reversible specific capacity of 142,138,131,125,117 and 109mAh/g, when electric current is restored to 1C times
When rate, specific capacity can be restored to 140mAh/g substantially, close to initial value, illustrate to prepare using positive electrode obtained by the present embodiment
Lithium ion battery have excellent high rate performance；After lithium ion battery recycles 200 times under 1C multiplying powers, specific discharge capacity is stablized
In 138mAh/g, coulombic efficiency reaches 98.01%, illustrates using the lithium ion battery that obtained by the present embodiment prepared by positive electrode
Cyclical stability is excellent.
Embodiment 4
(1) by 2mmol Ni (NO3)2·6H2O、6mmol Mn(NO3)2·6H2O and 26.7mmol glycine is dissolved in
In 50mL deionized waters, raw material mixed liquor is obtained；
(2) under stirring, the sodium hydroxide solution of a concentration of 8mol/L of 10mL is added dropwise in raw material mixed liquor, institute
It is 10min to state time for adding；After being added dropwise to complete, continues to stir 30min, obtain suspension；
(3) suspension being transferred in hydrothermal reaction kettle and carries out hydro-thermal reaction, the temperature of hydro-thermal reaction is 140 DEG C,
The time of hydro-thermal reaction is for 24 hours；After completing hydro-thermal reaction, after reaction kettle is cooled to room temperature, by centrifuging, precipitated
Object；It is washed with distilled water sediment 3 times, using 50mL centrifuge tubes, centrifuge washing is carried out at rotating speed 7500rpm, wash every time
With 25~35mL of water；By the sediment after washing in 80 DEG C of dry 12h, nickel manganese presoma is obtained；
(4) lithium carbonate and nickel manganese presoma is uniform by ground and mixed, the time of the grinding is 10~15min, institute
The molar ratio for stating lithium and nickel, manganese in lithium carbonate is 1.05:05:1.5；Gained mixture is placed in Muffle furnace, is warming up to 300
DEG C, the first calcining 2h is carried out, then heats to 850 DEG C, the second calcining 6h is carried out, obtains nickel lithium manganate cathode material；The liter
Temperature independently is 150 DEG C/h to 300 DEG C with the heating rate for being warming up to 850 DEG C.
Table is carried out to the surface topography of nickel manganese presoma obtained by the present embodiment step (3) using low power and high power scanning electron microscope
Sign, as a result similar to Fig. 2, the average length of nickel manganese presoma obtained by the present embodiment is 12 μm, and average diameter is 1.5 μm.
It is characterized using the pattern of nickel lithium manganate cathode material obtained by scanning electron microscope the present embodiment, it is as a result similar to Fig. 4,
The average length of gained nickel lithium manganate cathode material is 10 μm, and average diameter is 2.5 μm, the nickel ion doped anode material of club shaped structure
Material is made of the particle that average diameter is 250nm.
Nickel lithium manganate cathode material obtained by the present embodiment is characterized using transmission electron microscope, is as a result similar to Fig. 5, it is rodlike
Structure is assembled by nano particle, and micron bar has porous structure.
Nickel ion doped obtained by the present embodiment is subjected to X-ray diffraction test, Fig. 6 is as a result similar to, illustrates the present embodiment institute
It is pure nickel ion doped LiNi to obtain nickel ion doped0.5Mn1.5O4。
Nickel ion doped obtained by the present embodiment is subjected to the test of infrared and Raman spectrum, is as a result similar to Fig. 7 and Fig. 8.
Nickel lithium manganate cathode material obtained by the present embodiment is assembled according to electrochemical property test method described in embodiment 1
For lithium ion battery, its chemical property is tested, each performance is similar to Example 1.Lithium ion battery is following obtained by wherein
After ring 5 encloses, the resistance of battery is basically unchanged with excellent cyclical stability；Successively 5 are recycled under 1,2,5,15 and 20C multiplying powers
Secondary, lithium ion battery can provide the reversible specific capacity of 138,131,123,116,108 and 100mAh/g, when electric current is restored to 1C times
When rate, specific capacity can restore initial value 136mAh/g substantially, illustrate the lithium prepared using positive electrode obtained by the present embodiment from
Sub- battery has excellent high rate performance；After lithium ion battery recycles 200 times under 1C multiplying powers, specific discharge capacity is stablized
135mAh/g, coulombic efficiency reach 99.11%, illustrate following using the lithium ion battery that obtained by the present embodiment prepared by positive electrode
Ring excellent in stability.
