CN106549147B - Nickle cobalt lithium manganate that a kind of two-dimension nano materials are fixed and preparation method and application - Google Patents
Nickle cobalt lithium manganate that a kind of two-dimension nano materials are fixed and preparation method and application Download PDFInfo
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Abstract
Nickle cobalt lithium manganate fixed the invention provides a kind of two-dimension nano materials and preparation method and application.The nickle cobalt lithium manganate that the two-dimension nano materials are fixed is to be stacked to be combined in a manner of interlayer by the nickle cobalt lithium manganate of two-dimension nano materials and spherical structure, and the nickle cobalt lithium manganate of spherical structure is accumulated in the template of two-dimension nano materials with the pattern of Rotating fields.Tightly packed, tap density and energy density of the raising nickle cobalt lithium manganate as positive electrode can be realized；And the nickle cobalt lithium manganate surface of spherical structure is smooth, specific surface area is low, it is possible to reduce the generation with electrolyte side reaction, improves the first charge-discharge efficiency of lithium ion battery；Nickle cobalt lithium manganate is accumulated to form secondary spherical particle in the template of two-dimension nano materials with the pattern of Rotating fields, and the two-dimension nano materials can suppress Li+The defects of dislocation occurs during deintercalation in the layered structure, further improves the deintercalation ability of lithium ion, and can improve the electric conductivity of nickle cobalt lithium manganate and improve its charge-discharge performance.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries technical field, is related to the nickel cobalt manganese that a kind of two-dimension nano materials are fixed
Sour lithium and preparation method and application.
Background technology
With the fast development of power vehicle, lithium ion battery occupies leading position in power vehicle.In lithium ion
In electrokinetic cell industrialization promotion, the requirement to battery capacity, security, integrated cost is higher, and positive electrode turns into main bottle
Neck.At present, anode material for lithium-ion batteries mainly has cobalt acid lithium, lithium nickelate, LiMn2O4, LiFePO4, nickle cobalt lithium manganate ternary
Deng.Wherein LiFePO4（LiFePO4）Had a safety feature with it, cycle performance is excellent, environment-friendly, raw material sources are abundant, into
This low advantage and as the main positive electrode of lithium ion battery.However, LiFePO4（LiFePO4）As lithium battery anode
Material, however it remains defect, the electronic conductivity that is mainly manifested in LiFePO4 is poor, chargeable voltage is relatively low, is low
Temperature stability is poor, tap density is small, the electric energy stored by unit volume battery is less.At present, the energy density of LiFePO4 reaches
Summit is arrived, improved space is little.New material substitution is had to look for, new-energy automobile power battery could obtain great prominent
It is broken.
It has been studied that, the relatively low theoretical gram volume of the ratio energy of ferric phosphate lithium cell, only 170mAh/g, operating voltage is
3.2V, and the theoretical gram volume of cobalt nickel lithium manganate ternary material is then 278mAh/g, operating voltage 3.65V, therefore nickel cobalt manganese
Ternary battery energy density is apparently higher than ferric phosphate lithium cell.Nevertheless, nickel-cobalt-manganese ternary battery safety and cyclicity
Can be not as good as ferric phosphate lithium cell, this just constrains the application with high-energy-density ternary battery.The defects of its is maximum be
Occur self-heating more than 180 DEG C, cyclical stability is poor.And exothermic phenomenon just occurs in more than 250 DEG C of LiFePO 4 material.
