CN107946579A - A kind of nickel cobalt lithium aluminate cathode material of LiMn2O4 cladding and preparation method thereof - Google Patents
A kind of nickel cobalt lithium aluminate cathode material of LiMn2O4 cladding and preparation method thereof Download PDFInfo
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- 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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- 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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- Y02E60/10—Energy storage using batteries
Abstract
A kind of nickel cobalt lithium aluminate cathode material of LiMn2O4 cladding and preparation method thereof, the mass percentage of LiMn2O4 is 1~10wt% in the material, and the clad that LiMn2O4 forms 2~20nm of thickness is coated on nickel cobalt lithium aluminate；The positive electrode is the spheric granules of 5~15 μm of particle diameter.The method, comprises the following steps：（1）Surfactant is soluble in water, heating stirring；（2）Manganese source is added, after stirring and dissolving, adds nickel cobalt aluminum hydroxide, heating stirring, is evaporated；（3）Calcined, cooled down in air atmosphere；（4）Lithium salts is added, under the oxidizing atmosphere of flowing, carries out double sintering,.Positive electrode of the present invention has preferable cyclical stability and big multiplying power discharging property, and clad can stabilizing material structure, the effectively side reaction between suppression electrolyte and active material；The method of the present invention cost is low, and technique is simple, is suitable for big industrial production.
Description
Technical field
The present invention relates to a kind of positive electrode and preparation method thereof, and in particular to a kind of nickel cobalt lithium aluminate of LiMn2O4 cladding
Positive electrode and preparation method thereof.
Background technology
Lithium ion battery has voltage stabilization, capacity height, energy density is big, self discharge is few, has extended cycle life, is environmental-friendly
Etc. advantage, it is widely used in the fields such as electric car, electric tool, mobile phone, laptop.From mobile equipment to electric vehicle,
Continuous with energy-storage system application expands, and the demand of lithium ion battery with high energy density is also being increased, and lithium ion battery
Middle positive electrode be determine performance of lithium ion battery critical material, high-energy-density, long circulation life and high security cathode material
Material becomes the hot spot researched and developed and paid close attention in countries in the world.
Rich nickel high capacity type positive electrode, such as LiNi0.8Co0.15Al0.05O2, since such material has high power capacity and valency
The advantages that lattice are cheap, its application in lithium ion battery have received widespread attention.Higher Ni contents in the structure of the material
Although higher specific capacity can be obtained, with the increase of Ni contents, material is shown since cation mixing and surface are anti-
Should, so that decay and thermal instability caused by accelerating, particularly at elevated temperatures, the ill-effect is more obvious.Pin
To disadvantage mentioned above, many researchers are coated by using surface（Metal oxide, metal phosphate etc.）To improve its circulation
Stability.
For example CN106711444A discloses a kind of preparation side for the nickel cobalt lithium aluminate cathode material that in-stiu coating is modified
Method, CN106910881A disclose a kind of preparation method of metatitanic acid lithium cladding nickel cobalt lithium aluminate cathode material, employ original
Position cladding nickel cobalt lithium aluminate, is mixed by covering material and lithium source while with presoma, and dinectly bruning after drying.But
So operation may be such that clad is uneven, influence chemical property.
The content of the invention
The technical problems to be solved by the invention are to overcome drawbacks described above existing in the prior art, there is provided one kind utilizes table
Face cation mixing form stable entablature suppress surface reaction, specific capacity and cycle performance it is excellent LiMn2O4 cladding
Nickel cobalt lithium aluminate cathode material.
Further technical problems to be solved of the invention are to overcome drawbacks described above existing in the prior art, there is provided Yi Zhongcheng
This is low, and technique is simple, is suitable for the preparation method of the nickel cobalt lithium aluminate cathode material of big industrial LiMn2O4 cladding.
The technical solution adopted by the present invention to solve the technical problems is as follows：A kind of nickel cobalt lithium aluminate of LiMn2O4 cladding is just
Pole material, the mass percentage of the LiMn2O4 is 1~10wt%, and the clad that LiMn2O4 forms 2~20nm of thickness is coated on
On nickel cobalt lithium aluminate；The positive electrode is the spheric granules of 5~15 μm of particle diameter.