Embodiment 5
(1) by 2mmol Ni (NO3)2·6H2O、6mmol Mn(NO3)2·6H2O and 26.7mmol glycine is dissolved in
In 50mL deionized waters, raw material mixed liquor is obtained；
(2) under stirring, the sodium hydroxide solution of a concentration of 5mol/L of 10mL is added dropwise in raw material mixed liquor, institute
It is 10min to state time for adding；After being added dropwise to complete, continues to stir 1h, obtain suspension；
(3) suspension being transferred in hydrothermal reaction kettle and carries out hydro-thermal reaction, the temperature of hydro-thermal reaction is 140 DEG C,
The time of hydro-thermal reaction is for 24 hours；After completing hydro-thermal reaction, after reaction kettle is cooled to room temperature, by centrifuging, precipitated
Object；It is washed with distilled water sediment 3 times, using 50mL centrifuge tubes, centrifuge washing is carried out at rotating speed 7500rpm, wash every time
With 25~35mL of water；By the sediment after washing in 80 DEG C of dry 12h, nickel manganese presoma is obtained；
(4) lithium carbonate and nickel manganese presoma is uniform by ground and mixed, the time of the grinding is 10~15min, institute
The molar ratio for stating lithium and nickel, manganese in lithium carbonate is 1.05:05:1.5；Gained mixture is placed in Muffle furnace, is warming up to 300
DEG C, the first calcining 2h is carried out, then heats to 850 DEG C, the second calcining 6h is carried out, obtains nickel lithium manganate cathode material；The liter
Temperature independently is 150 DEG C/h to 300 DEG C with the heating rate for being warming up to 850 DEG C.
Table is carried out to the surface topography of nickel manganese presoma obtained by the present embodiment step (3) using low power and high power scanning electron microscope
Sign, as a result similar to Fig. 2, the average length of nickel manganese presoma obtained by the present embodiment is 10.5 μm, average diameter 850nm.
It is characterized using the pattern of nickel lithium manganate cathode material obtained by scanning electron microscope the present embodiment, it is as a result similar to Fig. 4,
The average length of gained nickel lithium manganate cathode material is 8.5 μm, and average diameter is 2.1 μm, the nickel ion doped anode of club shaped structure
Material is made of the particle that average diameter is 230nm.
Nickel lithium manganate cathode material obtained by the present embodiment is characterized using transmission electron microscope, is as a result similar to Fig. 5, it is rodlike
Structure is assembled by nano particle, and micron bar has porous structure.
Nickel ion doped obtained by the present embodiment is subjected to X-ray diffraction test, Fig. 6 is as a result similar to, illustrates the present embodiment institute
It is pure nickel ion doped LiNi to obtain nickel ion doped0.5Mn1.5O4。
Nickel ion doped obtained by the present embodiment is subjected to the test of infrared and Raman spectrum, is as a result similar to Fig. 7 and Fig. 8.
Nickel lithium manganate cathode material obtained by the present embodiment is assembled according to electrochemical property test method described in embodiment 1
For lithium ion battery, its chemical property is tested, each performance is similar to Example 1.Lithium ion battery is following obtained by wherein
After ring 5 encloses, the resistance of battery is basically unchanged with excellent cyclical stability；Successively 5 are recycled under 1,2,5,15 and 20C multiplying powers
Secondary, lithium ion battery can provide the reversible specific capacity of 142,139,132,126,115 and 108mAh/g, when electric current is restored to 1C times
When rate, specific capacity can be restored to 139mAh/g substantially, close to initial value, illustrate to prepare using positive electrode obtained by the present embodiment
Lithium ion battery have excellent high rate performance；After lithium ion battery recycles 200 times under 1C multiplying powers, specific discharge capacity is stablized
In 138mAh/g, coulombic efficiency reaches 98.32%, illustrates using the lithium ion battery that obtained by the present embodiment prepared by positive electrode
Cyclical stability is excellent.