When stratiform nickle cobalt lithium manganate is as tertiary cathode material, due to the cooperative effect of tri- kinds of elements of Ni, Co and Mn, tool
Have that specific discharge capacity is high, energy density is high, cost is relatively low and advantages of environment protection, combine LiCoO2, LiNiO2With
LiMnO2The advantages of three kinds of anode material for lithium-ion batteries, and performance is better than the positive electrode of any of the above one-component.The body
In system, the chemical property and physical property of material are different with the change of these three transition metal ratios.Introduce Ni,
Although being favorably improved the capacity of material, there is Li in stratiform cell positive material+Dislocation occurs with transition metal ions
Trend, Ni2+Meeting and Li during too high levels+Mixing, cycle performance is deteriorated because of dislocation phenomenon.Introducing Co can be reduced
Cation mixing occupy-place, the layer structure of effective stabilizing material, impedance value is reduced, improve electrical conductivity, but when the increasing of Co ratios
It is big to a and c can be caused to reduce and c/a increases during certain limit, capacity step-down.Mn is introduced, can not only reduce material cost, and
And the safety and stability of material can also be improved.
But due to the limitation of its preparation technology and self structure performance, ternary material LiNi1/3Co1/3Mn1/3O2As lithium from
Sub- cell positive material is in use, high rate performance still has sizable room for promotion.LiNi1/3Co1/3Mn1/3O2High rate performance compared with
Difference mainly has following reason：（1）LiNi1/3Co1/3Mn1/3O2It is a kind of ternary transition metal combined oxidation with layer structure
Thing crystalline material, influenceed that " cation mixing ", i.e. LiNi easily occurs by preparation technology1/3Co1/3Mn1/3O2In crystal structure
Part Ni2+Li can be occupied+Position, cause crystal partial structurtes to be caved in so that resistance to overturning reduces, influence the cyclicity of material
Energy, high rate performance；（2）Electrode material surface ion is easily dissolved in electrolyte in cyclic process, causes active material
Loss；（3）The LiNi of existing market1/3Co1/3Mn1/3O2Tertiary cathode material is close in order to ensure the tap density of product, compacting
Degree, material crystals size is larger, causes the migration path of electronics and ion to increase, and LiNi1/3Co1/3Mn1/3O2As semiconductor
Material own electronic electrical conductivity is relatively low（Belong to semi-conducting material）, so that its energy density is higher, power density is relatively low, i.e. multiplying power
Poor-performing.
Pin LiNi1/3Co1/3Mn1/3O2The problem of high rate performance is poor, current research are concentrated mainly on preparation method wound
Newly, surface coating modification of modification by ion-doping and metal oxide etc..In preparation method innovation, Rheological Phase Method is adapted to
Mixed in solid and liquid, help to realize the uniform mixing of presoma, although technique is very easy, it is desirable to it is relatively low, it is adapted to
Industrialized production, but be short of in terms of pattern is controlled；In terms of modification by ion-doping, current research mainly passes through sun
The methods of doping of ion equivalent state, cation non-equivalence state are adulterated or are anion doped improves the electronic conductance and ion-conductance of material
Lead, increase the stability of crystal structure, improve the power output of lithium ion battery, although the partial electro chemical of battery can be improved
Performance, but the reunion of Doped ions causes the effect run counter to desire；The surface coating modification of metal oxide is usually logical
Cross and coat one layer of suitable inert metal oxides material formation protective layer in material surface, to reduce the active matter under high potential
The side reaction of matter and electrolyte, structural stability of the material during repeated charge is kept, improve the stable circulation of material
Property and high rate performance, but the electrical conductivity of material can be reduced, and technique is more complicated, the implementation time of the technology is also longer.As in
State patent application CN201510659208.9, disclose a kind of nickle cobalt lithium manganate/graphene/carbon nano-tube composite positive pole and
Preparation method.Composite positive pole is by LiNi1/3Co1/3Mn1/3O2, Graphene and CNTs compositions, Graphene and CNTs institutes
The quality accounted for very content is that 0.1%-20%, Graphene and CNTs mass ratio are 10:1-1:10；Its preparation method
For：With Graphene and CNTs stable suspension, nickel, cobalt, the acetate of manganese or nitrate and lithium carbonate are raw material, pass through stream
Covert method prepares nickle cobalt lithium manganate/graphene/carbon nano-tube composite positive pole.The technical step is more complicated, and raw material is more, when
Between it is longer, and need in technique strict controlling reaction temperature.