Preferably, the LiMn2O4 is LiMn2O4、LiMnO2、Li2MnO3Or LiMn3O4One or more in.
Technical solution is used by the present invention further solves its technical problem：A kind of nickel cobalt aluminic acid of LiMn2O4 cladding
The preparation method of lithium anode material, comprises the following steps：
（1）Surfactant is soluble in water, and heating stirring, obtains surfactant solution；
（2）In step（1）Add manganese source in gained surfactant solution, after stirring and dissolving, add nickel cobalt aluminum hydroxide, add
Thermal agitation, stirs under the conditions of oil bath and is evaporated, and obtains the nickel cobalt aluminum hydroxide presoma of manganese source cladding；
（3）By step（2）The nickel cobalt aluminum hydroxide presoma of gained manganese source cladding is calcined in air atmosphere, natural cooling
To room temperature, the cobalt nickel oxide aluminium presoma that manganese oxide coats is obtained；
（4）In step（3）Lithium salts is added in the cobalt nickel oxide aluminium presoma of gained manganese oxide cladding, in the oxidizing atmosphere of flowing
Under, double sintering is carried out, obtains the nickel cobalt lithium aluminate cathode material of LiMn2O4 cladding.
Preferably, step（1）In, the mass volume ratio of the surfactant and water（g/mL）For 2~10:100（It is more excellent
Select 4~6:100）.
Preferably, step（1）In, the temperature of the heating stirring is 30~60 DEG C, and the time is 12~20h.
Preferably, step（1）In, the surfactant is polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol or poly-
One or more in acrylamide etc..The manganese source or nickel cobalt aluminum hydroxide of the dispersible reunion of addition of water soluble surfactant active
Solid particle, is more advantageous to subsequently that manganese salt uniformly coats nickel cobalt aluminum hydroxide under liquid phase environment.
Preferably, step（2）In, the mass volume ratio of the nickel cobalt aluminum hydroxide and surfactant solution（g/mL）For
2~10:100.If the ratio is excessive, it is unfavorable for the scattered of nickel cobalt aluminum hydroxide.
Preferably, step（2）In, the molar ratio of manganese atom and nickel cobalt aluminum hydroxide is 2~30 in the manganese source:100（More
It is preferred that 2.2~12.0:100）.
Preferably, step（2）In, the manganese source is manganese acetate, manganese chloride, manganese nitrate or manganese sulfate, and its hydrate etc.
In one or more.
Preferably, step（2）In, the particle diameter of the nickel cobalt aluminum hydroxide is 5~15 μm.
Preferably, step（2）In, the temperature of the heating stirring reaction is 30~60 DEG C, and the time is 12~20h.Heating
Stirring reaction can promote the dissolving of manganese salt.
Preferably, step（2）In, the temperature being evaporated that stirs is 100~150 DEG C（More preferably 120~140 DEG C）.Adopt
Being evaporated with stirring can effectively prevent from reuniting than other drying modes.
Preferably, step（3）In, the calcining refers to：450~500 DEG C are warming up to the speed of 3~5 DEG C/min, calcining
4~6h.The effect of calcining is manganese salt is oxidized to manganese oxide, is so more advantageous to before it is uniformly coated on cobalt nickel oxide aluminium
Body surface face is driven, the temperature is more advantageous to the oxidation of manganese salt.
Preferably, step（4）In, the addition of the lithium salts cause the molal quantity of lithium in lithium salts=（0.2~2.0）* manganese source
The molal quantity of middle manganese+（1.01~1.10）* the molal quantity of nickel cobalt aluminum hydroxide.