Embodiment 6
(1) by 2mmol Ni (NO3)2·6H2O、6mmol Mn(NO3)2·6H2O and 26.7mmol glycine is dissolved in
In 50mL deionized waters, raw material mixed liquor is obtained；
(2) under stirring, the sodium hydroxide solution of a concentration of 5mol/L of 10mL is added dropwise in raw material mixed liquor, institute
It is 10min to state time for adding；After being added dropwise to complete, continues to stir 2h, obtain suspension；
(3) suspension being transferred in hydrothermal reaction kettle and carries out hydro-thermal reaction, the temperature of hydro-thermal reaction is 140 DEG C,
The time of hydro-thermal reaction is for 24 hours；After completing hydro-thermal reaction, after reaction kettle is cooled to room temperature, by centrifuging, precipitated
Object；It is washed with distilled water sediment 3 times, using 50mL centrifuge tubes, centrifuge washing is carried out at rotating speed 7500rpm, wash every time
With 25~35mL of water；By the sediment after washing in 80 DEG C of dry 12h, nickel manganese presoma is obtained；
(4) lithium carbonate and nickel manganese presoma is uniform by ground and mixed, the time of the grinding is 10~15min, institute
The molar ratio for stating lithium and nickel, manganese in lithium carbonate is 1.05:05:1.5；Gained mixture is placed in Muffle furnace, is warming up to 300
DEG C, the first calcining 2h is carried out, then heats to 850 DEG C, the second calcining 6h is carried out, obtains nickel lithium manganate cathode material；The liter
Temperature independently is 150 DEG C/h to 300 DEG C with the heating rate for being warming up to 850 DEG C.
Table is carried out to the surface topography of nickel manganese presoma obtained by the present embodiment step (3) using low power and high power scanning electron microscope
Sign, as a result similar to Fig. 2, the average length of nickel manganese presoma obtained by the present embodiment is 11 μm, average diameter 900nm.
It is characterized using the pattern of nickel lithium manganate cathode material obtained by scanning electron microscope the present embodiment, it is as a result similar to Fig. 4,
The average length of gained nickel lithium manganate cathode material is 10 μm, and average diameter is 2.3 μm, the nickel ion doped anode material of club shaped structure
Material is made of the particle that average diameter is 240nm.
Nickel lithium manganate cathode material obtained by the present embodiment is characterized using transmission electron microscope, is as a result similar to Fig. 5, it is rodlike
Structure is assembled by nano particle, and micron bar has porous structure.
Nickel ion doped obtained by the present embodiment is subjected to X-ray diffraction test, Fig. 6 is as a result similar to, illustrates the present embodiment institute
It is pure nickel ion doped LiNi to obtain nickel ion doped0.5Mn1.5O4。
Nickel ion doped obtained by the present embodiment is subjected to the test of infrared and Raman spectrum, is as a result similar to Fig. 7 and Fig. 8.
Nickel lithium manganate cathode material obtained by the present embodiment is assembled according to electrochemical property test method described in embodiment 1
For lithium ion battery, its chemical property is tested, each performance is similar to Example 1.Lithium ion battery is following obtained by wherein
After ring 5 encloses, the resistance of battery is basically unchanged with excellent cyclical stability；Successively 5 are recycled under 1,2,5,15 and 20C multiplying powers
Secondary, lithium ion battery can provide the reversible specific capacity of 138,132,122,121,111 and 102mAh/g, when electric current is restored to 1C times
When rate, specific capacity can restore initial value 135mAh/g substantially, illustrate the lithium prepared using positive electrode obtained by the present embodiment from
Sub- battery has excellent high rate performance；After lithium ion battery recycles 200 times under 1C multiplying powers, specific discharge capacity is stablized
134mAh/g, coulombic efficiency reach 97.46%, illustrate following using the lithium ion battery that obtained by the present embodiment prepared by positive electrode
Ring excellent in stability.