To sum up, being badly in need of one kind now at present can be to LiNi1/3Co1/3Mn1/3O2The method for carrying out suitable moditied processing, with
Effectively improve its high rate performance and cycle performance.
The content of the invention
In view of the shortcomings that above-mentioned prior art, it is an object of the invention to provide the nickel cobalt that a kind of two-dimension nano materials are fixed
LiMn2O4 and preparation method and application.The nickle cobalt lithium manganate that the two-dimension nano materials are fixed can make nickle cobalt lithium manganate in two dimension
Accumulate to form secondary spherical particle with the pattern of Rotating fields in the template of nano material, and the two-dimension nano materials can suppress Li+The defects of dislocation occurs during deintercalation in the layered structure.
In order to reach foregoing goal of the invention, the present invention provides the nickle cobalt lithium manganate that a kind of two-dimension nano materials are fixed, its
It is to be stacked to be combined in a manner of interlayer by the nickle cobalt lithium manganate of two-dimension nano materials and spherical structure, the nickel of the spherical structure
Cobalt manganic acid lithium is accumulated in the template of two-dimension nano materials with the pattern of Rotating fields.
In the nickle cobalt lithium manganate that above-mentioned two-dimension nano materials are fixed, it is preferable that the two-dimension nano materials include two sulphur
Change any of tungsten, molybdenum disulfide, stannic disulfide, silene.
In the nickle cobalt lithium manganate that above-mentioned two-dimension nano materials are fixed, it is preferable that the nickel that the two-dimension nano materials are fixed
The thickness of cobalt manganic acid lithium is 10nm-35nm.
The nickle cobalt lithium manganate that above-mentioned two-dimension nano materials are fixed has regular appearance, the spherical structure nickel cobalt of good fluidity
LiMn2O4, can realize tightly packed, greatly improve tap density and energy density of the nickle cobalt lithium manganate as positive electrode；And ball
The nickle cobalt lithium manganate surface of shape structure is smooth, specific surface area is low, it is possible to reduce the generation with electrolyte side reaction, improves lithium ion
The first charge-discharge efficiency of battery, in addition, nickle cobalt lithium manganate is accumulated in the template of two-dimension nano materials with the pattern of Rotating fields
Secondary spherical particle is formed, the two-dimension nano materials can suppress Li+The defects of dislocation occurs during deintercalation in the layered structure, enters
One step improves the deintercalation ability of lithium ion, and can improve the electric conductivity of nickle cobalt lithium manganate and improve its charge-discharge performance.
The present invention also provides the preparation method for the nickle cobalt lithium manganate that above-mentioned two-dimension nano materials are fixed, and it includes following step
Suddenly：
Step 1：With the stoichiometric proportion of nickle cobalt lithium manganate in deionized water, then nickel salt, cobalt salt and manganese salt are dissolved
Add two-dimension nano materials to mix as template, obtain suspension；
Step 2：Lithium salts is weighed by the mol ratio of lithium in the nickle cobalt lithium manganate, dissolving in deionized water, obtains lithium salts
Solution；
Step 3：The lithium salt solution is added drop-wise in the suspension, stirred when being added dropwise, its mixing speed is
2500-5000rpm, then filter, and 10h-16h is dried in vacuo at 80 DEG C -100 DEG C, obtain powder；
Step 4：By the powder mull, it is subsequently placed in protection gas in 700 DEG C of -800 DEG C of temperature lower calcination 4h-6h, obtains
The nickle cobalt lithium manganate fixed to two-dimension nano materials；
Wherein, the mol ratio of the two-dimension nano materials and lithium salts is（1-5）：1.
In above-mentioned preparation method, it is preferable that in the nickel salt, cobalt salt, manganese salt and lithium salts, at least one kind is nitric acid
Salt or acetate.
In above-mentioned preparation method, it is preferable that the nickel salt includes nickel sulfate, nickel nitrate, nickel acetate, citric acid nickel, ammonia
One or more of combinations in base nickel sulphonic acid and nickel halogenide.