Preferably, step（4）In, the lithium salts is lithium carbonate, lithium hydroxide, lithium nitrate or lithium acetate, and its hydrate
One or more in.Lithium salts should form nickel cobalt lithium aluminate with cobalt nickel oxide reactive aluminum and be nucleated matrix as positive electrode,
React to form LiMn2O4 with manganese source again.Calcining for the first time primarily to form manganese oxide and be coated on cobalt nickel oxide aluminium,
Then add lithium salts and be sintered reaction, to obtain positive electrode, therefore, row addition again after lithium salts is calcined in first time.
Preferably, step（4）In, the oxidizing atmosphere refers to the oxygen of ozone atmosphere, air atmosphere or purity >=99.9%
Gas atmosphere.
Preferably, step（4）In, the speed of the flowing is 0.05~0.10m3/h。
Preferably, step（4）In, the double sintering refers to：First 400~550 are warming up to the speed of 3~5 DEG C/min
DEG C, sinter 3~8h（More preferably 4~6h）, then with the speed of 3~5 DEG C/min it is warming up to 700~850 DEG C, sinter 10~20h（More
It is preferred that 15~18h）.The method of the present invention utilizes the diffusion rate difference of manganese and lithium at high temperature, and shell structure is formed by sintering,
I.e. when first segment sinters, lithium salts melts, and diffuses into cobalt nickel oxide aluminum substrate, when second segment sinters, lithium salts and oxidation
Nickel cobalt reactive aluminum generates nickel cobalt lithium aluminate, and lithium salts and manganese oxide reaction generation LiMn2O4 are wrapped in the surface of nickel cobalt lithium aluminate.Control
Heating rate processed primarily to control second particle in primary particle gap, avoid causing physical property to drop because gap is excessive
It is low.
The molecular formula of sodium hydroxide nickel cobalt aluminium of the present invention is Ni0.8Co0.15Al0.05(OH)2, the nickel cobalt lithium aluminate
Molecular formula is LiNi0.8Co0.15Al0.05O2。
The principle of the present invention is：The present invention is using nickel cobalt aluminum hydroxide as matrix, first by manganese source surfactant-dispersed,
Under liquid phase environment, it is evaporated and is coated on nickel cobalt aluminum hydroxide particle by stirring, then by calcined oxide into manganese oxide, in its table
Face closely deposits, finally by gained powder body material by double sintering, during nickel cobalt lithium aluminate is generated, while in its table
Face generates LiMn2O4, finally obtains the nickel cobalt aluminic acid anode material of lithium battery of LiMn2O4 cladding.LiMn2O4 coats nickel cobalt lithium aluminate
Afterwards, surface can generate Mn during charge and discharge cycles4+, in order to keep valence state to balance, promote nickel to be changed into Ni2+, such surface meeting
The nano-pillars layer due to nickel lithium mixing formation is formed with rock-steady structure, furthermore it is also possible to effectively suppress electrolyte and active matter
Side reaction between matter, improves its cyclical stability.
Beneficial effects of the present invention are as follows：
（1）In the nickel cobalt lithium aluminate cathode material of LiMn2O4 cladding of the present invention, LiMn2O4 forms the clad of 2~20nm of thickness,
The positive electrode is the spheric granules of 5~15 μm of particle diameter；
（2）The nickel cobalt lithium aluminate cathode material that LiMn2O4 of the present invention coats is assembled into battery, it is first under 2.7~4.3V, 0.1C
Secondary electric discharge gram volume may be up to 209.7mAh/g；The gram volume that discharges first under 1C may be up to 184.4mAh/g, the circle of circulation 100
Afterwards, capacity retention ratio may be up to 84.1%；Respectively under the multiplying power of 0.5C, 1C, 2C, 5C, discharge capacity may be up to respectively first
196.3mAh/g, 184.4mAh/g, 167.8mAh/g, 139.7mAh/g, illustrate the nickel cobalt lithium aluminate of LiMn2O4 cladding of the present invention
Positive electrode has preferable cyclical stability and big multiplying power discharging property；
（3）The method of the present invention after coated manganese oxide, causes in nickel cobalt aluminic acid on nickel cobalt lithium aluminate in electrochemistry cyclic process
Lithium surface forms the nano-pillars layer due to nickel lithium mixing formation with rock-steady structure, can also effectively suppress electrolyte and active material
Between side reaction, improve its cyclical stability；
（4）The method of the present invention cost is low, and technique is simple, is suitable for big industrial production.