Embodiment 7
(1) by 2mmol Ni (NO3)2·6H2O、6mmol Mn(NO3)2·6H2O and 26.7mmol glycine is dissolved in
In 50mL deionized waters, raw material mixed liquor is obtained；
(2) under stirring, the sodium hydroxide solution of a concentration of 5mol/L of 10mL is added dropwise in raw material mixed liquor, institute
It is 10min to state time for adding；After being added dropwise to complete, continues to stir 30min, obtain suspension；
(3) suspension being transferred in hydrothermal reaction kettle and carries out hydro-thermal reaction, the temperature of hydro-thermal reaction is 140 DEG C,
The time of hydro-thermal reaction is for 24 hours；After completing hydro-thermal reaction, after reaction kettle is cooled to room temperature, by centrifuging, precipitated
Object；It is washed with distilled water sediment 3 times, using 50mL centrifuge tubes, centrifuge washing is carried out at rotating speed 7500rpm, wash every time
With 25~35mL of water；By the sediment after washing in 80 DEG C of dry 12h, nickel manganese presoma is obtained；
(4) lithium carbonate and nickel manganese presoma is uniform by ground and mixed, the time of the grinding is 10~15min, institute
The molar ratio for stating lithium and nickel, manganese in lithium carbonate is 1.05:05:1.5；Gained mixture is placed in Muffle furnace, is warming up to 350
DEG C, the first calcining 2h is carried out, then heats to 800 DEG C, the second calcining 6h is carried out, obtains nickel lithium manganate cathode material；The liter
Temperature independently is 150 DEG C/h to 350 DEG C with the heating rate for being warming up to 800 DEG C.
Table is carried out to the surface topography of nickel manganese presoma obtained by the present embodiment step (3) using low power and high power scanning electron microscope
Sign, as a result similar to Fig. 2, the average length of nickel manganese presoma obtained by the present embodiment is 10 μm, average diameter 800nm.
It is characterized using the pattern of nickel lithium manganate cathode material obtained by scanning electron microscope the present embodiment, it is as a result similar to Fig. 4,
The average length of gained nickel lithium manganate cathode material is 8.5 μm, and average diameter is 2.1 μm, the nickel ion doped anode of club shaped structure
Material is made of the particle that average diameter is 210nm.
Nickel lithium manganate cathode material obtained by the present embodiment is characterized using transmission electron microscope, is as a result similar to Fig. 5, it is rodlike
Structure is assembled by nano particle, and micron bar has porous structure.
Nickel ion doped obtained by the present embodiment is subjected to X-ray diffraction test, Fig. 6 is as a result similar to, illustrates the present embodiment institute
It is pure nickel ion doped LiNi to obtain nickel ion doped0.5Mn1.5O4。
Nickel ion doped obtained by the present embodiment is subjected to the test of infrared and Raman spectrum, is as a result similar to Fig. 7 and Fig. 8.
Nickel lithium manganate cathode material obtained by the present embodiment is assembled according to electrochemical property test method described in embodiment 1
For lithium ion battery, its chemical property is tested, each performance is similar to Example 1.Lithium ion battery is following obtained by wherein
After ring 5 encloses, the resistance of battery is basically unchanged with excellent cyclical stability；Successively 5 are recycled under 1,2,5,15 and 20C multiplying powers
Secondary, lithium ion battery can provide the reversible specific capacity of 140,138,127,122,114 and 108mAh/g, when electric current is restored to 1C times
When rate, specific capacity can restore initial value 138mAh/g substantially, illustrate the lithium prepared using positive electrode obtained by the present embodiment from
Sub- battery has excellent high rate performance；After lithium ion battery recycles 200 times under 1C multiplying powers, specific discharge capacity is stablized
136mAh/g, coulombic efficiency reach 97.46%, illustrate following using the lithium ion battery that obtained by the present embodiment prepared by positive electrode
Ring excellent in stability.