In above-mentioned preparation method, it is preferable that the cobalt salt includes cobaltous sulfate, cobalt acetate, cobalt nitrate, citric acid cobalt, halogen
Change one or more of combinations in cobalt.
In above-mentioned preparation method, it is preferable that the manganese salt includes manganese sulfate, manganese acetate, manganese nitrate, manganese citrate and halogen
Change one or more of combinations in manganese.
In above-mentioned preparation method, it is preferable that the lithium salts includes lithium carbonate, lithium sulfate, lithium nitrate, lithium acetate, lemon
One or more of combinations in sour lithium and lithium halide.
In above-mentioned preparation method, it is preferable that the total mass concentration of nickel salt, cobalt salt and manganese salt is 50 in the suspension
G/L -70g/L, the mass concentration of lithium salts is 5 g/L -10g/L in the lithium salt solution.
Above-mentioned preparation method, in the preparation process of cobalt nickel lithium manganate ternary material, introduce two-dimension nano materials（Curing
Tungsten, molybdenum disulfide, stannic disulfide, silene）As template, nickle cobalt lithium manganate is in the template of two-dimension nano materials with Rotating fields
Pattern accumulate to form secondary spherical particle, form the nickle cobalt lithium manganate fixed by two-dimension nano materials, it is similar to be layering
Shape.The two-dimension nano materials can suppress Li+The defects of dislocation occurs during deintercalation in the layered structure, further improves lithium ion
Deintercalation ability, and the electric conductivity of nickle cobalt lithium manganate can be improved and improve its charge-discharge performance.Mixed with traditional ion
Miscellaneous modification and surface coating modification etc. are compared, and the nickle cobalt lithium manganate that the two-dimension nano materials that the preparation method obtains are fixed is more equal
It is even, steady quality.The electric conductivity and quality stability of current ferric phosphate lithium cell can be substantially improved.
The present invention also provides lithium ion battery of the nickle cobalt lithium manganate of above-mentioned two-dimension nano materials fixation as positive electrode.
The lithium ion battery includes battery case, pole piece and electrolyte, and the pole piece and electrolyte are sealingly received within described
In battery case, the pole piece includes positive pole, negative pole and the barrier film between positive pole and negative pole, the positive pole include collector and
Load positive electrode on a current collector, the negative pole include the negative material of collector and load on a current collector, it is described just
Pole material is the nickle cobalt lithium manganate that the two-dimension nano materials are fixed.
Nickle cobalt lithium manganate that a kind of two-dimension nano materials provided by the invention are fixed and preparation method and application, it is and existing
The characteristics of technology is compared, and it is protruded and excellent effect are：
（1）Nickle cobalt lithium manganate that two-dimension nano materials provided by the invention are fixed has regular appearance, good fluidity
Spherical structure nickle cobalt lithium manganate, can realize it is tightly packed, greatly improve nickle cobalt lithium manganate as positive electrode tap density and
Energy density；And the nickle cobalt lithium manganate surface of spherical structure is smooth, specific surface area is low, it is possible to reduce the hair with electrolyte side reaction
It is raw, the first charge-discharge efficiency of lithium ion battery is improved, in addition, nickle cobalt lithium manganate is tied in the template of two-dimension nano materials with layer
The pattern of structure accumulates to form secondary spherical particle, and the two-dimension nano materials can suppress Li+Occur in the layered structure during deintercalation
The defects of dislocation, the deintercalation ability of lithium ion is further improved, and the electric conductivity of nickle cobalt lithium manganate can be improved and improve it and filled
Discharge cycle performance；
（2）The preparation method for the nickle cobalt lithium manganate that two-dimension nano materials provided by the invention are fixed is in nickle cobalt lithium manganate ternary
In the preparation process of material, two-dimension nano materials are introduced（Tungsten disulfide, molybdenum disulfide, stannic disulfide, silene）As template,
Form the nickle cobalt lithium manganate fixed by two-dimension nano materials, the similar shape that is layering.With traditional modification by ion-doping and table
Face coating modification etc. is compared, and the nickle cobalt lithium manganate that the two-dimension nano materials that the preparation method obtains are fixed is more uniformly distributed, and quality is steady
It is fixed.The electric conductivity and high temperature quality stability of current ferric phosphate lithium cell can be substantially improved；
（3）Lithium ion battery provided by the invention is used by the nickle cobalt lithium manganate of two-dimension nano materials and spherical structure with layer
Between the nickle cobalt lithium manganate fixed of the two-dimension nano materials that are combined of mode as positive electrode, improve nickle cobalt lithium manganate positive pole
The charge-discharge performance of material.