Brief description of the drawings
Fig. 1 is 1 gained Li of the embodiment of the present invention2MnO3/LiNi0.8Co0.15Al0.05O2The SEM figures of positive electrode；
Fig. 2 is 1 gained Li of the embodiment of the present invention2MnO3/LiNi0.8Co0.15Al0.05O2The TEM figures of positive electrode；
Fig. 3 is 1 gained Li of the embodiment of the present invention2MnO3/LiNi0.8Co0.15Al0.05O2The XRD figures of positive electrode；
Fig. 4 is 1 gained LiNi of comparative example of the present invention0.8Co0.15Al0.05O2The SEM figures of positive electrode；
The capacity circulating that Fig. 5 is the embodiment of the present invention 1 with the battery of 1 gained positive electrode of comparative example assembling under 1C multiplying powers contrasts
Figure.
Embodiment
With reference to embodiment and attached drawing, the invention will be further described.
Nickel cobalt aluminum hydroxide used in the embodiment of the present invention is purchased from Ningbo Jinhe New Materials Co., Ltd., and particle diameter is
5~15 μm；Chemical reagent used in the embodiment of the present invention, unless otherwise specified, is obtained by routine business approach.
Embodiment 1
A kind of nickel cobalt lithium aluminate cathode material of LiMn2O4 cladding：
Li2MnO3Mass percentage be 3wt%, Li2MnO3The clad for forming thickness 3nm is coated on nickel cobalt lithium aluminate；
The positive electrode be 5~15 μm of particle diameter spheric granules, molecular formula Li2MnO3/LiNi0.8Co0.15Al0.05O2。
As shown in Figure 1, the nickel cobalt lithium aluminate cathode material of LiMn2O4 cladding is 5~15 μm of particle diameter obtained by the embodiment of the present invention
Spheric granules, there is LiMn2O4 clad on surface.
As shown in Fig. 2, the body portion of the nickel cobalt lithium aluminate cathode material of LiMn2O4 cladding is obtained by the embodiment of the present invention
Nickel cobalt lithium aluminate, its surface form the LiMn2O4 clad that thickness is 3nm.
As shown in figure 3,006 and 102,108 being separated substantially with 110 faces in XRD data, illustrate manganese obtained by the embodiment of the present invention
The nickel cobalt lithium aluminate cathode material layer structure of sour lithium cladding is obvious, does not have to destroy nickel cobalt lithium aluminate after the cladding LiMn2O4 of surface
Layer structure.
A kind of preparation method of the nickel cobalt lithium aluminate cathode material of LiMn2O4 cladding：
（1）2g polyvinylpyrrolidones are dissolved in 50mL deionized waters, at 50 DEG C, 12h is stirred, it is molten to obtain surfactant
Liquid；
（2）In step（1）0.3024g is added in gained surfactant solution（1.234mmol）Four water manganese acetates, stirring and dissolving
Afterwards, 4.589g is added（50mmol）Nickel cobalt aluminum hydroxide, at 50 DEG C, stirs 12h, stirs and be evaporated under 120 DEG C of oil bath,
Obtain the nickel cobalt aluminum hydroxide presoma of manganese source cladding；
（3）By step（2）The nickel cobalt aluminum hydroxide presoma of gained manganese source cladding is in air atmosphere, with the speed of 5 DEG C/min
450 DEG C are warming up to, calcines 6h, cooled to room temperature, obtains manganese oxide cladding cobalt nickel oxide aluminium presoma；
（4）In step（3）2.313g is added in the cobalt nickel oxide aluminium presoma of gained manganese oxide cladding（31.3mmol）Li2CO3,
It is placed in tube furnace, with 0.05m3Under the oxygen atmosphere of purity >=99.9% of/h flowings, first heated up with the speed of 5 DEG C/min
To 480 DEG C, 5h is sintered, then 780 DEG C are warming up to the speed of 5 DEG C/min, 15h is sintered, obtains Li2MnO3/
LiNi0.8Co0.15Al0.05O2Positive electrode.