Embodiment 8
(1) by 2mmol Ni (NO3)2·6H2O、6mmol Mn(NO3)2·6H2O and 26.7mmol glycine is dissolved in
In 50mL deionized waters, raw material mixed liquor is obtained；
(2) under stirring, the sodium hydroxide solution of a concentration of 5mol/L of 10mL is added dropwise in raw material mixed liquor, institute
It is 10min to state time for adding；After being added dropwise to complete, continues to stir 30min, obtain suspension；
(3) suspension being transferred in hydrothermal reaction kettle and carries out hydro-thermal reaction, the temperature of hydro-thermal reaction is 160 DEG C,
The time of hydro-thermal reaction is 20h；After completing hydro-thermal reaction, after reaction kettle is cooled to room temperature, by centrifuging, precipitated
Object；It is washed with distilled water sediment 3 times, using 50mL centrifuge tubes, centrifuge washing is carried out at rotating speed 7500rpm, wash every time
With 25~35mL of water；By the sediment after washing in 80 DEG C of dry 12h, nickel manganese presoma is obtained；
(4) lithium carbonate and nickel manganese presoma is uniform by ground and mixed, the time of the grinding is 10~15min, institute
The molar ratio for stating lithium and nickel, manganese in lithium carbonate is 1.05:05:1.5；Gained mixture is placed in Muffle furnace, is warming up to 300
DEG C, the first calcining 2h is carried out, then heats to 850 DEG C, the second calcining 6h is carried out, obtains nickel lithium manganate cathode material；The liter
Temperature independently is 150 DEG C/h to 300 DEG C with the heating rate for being warming up to 850 DEG C.
Table is carried out to the surface topography of nickel manganese presoma obtained by the present embodiment step (3) using low power and high power scanning electron microscope
Sign, as a result similar to Fig. 2, the average length of nickel manganese presoma obtained by the present embodiment is 11 μm, average diameter 950nm.
It is characterized using the pattern of nickel lithium manganate cathode material obtained by scanning electron microscope the present embodiment, it is as a result similar to Fig. 4,
The average length of gained nickel lithium manganate cathode material is 11 μm, and average diameter is 2.3 μm, the nickel ion doped anode material of club shaped structure
Material is made of the particle that average diameter is 250nm.
Nickel lithium manganate cathode material obtained by the present embodiment is characterized using transmission electron microscope, is as a result similar to Fig. 5, it is rodlike
Structure is assembled by nano particle, and micron bar has porous structure.
Nickel ion doped obtained by the present embodiment is subjected to X-ray diffraction test, Fig. 6 is as a result similar to, illustrates the present embodiment institute
It is pure nickel ion doped LiNi to obtain nickel ion doped0.5Mn1.5O4。
Nickel ion doped obtained by the present embodiment is subjected to the test of infrared and Raman spectrum, is as a result similar to Fig. 7 and Fig. 8.
Nickel lithium manganate cathode material obtained by the present embodiment is assembled according to electrochemical property test method described in embodiment 1
For lithium ion battery, its chemical property is tested, each performance is similar to Example 1.Lithium ion battery is following obtained by wherein
After ring 5 encloses, the resistance of battery is basically unchanged with excellent cyclical stability；Successively 5 are recycled under 1,2,5,15 and 20C multiplying powers
Secondary, lithium ion battery can provide the reversible specific capacity of 138,136,130,123,113 and 106mAh/g, when electric current is restored to 1C times
When rate, specific capacity can restore initial value 134mAh/g substantially, illustrate the lithium prepared using positive electrode obtained by the present embodiment from
Sub- battery has excellent high rate performance；After lithium ion battery recycles 200 times under 1C multiplying powers, specific discharge capacity is stablized
132mAh/g, coulombic efficiency reach 96.46%, illustrate following using the lithium ion battery that obtained by the present embodiment prepared by positive electrode
Ring excellent in stability.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of nickel lithium manganate cathode material, for the micron bar that nickel ion doped nano particle assembles, the nickel ion doped is received
The average grain diameter of rice grain is 150~250nm, and the average diameter of the micron bar is 1.5~2.5 μm, and the micron bar is put down
Equal length is 6~12 μm.
2. a kind of preparation method of nickel lithium manganate cathode material described in claim 1, includes the following steps：
(1) nickel nitrate, manganese nitrate and glycine are dissolved in the water, obtain raw material mixed liquor；
(2) strong base solution is added dropwise in the raw material mixed liquor, carries out hydro-thermal reaction, obtains nickel manganese presoma；
(3) it is calcined after mixing the nickel manganese presoma with lithium carbonate, obtains nickel lithium manganate cathode material.