Embodiment
Below by way of embodiment, the present invention is described in further detail, but this should not be interpreted as to the present invention
Scope be only limitted to following example.In the case where not departing from above method thought of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
A kind of preparation method for the nickle cobalt lithium manganate that molybdenum disulfide is fixed is present embodiments provided, it comprises the following steps：
Step 1：1mol nickel acetates, 1mol cobalt acetates and 1mol manganese acetates are dissolved in 50ml deionized waters, fully stirred
Mix, then add 1mol molybdenum disulfide as template, stir 60min, obtain suspension；
Step 2：3mol lithium acetates are weighed, is sufficiently stirred and is dissolved in 100ml deionized waters, obtain lithium acetate solution；
Step 3：Lithium acetate solution is added drop-wise in above-mentioned suspension with 20m1/min speed, stirred when being added dropwise, its
Mixing speed is 2500rpm, then 2. 5h are stirred at room temperature, and is then filtered, and is dried in vacuo 16h at 100 DEG C, obtains powder
End；
Step 4：15min will be ground in the powder dry environment, it is subsequently placed in tube furnace, under argon gas protection
800 DEG C of temperature lower calcination 4h, obtain the nickle cobalt lithium manganate of molybdenum disulfide fixation.
The nickle cobalt lithium manganate for the present embodiment being made molybdenum disulfide fixation is tested, and finds the nickel that the molybdenum disulfide is fixed
The average thickness of cobalt manganic acid lithium is 20nm, and by the molybdenum disulfide of layer structure and the nickle cobalt lithium manganate of spherical structure with interlayer side
Formula is stacked and is combined, and the nickle cobalt lithium manganate of the spherical structure is accumulated in the template of molybdenum disulfide with the pattern of Rotating fields.
Knob is made as the positive electrode of lithium ion battery in the nickle cobalt lithium manganate that the present embodiment is made to molybdenum disulfide fixation
Fastening lithium ionic cell, in the lithium ion battery lithium ion battery, specific discharge capacity is 220 mAh/g, 10C under 0.1C multiplying powers
Specific discharge capacity is 210 mAh/g under multiplying power.
Embodiment 2
A kind of preparation method for the nickle cobalt lithium manganate that tungsten disulfide is fixed is present embodiments provided, it comprises the following steps：
Step 1：1mol nickel sulfates, 1mol cobaltous sulfates and 1mol manganese sulfates are dissolved in 50ml deionized waters, fully stirred
Mix, then add 1mol tungsten disulfides as template, stir 60min, obtain suspension；
Step 2：3mol lithium acetates are weighed, is sufficiently stirred and is dissolved in 100ml deionized waters, obtain lithium acetate solution；
Step 3：Lithium acetate solution is added drop-wise in above-mentioned suspension with 20m1/min speed, stirred when being added dropwise, its
Mixing speed is 3000rpm, then 2.5h is stirred at room temperature, and is then filtered, and is dried in vacuo 12h at 100 DEG C, obtains powder
End；
Step 4：15min will be ground in the powder dry environment, it is subsequently placed in tube furnace, under argon gas protection
750 DEG C of temperature lower calcination 5h, obtain the nickle cobalt lithium manganate of tungsten disulfide fixation.