The assembling of battery：Weigh Li obtained by the 0.4g embodiment of the present invention2MnO3/LiNi0.8Co0.15Al0.05O2Positive electrode,
Add 0.05g acetylene blacks and make conductive agent and 0.05 g PVDF（Kynoar）Make binding agent, be applied to after mixing on aluminium foil
Positive plate is made, is membrane with Celgard 2300 using metal lithium sheet as anode in vacuum glove box, 1mol/L LiPF6/
EC:DMC（Volume ratio 1:1）For electrolyte, CR2025 button cells are assembled into.
After testing, the battery assembled is in 2.7~4.3V voltage ranges, and under 0.1C multiplying powers, first discharge specific capacity is
209.7mAh/g。
As shown in figure 5, the battery assembled, in 2.7~4.3V voltage ranges, under 1C multiplying powers, first discharge specific capacity is
184.4mAh/g, the circle of circulation 100, capacity retention ratio 83.2%.
After testing, the battery assembled is in 2.7~4.3 V voltage ranges, respectively in the multiplying power of 0.5C, 1C, 2C, 5C
Under, discharge capacity is respectively 193.2mAh/g, 184.4mAh/g, 163.1mAh/g, 139.2mAh/g first.
Embodiment 2
A kind of nickel cobalt lithium aluminate cathode material of LiMn2O4 cladding：
LiMnO2Mass percentage be 8wt%, LiMnO2The clad for forming thickness 6nm is coated on nickel cobalt lithium aluminate；Institute
State the spheric granules that positive electrode is 5~15 μm of particle diameter, molecular formula LiMnO2/LiNi0.8Co0.15Al0.05O2。
After testing, the nickel cobalt lithium aluminate cathode material of LiMn2O4 cladding is 5~15 μm of particle diameter obtained by the embodiment of the present invention
There is LiMn2O4 clad on spheric granules, surface.
After testing, the body portion of the nickel cobalt lithium aluminate cathode material of LiMn2O4 cladding is nickel cobalt obtained by the embodiment of the present invention
Lithium aluminate, its surface form the LiMn2O4 clad that thickness is 6nm.
After testing, 006 and 102,108 separated substantially with 110 faces in XRD data, illustrate mangaic acid obtained by the embodiment of the present invention
The nickel cobalt lithium aluminate cathode material layer structure of lithium cladding is obvious, does not have the layer for destroying nickel cobalt lithium aluminate after the cladding LiMn2O4 of surface
Shape structure.
A kind of preparation method of the nickel cobalt lithium aluminate cathode material of LiMn2O4 cladding：
（1）3g polyvinyl alcohol is dissolved in 60mL deionized waters, at 50 DEG C, 15h is stirred, obtains surfactant solution；
（2）In step（1）0.728g is added in gained surfactant solution（4.5mmol）Two chloride hydrate manganese, stirring and dissolving
Afterwards, 5.048g is added（55mmol）Nickel cobalt aluminum hydroxide, at 50 DEG C, stirs 13h, stirs and be evaporated under 120 DEG C of oil bath,
Obtain the nickel cobalt aluminum hydroxide presoma of manganese source cladding；
（3）By step（2）The nickel cobalt aluminum hydroxide presoma of gained manganese source cladding is in air atmosphere, with the speed of 5 DEG C/min
480 DEG C are warming up to, calcines 5h, cooled to room temperature, obtains the cobalt nickel oxide aluminium presoma that manganese oxide coats；
（4）In step（3）2.631g is added in the cobalt nickel oxide aluminium presoma of gained manganese oxide cladding（62.7mmol）LiOH·
H2O, is placed in tube furnace, with 0.08m3Under the oxygen atmosphere of purity >=99.9% of/h flowings, first with the speed liter of 5 DEG C/min
Temperature sinters 5h to 500 DEG C, then is warming up to 800 DEG C with the speed of 5 DEG C/min, sinters 18h, obtains LiMnO2/
LiNi0.8Co0.15Al0.05O2Positive electrode.