3. preparation method according to claim 2, which is characterized in that the molar ratio of the nickel nitrate and glycine is 1:10
~15.
4. preparation method according to claim 2, which is characterized in that the strong base solution is sodium hydroxide and/or hydrogen-oxygen
Change the aqueous solution of potassium.
5. preparation method according to claim 4, which is characterized in that a concentration of 5~8mol/ of alkali in the strong base solution
L；The ratio between the amount of the substance of the nickel nitrate and the volume of strong base solution are 1mmol:3~5mL.
6. preparation method according to claim 2, which is characterized in that the temperature of the hydro-thermal reaction is 120~160 DEG C,
The time of the hydro-thermal reaction is 20~26h.
7. preparation method according to claim 2, which is characterized in that the calcining includes the first calcining and the second calcining；
The temperature of first calcining is 300~400 DEG C, and the time of first calcining is 2~3h；It is described second calcining temperature be
800~850 DEG C, the time of second calcining is 6~8h.
8. preparation method according to claim 7, which is characterized in that be warming up to the first calcining and be warming up to the second calcining institute
The heating rate of temperature is needed independently to be 100~150 DEG C/h.
9. preparation method according to claim 2, which is characterized in that the lithium atom in the lithium carbonate and nickel nitrate, nitre
The molar ratio of sour manganese is 1.03~1.06:0.5:1.5.
10. the preparation method according to claim 2 or 9, which is characterized in that the grinding that is mixed into the step (4) mixes
It closes.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109935827A (en) * | 2019-03-25 | 2019-06-25 | 合肥学院 | A kind of preparation method of nano bar-shape nickel ion doped and its application in cell positive material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000228196A (en) * | 1998-11-30 | 2000-08-15 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery |
| CN103943848A (en) * | 2014-04-23 | 2014-07-23 | 合肥工业大学 | Preparation method of positive pole material of cobalt-based lithium ion battery with porous rod-like structure |
| CN103985854A (en) * | 2014-04-14 | 2014-08-13 | 江苏中欧材料研究院有限公司 | Preparation method of nanoscale nickel lithium manganate positive pole material |
| CN104409717A (en) * | 2014-11-06 | 2015-03-11 | 奇瑞汽车股份有限公司 | Nano rod-shaped nickel-lithium manganate cathode material and preparation method thereof |
| CN104966830A (en) * | 2015-05-25 | 2015-10-07 | 哈尔滨工业大学 | Preparation method and application of rod-shaped lithium nickel manganese oxide material |
| CN106505186A (en) * | 2016-11-28 | 2017-03-15 | 湖南大学 | A kind of lithium iron phosphate positive material of in-stiu coating graphene film and preparation method thereof |
-
2018
- 2018-03-21 CN CN201810234855.9A patent/CN108417830B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000228196A (en) * | 1998-11-30 | 2000-08-15 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery |
| CN103985854A (en) * | 2014-04-14 | 2014-08-13 | 江苏中欧材料研究院有限公司 | Preparation method of nanoscale nickel lithium manganate positive pole material |
| CN103943848A (en) * | 2014-04-23 | 2014-07-23 | 合肥工业大学 | Preparation method of positive pole material of cobalt-based lithium ion battery with porous rod-like structure |
| CN104409717A (en) * | 2014-11-06 | 2015-03-11 | 奇瑞汽车股份有限公司 | Nano rod-shaped nickel-lithium manganate cathode material and preparation method thereof |
| CN104966830A (en) * | 2015-05-25 | 2015-10-07 | 哈尔滨工业大学 | Preparation method and application of rod-shaped lithium nickel manganese oxide material |
| CN106505186A (en) * | 2016-11-28 | 2017-03-15 | 湖南大学 | A kind of lithium iron phosphate positive material of in-stiu coating graphene film and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109935827A (en) * | 2019-03-25 | 2019-06-25 | 合肥学院 | A kind of preparation method of nano bar-shape nickel ion doped and its application in cell positive material |
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