The nickle cobalt lithium manganate for the present embodiment being made tungsten disulfide fixation is tested, and finds the nickel that the tungsten disulfide is fixed
The average thickness of cobalt manganic acid lithium is 26nm, and by the tungsten disulfide of layer structure and the nickle cobalt lithium manganate of spherical structure with interlayer side
Formula is stacked and is combined, and the nickle cobalt lithium manganate of the spherical structure is accumulated in the template of tungsten disulfide with the pattern of Rotating fields.
Knob is made as the positive electrode of lithium ion battery in the nickle cobalt lithium manganate that the present embodiment is made to molybdenum disulfide fixation
Fastening lithium ionic cell, in the lithium ion battery lithium ion battery, specific discharge capacity is 235 mAh/g, 10C under 0.1C multiplying powers
Specific discharge capacity is 215mAh/g under multiplying power.
Embodiment 3
A kind of preparation method for the nickle cobalt lithium manganate that stannic disulfide is fixed is present embodiments provided, it comprises the following steps：
Step 1：1mol citric acids nickel, 1mol citric acids cobalt and 1mol manganese citrates are dissolved in 50ml deionized waters,
It is sufficiently stirred, then adds 1mol stannic disulfides as template, stir 60min, obtain suspension；
Step 2：3mol lithium acetates are weighed, is sufficiently stirred and is dissolved in 100ml deionized waters, obtain lithium acetate solution；
Step 3：Lithium acetate solution is added drop-wise in above-mentioned suspension with 20m1/min speed, stirred when being added dropwise, its
Mixing speed is that 2. 5h are stirred at room temperature in 3500rpm again, is then filtered, and is dried in vacuo 10h at 100 DEG C, obtains powder
End；
Step 4：15min will be ground in the powder dry environment, it is subsequently placed in tube furnace, under argon gas protection
750 DEG C of temperature lower calcination 5h, obtain the nickle cobalt lithium manganate of stannic disulfide fixation.
The nickle cobalt lithium manganate for the present embodiment being made stannic disulfide fixation is tested, and finds the nickel that the stannic disulfide is fixed
The average thickness of cobalt manganic acid lithium is 25nm, and by the stannic disulfide of layer structure and the nickle cobalt lithium manganate of spherical structure with interlayer side
Formula is stacked and is combined, and the nickle cobalt lithium manganate of the spherical structure is accumulated in the template of stannic disulfide with the pattern of Rotating fields.
Using the present embodiment be made molybdenum disulfide fixation nickle cobalt lithium manganate be made as the positive electrode of lithium ion battery it is dynamic
Power battery, this capacity reach more than 195mAh/g, normal temperature circulation life-span 2000 times, 10C discharge and recharges more than 90%.
Embodiment 4
A kind of preparation method for the nickle cobalt lithium manganate that graphene is fixed is present embodiments provided, it comprises the following steps：
Step 1：1mol nickel acetates, 1mol cobaltous sulfates and 1mol manganese sulfates are dissolved in 50ml deionized waters, fully stirred
Mix, then add 1mol graphenes as template, stir 60min, obtain suspension；
Step 2：3mol lithium acetates are weighed, is sufficiently stirred and is dissolved in 100ml deionized waters, obtain lithium acetate solution；
Step 3：Lithium acetate solution is added drop-wise in above-mentioned suspension with 20m1/min speed, stirred when being added dropwise, its
Mixing speed is that 2. 5h are stirred at room temperature in 4000rpm again, is then filtered, and is dried in vacuo 15h at 100 DEG C, obtains powder
End；
Step 4：15min will be ground in the powder dry environment, it is subsequently placed in tube furnace, under argon gas protection
700 DEG C of temperature lower calcination 6h, obtain the nickle cobalt lithium manganate of graphene fixation.
The nickle cobalt lithium manganate for the present embodiment being made graphene fixation is tested, and finds the nickel cobalt manganese that the graphene is fixed
The average thickness of sour lithium is 15nm, and is stacked by the graphene of layer structure and the nickle cobalt lithium manganate of spherical structure in a manner of interlayer
It is combined, the nickle cobalt lithium manganate of the spherical structure is accumulated in the template of graphene with the pattern of Rotating fields.