The assembling of battery：Weigh LiMnO obtained by the 0.4g embodiment of the present invention2/LiNi0.8Co0.15Al0.05O2Positive electrode,
Add 0.05g acetylene blacks and make conductive agent and 0.05 g PVDF（Kynoar）Make binding agent, be applied to after mixing on aluminium foil
Positive plate is made, is membrane with Celgard 2300 using metal lithium sheet as anode in vacuum glove box, 1mol/L LiPF6/
EC:DMC（Volume ratio 1:1）For electrolyte, CR2025 button cells are assembled into.
After testing, the battery assembled is in 2.7~4.3V voltage ranges, and under 0.1C multiplying powers, first discharge specific capacity is
200.8mAh/g。
After testing, the battery assembled is in 2.7~4.3V voltage ranges, and under 1C multiplying powers, first discharge specific capacity is
179.8mAh/g, the circle of circulation 100, capacity retention ratio 84.1%.
After testing, the battery assembled is in 2.7~4.3V voltage ranges, respectively under the multiplying power of 0.5C, 1C, 2C, 5C,
Discharge capacity is respectively 191.4mAh/g, 179.8mAh/g, 167.8mAh/g, 139.7mAh/g first.
Embodiment 3
A kind of nickel cobalt lithium aluminate cathode material of LiMn2O4 cladding：
LiMn2O4Mass percentage be 10wt%, LiMn2O4The clad for forming thickness 15nm is coated on nickel cobalt lithium aluminate
On；The positive electrode be 5~15 μm of particle diameter spheric granules, molecular formula LiMn2O4/LiNi0.8Co0.15Al0.05O2。
After testing, the nickel cobalt lithium aluminate cathode material of LiMn2O4 cladding is 5~15 μm of particle diameter obtained by the embodiment of the present invention
There is LiMn2O4 clad on spheric granules, surface.
After testing, the body portion of the nickel cobalt lithium aluminate cathode material of LiMn2O4 cladding is nickel cobalt obtained by the embodiment of the present invention
Lithium aluminate, its surface form the LiMn2O4 clad that thickness is 15nm.
After testing, 006 and 102,108 separated substantially with 110 faces in XRD data, illustrate mangaic acid obtained by the embodiment of the present invention
The nickel cobalt lithium aluminate cathode material layer structure of lithium cladding is obvious, does not have the layer for destroying nickel cobalt lithium aluminate after the cladding LiMn2O4 of surface
Shape structure.
A kind of preparation method of the nickel cobalt lithium aluminate cathode material of LiMn2O4 cladding：
（1）5g polyethylene glycol is dissolved in 100mL deionized waters, at 40 DEG C, 20h is stirred, obtains surfactant solution；
（2）In step（1）1.302g is added in gained surfactant solution（5.314mmol）Four water manganese acetates, stirring and dissolving
Afterwards, 4.589g is added（50mmol）Nickel cobalt aluminum hydroxide, at 40 DEG C, stirs 15h, stirs and be evaporated under 130 DEG C of oil bath,
Obtain the nickel cobalt aluminum hydroxide presoma of manganese source cladding；
（3）By step（2）The nickel cobalt aluminum hydroxide presoma of gained manganese source cladding is in air atmosphere, with the speed of 4 DEG C/min
500 DEG C are warming up to, calcines 4h, cooled to room temperature, obtains the cobalt nickel oxide aluminium presoma that manganese oxide coats；
（4）In step（3）2.039g is added in the cobalt nickel oxide aluminium presoma of gained manganese oxide cladding（27.6mmol）Li2CO3,
It is placed in tube furnace, with 0.1m3Under the air atmosphere of/h flowings, 550 DEG C first are warming up to the speed of 4 DEG C/min, sinters 4h,
820 DEG C are warming up to the speed of 4 DEG C/min again, 18h is sintered, obtains LiMn2O4/LiNi0.8Co0.15Al0.05O2Positive electrode.