Power is made as the positive electrode of lithium ion battery in the nickle cobalt lithium manganate that the present embodiment is made to graphene fixation
Battery, remain to during 192 DEG C of high temperature keep form, improve the security performance of battery.
Embodiment 5
A kind of preparation method for the nickle cobalt lithium manganate that molybdenum disulfide is fixed is present embodiments provided, it comprises the following steps：
Step 1：1mol citric acids nickel, 1mol cobalt chlorides and 1mol manganese chlorides are dissolved in 50ml deionized waters, fully
Stirring, 1mol molybdenum disulfide is then added as template, 60min is stirred, obtains suspension；
Step 2：3mol lithium acetates are weighed, is sufficiently stirred and is dissolved in 100ml deionized waters, obtain lithium acetate solution；
Step 3：Lithium acetate solution is added drop-wise in above-mentioned suspension with 20m1/min speed, stirred when being added dropwise, its
Mixing speed is that 2. 5h are stirred at room temperature in 5000rpm again, is then filtered, and is dried in vacuo 12h at 100 DEG C, obtains powder
End；
Step 4：15min will be ground in the powder dry environment, it is subsequently placed in tube furnace, under argon gas protection
800 DEG C of temperature lower calcination 4h, obtain the nickle cobalt lithium manganate of molybdenum disulfide fixation.
The nickle cobalt lithium manganate for the present embodiment being made molybdenum disulfide fixation is tested, and finds the nickel that the molybdenum disulfide is fixed
The average thickness of cobalt manganic acid lithium is 22nm, and by the molybdenum disulfide of layer structure and the nickle cobalt lithium manganate of spherical structure with interlayer side
Formula is stacked and is combined, and the nickle cobalt lithium manganate of the spherical structure is accumulated in the template of molybdenum disulfide with the pattern of Rotating fields.
Embodiment 6
A kind of preparation method for the nickle cobalt lithium manganate that molybdenum disulfide is fixed is present embodiments provided, it comprises the following steps：
Step 1：1mol nickel acetates, 1mol citric acids cobalt and 1mol manganese citrates are dissolved in 50ml deionized waters, filled
Divide stirring, then add 1mol molybdenum disulfide as template, stir 60min, obtain suspension；
Step 2：3mol lithium carbonates are weighed, is sufficiently stirred and is dissolved in 100ml deionized waters, obtain Lithium carbonate solution；
Step 3：Lithium carbonate solution is added drop-wise in above-mentioned suspension with 20m1/min speed, stirred when being added dropwise, its
Mixing speed is 4500rpm, then 2. 5h are stirred at room temperature, and is then filtered, and is dried in vacuo 16h at 100 DEG C, obtains powder
End；
Step 4：15min will be ground in the powder dry environment, it is subsequently placed in tube furnace, under argon gas protection
700 DEG C of temperature lower calcination 6h, obtain the nickle cobalt lithium manganate of molybdenum disulfide fixation.
The nickle cobalt lithium manganate for the present embodiment being made molybdenum disulfide fixation is tested, and finds the nickel that the molybdenum disulfide is fixed
The average thickness of cobalt manganic acid lithium is 28nm, and by the molybdenum disulfide of layer structure and the nickle cobalt lithium manganate of spherical structure with interlayer side
Formula is stacked and is combined, and the nickle cobalt lithium manganate of the spherical structure is accumulated in the template of molybdenum disulfide with the pattern of Rotating fields.
Claims (7)
- A kind of 1. nickle cobalt lithium manganate that two-dimension nano materials are fixed, it is characterised in that：The nickel cobalt that the two-dimension nano materials are fixed LiMn2O4 is to be stacked to be combined in a manner of interlayer by the nickle cobalt lithium manganate of two-dimension nano materials and spherical structure, the spherical junctions The nickle cobalt lithium manganate of structure is accumulated in the template of two-dimension nano materials with the pattern of Rotating fields；Its preparation method comprises the following steps：Step 1：Nickel salt, cobalt salt and manganese salt are dissolved in deionized water with the stoichiometric proportion of nickle cobalt lithium manganate, then added Two-dimension nano materials mix as template, obtain suspension；Step 2：Lithium salts is weighed by the mol ratio of lithium in the nickle cobalt lithium manganate, dissolving in deionized water, it is molten to obtain lithium salts Liquid；Step 3：The lithium salt solution is added drop-wise in the suspension, stirred when being added dropwise, its mixing speed is 2500- 5000rpm, then filter, and 10h-16h is dried in vacuo at 80 DEG C -100 DEG C, obtain powder；Step 4：By the powder mull, it is subsequently placed in protection gas in 700 DEG C of -800 DEG C of temperature lower calcination 4h-6h, obtains two The nickle cobalt lithium manganate that dimension nano material is fixed；Wherein, the mol ratio of the two-dimension nano materials and lithium salts is（1-5）：1.
- 2. the nickle cobalt lithium manganate that two-dimension nano materials according to claim 1 are fixed, it is characterised in that：The two-dimensional nano Material includes any of tungsten disulfide, molybdenum disulfide, stannic disulfide, silene.
- 3. the nickle cobalt lithium manganate that two-dimension nano materials according to claim 1 are fixed, it is characterised in that：The two-dimensional nano The thickness for the nickle cobalt lithium manganate that material is fixed is 10nm-35nm.
- 4. claim requires the preparation method for the nickle cobalt lithium manganate that the two-dimension nano materials described in any one of 1-3 are fixed, it is wrapped Include following steps：Step 1：Nickel salt, cobalt salt and manganese salt are dissolved in deionized water with the stoichiometric proportion of nickle cobalt lithium manganate, then added Two-dimension nano materials mix as template, obtain suspension；Step 2：Lithium salts is weighed by the mol ratio of lithium in the nickle cobalt lithium manganate, dissolving in deionized water, it is molten to obtain lithium salts Liquid；Step 3：The lithium salt solution is added drop-wise in the suspension, stirred when being added dropwise, its mixing speed is 2500- 5000rpm, then filter, and 10h-16h is dried in vacuo at 80 DEG C -100 DEG C, obtain powder；Step 4：By the powder mull, it is subsequently placed in protection gas in 700 DEG C of -800 DEG C of temperature lower calcination 4h-6h, obtains two The nickle cobalt lithium manganate that dimension nano material is fixed；Wherein, the mol ratio of the two-dimension nano materials and lithium salts is（1-5）：1.
- 5. preparation method according to claim 4, it is characterised in that：In the nickel salt, cobalt salt, manganese salt and lithium salts, extremely Rare one kind is nitrate or acetate.
- 6. the preparation method according to claim 4 or 5, it is characterised in that：The nickel salt includes nickel sulfate, nickel nitrate, second One or more of combinations in sour nickel, citric acid nickel, nickel sulfamic acid and nickel halogenide；The cobalt salt includes cobaltous sulfate, acetic acid One or more of combinations in cobalt, cobalt nitrate, citric acid cobalt, halogenation cobalt；The manganese salt includes manganese sulfate, manganese acetate, nitric acid One or more of combinations in manganese, manganese citrate and manganese halide；The lithium salts includes lithium carbonate, lithium sulfate, lithium nitrate, acetic acid One or more of combinations in lithium, lithium citrate and lithium halide.
- 7. preparation method according to claim 4, it is characterised in that：Nickel salt in the suspension, cobalt salt and manganese salt it is total Mass concentration is 50 g/L -70g/L, and the mass concentration of lithium salts is 5 g/L-10g/L in the lithium salt solution.
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