The assembling of battery：Weigh LiMn obtained by the 0.4g embodiment of the present invention2O4/LiNi0.8Co0.15Al0.05O2Positive electrode,
Add 0.05g acetylene blacks and make conductive agent and 0.05 g PVDF（Kynoar）Make binding agent, be applied to after mixing on aluminium foil
Positive plate is made, is membrane with Celgard 2300 using metal lithium sheet as anode in vacuum glove box, 1mol/L LiPF6/
EC:DMC（Volume ratio 1:1）For electrolyte, CR2025 button cells are assembled into.
After testing, the battery assembled is in 2.7~4.3 V voltage ranges, and under 0.1C multiplying powers, first discharge specific capacity is
204.2mAh/g。
After testing, the battery assembled is in 2.7~4.3 V voltage ranges, and under 1C multiplying powers, first discharge specific capacity is
180.7mAh/g, the circle of circulation 100, capacity retention ratio 82.9%.
After testing, the battery assembled is in 2.7~4.3 V voltage ranges, respectively in the multiplying power of 0.5C, 1C, 2C, 5C
Under, discharge capacity is respectively 196.3mAh/g, 180.7mAh/g, 163.9mAh/g, 134.2mAh/g first.
Comparative example 1
In 4.589g（50mmol）2.313g is added in nickel cobalt aluminum hydroxide（31.3mmol）Li2CO3, it is placed in tube furnace,
With 0.05m3Under the oxygen atmosphere of purity >=99.9% of/h flowings, 480 DEG C first are warming up to the speed of 5 DEG C/min, sinters 5h,
780 DEG C are warming up to the speed of 5 DEG C/min again, 15h is sintered, obtains LiNi0.8Co0.15Al0.05O2Positive electrode.
The assembling of battery：Weigh nickel cobalt lithium aluminate cathode material obtained by 0.4g, add 0.05g acetylene blacks make conductive agent and
0.05 g PVDF（Kynoar）Make binding agent, be applied on aluminium foil positive plate is made after mixing, in vacuum glove box
It is membrane with Celgard 2300 using metal lithium sheet as anode, 1mol/L LiPF6/EC:DMC（Volume ratio 1:1）For electrolysis
Liquid, is assembled into CR2025 button cells.
As shown in figure 4, nickel cobalt lithium aluminate cathode material obtained by comparative example of the present invention is the spheric granules of 5~15 μm of particle diameter.
After testing, the battery assembled is in 2.7~4.3V voltage ranges, and under 0.1C multiplying powers, first discharge specific capacity is
201.4mAh/g。
As shown in figure 5, the battery assembled, in 2.7~4.3V voltage ranges, under 1C multiplying powers, first discharge specific capacity is
180.4mAh/g, the circle of circulation 100, capacity retention ratio 64.4%.
After testing, the battery assembled is in 2.7~4.3V voltage ranges, respectively under the multiplying power of 0.5C, 1C, 2C, 5C,
Discharge capacity is respectively 194.3mAh/g, 180.4mAh/g, 158.9mAh/g, 128.4mAh/g first.
To sum up, LiMn2O4 can be equably coated on nickel cobalt lithium aluminate by the method for the present invention, more uncoated LiMn2O4
Nickel cobalt lithium aluminate, effectively raises the circulation conservation rate of the material and big multiplying power discharging property, and technique is simple, is suitable for big
Industrial production.
Claims (10)
- A kind of 1. nickel cobalt lithium aluminate cathode material of LiMn2O4 cladding, it is characterised in that：The mass percentage of the LiMn2O4 For 1~10wt%, the clad that LiMn2O4 forms 2~20nm of thickness is coated on nickel cobalt lithium aluminate；The positive electrode is particle diameter 5~15 μm of spheric granules.
- 2. the nickel cobalt lithium aluminate cathode material of LiMn2O4 cladding according to claim 1, it is characterised in that：The LiMn2O4 is LiMn2O4、LiMnO2、Li2MnO3Or LiMn3O4In one or more.
- 3. a kind of preparation method of the nickel cobalt lithium aluminate cathode material of the cladding of LiMn2O4 as claimed in claim 1 or 2, its feature exist In comprising the following steps：（1）Surfactant is soluble in water, and heating stirring, obtains surfactant solution；（2）In step（1）Add manganese source in gained surfactant solution, after stirring and dissolving, add nickel cobalt aluminum hydroxide, add Thermal agitation, stirs under the conditions of oil bath and is evaporated, and obtains the nickel cobalt aluminum hydroxide presoma of manganese source cladding；（3）By step（2）The nickel cobalt aluminum hydroxide presoma of gained manganese source cladding is calcined in air atmosphere, natural cooling To room temperature, the cobalt nickel oxide aluminium presoma that manganese oxide coats is obtained；（4）In step（3）Lithium salts is added in the cobalt nickel oxide aluminium presoma of gained manganese oxide cladding, in the oxidizing atmosphere of flowing Under, double sintering is carried out, obtains the nickel cobalt lithium aluminate cathode material of LiMn2O4 cladding.
- 4. the preparation method of the nickel cobalt lithium aluminate cathode material of LiMn2O4 cladding according to claim 3, it is characterised in that：Step Suddenly（1）In, the mass volume ratio of the surfactant and water is 2~10:100；The temperature of the heating stirring is 30~60 DEG C, the time is 12~20h；The surfactant is polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol or polyacrylamide In one or more.
- 5. the preparation method of the nickel cobalt lithium aluminate cathode material coated according to the LiMn2O4 of claim 3 or 4, its feature exist In：Step（2）In, the mass volume ratio of the nickel cobalt aluminum hydroxide and surfactant solution is 2~10:100；The manganese source The molar ratio of middle manganese atom and nickel cobalt aluminum hydroxide is 2~30:100；The manganese source is manganese acetate, manganese chloride, manganese nitrate or sulphur Sour manganese, and its one or more in hydrate；The particle diameter of the nickel cobalt aluminum hydroxide is 5~15 μm.
- 6. the preparation method of the nickel cobalt lithium aluminate cathode material coated according to one of claim 3~5 LiMn2O4, its feature It is：Step（2）In, the temperature of the heating stirring reaction is 30~60 DEG C, and the time is 12~20h；It is described to stir what is be evaporated Temperature is 100~150 DEG C.
- 7. the preparation method of the nickel cobalt lithium aluminate cathode material coated according to one of claim 3~6 LiMn2O4, its feature It is：Step（3）In, the calcining refers to：450~500 DEG C are warming up to the speed of 3~5 DEG C/min, calcines 4~6h.
- 8. the preparation method of the nickel cobalt lithium aluminate cathode material coated according to one of claim 3~7 LiMn2O4, its feature It is：Step（4）In, the addition of the lithium salts cause the molal quantity of lithium in lithium salts=（0.2~2.0）* in manganese source manganese mole Number+（1.01~1.10）* the molal quantity of nickel cobalt aluminum hydroxide；The lithium salts is lithium carbonate, lithium hydroxide, lithium nitrate or acetic acid One or more in lithium, and its hydrate.
- 9. the preparation method of the nickel cobalt lithium aluminate cathode material coated according to one of claim 3~8 LiMn2O4, its feature It is：Step（4）In, the oxidizing atmosphere refers to the oxygen atmosphere of ozone atmosphere, air atmosphere or purity >=99.9%；Institute The speed for stating flowing is 0.05~0.10m3/h。
- 10. the preparation method of the nickel cobalt lithium aluminate cathode material coated according to one of claim 3~9 LiMn2O4, it is special Sign is：Step（4）In, the double sintering refers to：400~550 DEG C first are warming up to the speed of 3~5 DEG C/min, sintering 3 ~8h, then 700~850 DEG C are warming up to the speed of 3~5 DEG C/min, sinter 10~20h.
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